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Sample records for fe iii citrate

  1. Ab initio calculations of the Fe(II) and Fe(III) isotopic effects in citrates, nicotianamine, and phytosiderophore, and new Fe isotopic measurements in higher plants

    Science.gov (United States)

    Moynier, Frédéric; Fujii, Toshiyuki; Wang, Kun; Foriel, Julien

    2013-05-01

    Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ˜3‰ (56Fe/54Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ˜1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate2 and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ56Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.

  2. Iron(III) citrate speciation in aqueous solution.

    Science.gov (United States)

    Silva, Andre M N; Kong, XiaoLe; Parkin, Mark C; Cammack, Richard; Hider, Robert C

    2009-10-28

    Citrate is an iron chelator and it has been shown to be the major iron ligand in the xylem sap of plants. Furthermore, citrate has been demonstrated to be an important ligand for the non-transferrin bound iron (NTBI) pool occurring in the plasma of individuals suffering from iron-overload. However, ferric citrate chemistry is complicated and a definitive description of its aqueous speciation at neutral pH remains elusive. X-Ray crystallography data indicates that the alcohol function of citrate (Cit4-) is involved in Fe(III) coordination and that deprotonation of this functional group occurs upon complex formation. The inability to include this deprotonation in the affinity constant calculations has been a major source of divergence between various reports of iron(III)-citrate affinity constants. However the recent determination of the alcoholic pKa of citric acid (H4Cit) renders the reassessment of the ferric citrate system possible. The aqueous speciation of ferric citrate has been investigated by mass spectrometry and EPR spectroscopy. It was observed that the most relevant species are a monoiron dicitrate species and dinuclear and trinuclear oligomeric complexes, the relative concentration of which depends on the solution pH value and the iron : citric acid molar ratio. Spectrophotometric titration was utilized for affinity constant determination and the formation constant for the biologically relevant [Fe(Cit)2]5- is reported for the first time.

  3. Immobilization of selenium by biofilm of Shewanella putrefaciens with and without Fe(III)-citrate complex

    International Nuclear Information System (INIS)

    Suzuki, Yoshinori; Sakama, Yosuke; Saiki, Hiroshi; Kitamura, Akira; Yoshikawa, Hideki; Tanaka, Kazuya

    2014-01-01

    To investigate the effect of biofilms on selenium migration, we examined selenite reduction by biofilms of an iron-reducing bacterium, Shewanella putrefaciens, under anaerobic conditions. The biofilms were grown under static conditions on culture cover glasses coated with poly-L-lysine. Optical microscopic observation of the biofilms after staining with 0.1% crystal violet solution revealed that the cells were surrounded by filamentous extracellular polymer substances. Exposure of the biofilms to aqueous selenite resulted in the formation of red precipitates, which were assigned to nanoparticulate elemental selenium using X-ray absorption near-edge structure analysis. Micrographic observation showed that the precipitates immobilized at the biofilms. We also examined the selenite reduction in the presence of Fe(III)-citrate complex. In this case, a dark brown precipitate formed at the biofilms. X-ray absorption near-edge structure analysis revealed that the precipitate was a mixed compound with elemental selenium and iron selenide. These findings indicate that biofilms of iron-reducing bacteria in the environment can immobilize selenium by reducing Se(IV) to Se(0), and Fe(III)-citrate complex promotes the reduction of Se(0) to Se(-II). (author)

  4. A Fe(II)/citrate/UV/PMS process for carbamazepine degradation at a very low Fe(II)/PMS ratio and neutral pH: The mechanisms.

    Science.gov (United States)

    Ling, Li; Zhang, Dapeng; Fan, Chihhao; Shang, Chii

    2017-11-01

    A novel Fe(II)/citrate/UV/PMS process for degrading a model micropollutant, carbamazepine (CBZ), at a low Fe(II)/PMS ratio and neutral pH has been proposed in this study, and the mechanisms of radical generation in the system was explored. With a UV dose of 302.4 mJ/cm 2 , an initial pH of 7, and CBZ, PMS, Fe(II) and citrate at initial concentrations of 10, 100, 12 and 26 μM, respectively, the CBZ degradation efficiency reached 71% in 20 min in the Fe(II)/citrate/UV/PMS process, which was 4.7 times higher than that in either the citrate/UV/PMS or Fe(II)/citrate/PMS process. The enhanced CBZ degradation in the Fe(II)/citrate/UV/PMS process was mainly attributed to the continuous activation of PMS by the UV-catalyzed regenerated Fe(II) from a Fe(III)-citrate complex, [Fe 3 O(cit) 3 H 3 ] 2- , which not only maintained Fe(III) soluble at neutral pH, but also increased 6.6 and 2.6 times of its molar absorbance and quantum yield as compared to those of ionic Fe(III), respectively. In the Fe(II)/citrate/UV/PMS process, the SO 4 •- produced from the fast reaction between PMS and the initially-added Fe(II) contributed 11% of CBZ degradation. The PMS activation by the UV radiation and regenerated Fe(II) contributed additional 14% and 46% of CBZ removal, respectively. The low iron and citrate doses and the fast radical generation at neutral pH make the Fe(II)/citrate/UV/PMS process suitable for degrading recalcitrant organic compounds in potable water. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Biotransformation of uranium and transition metal citrate complexes by clostridia

    International Nuclear Information System (INIS)

    Francis, A.J.; Joshi-Tope, G.A.; Dodge, C.J.; Gillow, J.B.

    2002-01-01

    Clostridium sphenoides, which uses citric acid as its sole carbon source, metabolized equimolar Fe(III)-citrate with the degradation of citric acid and the reduction of Fe(III) to Fe(II), but not the U(VI)-citrate complex. However, in the presence of excess citric acid or added glucose it was reduced to U(IV)-citrate. In contrast, Clostridium sp., which ferments glucose but not citrate, reduced Fe(III)-citrate to Fe(II)-citrate and U(VI)-citrate to U(IV)-citrate only when supplied with glucose. These results show that complexed uranium is readily accessible as an electron acceptor despite the bacterium's inability to metabolize the organic ligand complexed to the actinide. These results also show that the metabolism of the metal-citrate complex depends upon the type of complex formed between the metal and citric acid. Fe(III) forms a bidentate complex with citric acid and was metabolized, whereas U forms a binuclear complex with citric acid and was recalcitrant. (author)

  6. Effects of citrate on hexavalent chromium reduction by structural Fe(II) in nontronite

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xiaolei; Dong, Hailiang; Yang, Xuewei; Kovarik, Libor; Chen, Yu; Zeng, Qiang

    2018-02-01

    Iron-bearing clay minerals and organic matter are two important components in natural environments that influence hexavalent chromium (Cr(VI)) reduction. Previous studies have shown that organic ligands could influence Cr(VI) reduction by aqueous Fe2+ and pyrite. However, the effects of organic ligands on Cr(VI) reduction by structural Fe(II) in clays are not well understood. In this study, the effects of citrate on Cr(VI) reduction by nontronite (NAu-2) were investigated under near neutral pH condition (pH=6). Our results showed that the presence of citrate decreased the rate but increased the amount of Cr(VI) reduction by structural Fe(II) in NAu-2. The decreased reaction rate was likely due to competitive sorption of citrate and polyanionic dichromate (Cr2O7- ), because sorption of dichromate appeared to be the first step for subsequent Cr(VI) reduction. The increased amount of Cr(VI) reduction in the presence of citrate was likely because citrate provided additional reducing power through ligand-metal electron transfer in the presence of soluble Fe 3+ derived from dissolution of reduced NAu-2. Soluble Cr(III)-citrate complex was the possible form of reduced chromium when citrate was present. In contrast, nanometer-sized Cr2O3 particles were the product of Cr(VI) reduction by reduced NAu-2 without citrate. Our study highlights the importance of organic ligands on Cr(VI) reduction and immobilization when iron-bearing clay minerals are applied to treat Cr(VI) contaminant in organic matter rich environments.

  7. Direct Involvement of ombB, omaB and omcB Genes in Extracellular Reduction of Fe(III by Geobacter sulfurreducens PCA

    Directory of Open Access Journals (Sweden)

    Yimo eLiu

    2015-10-01

    Full Text Available The tandem gene clusters orfR-ombB-omaB-omcB and orfS-ombC-omaC-omcC of the metal-reducing bacterium Geobacter sulfurreducens PCA are responsible for trans-outer membrane electron transfer during extracellular reduction of Fe(III-citrate and ferrihydrite [a poorly crystalline Fe(III oxide]. Each gene cluster encodes a putative transcriptional factor (OrfR/OrfS, a porin-like outer-membrane protein (OmbB/OmbC, a periplasmic c-type cytochrome (c-Cyt, OmaB/OmaC and an outer-membrane c-Cyt (OmcB/OmcC. The individual roles of OmbB, OmaB and OmcB in extracellular reduction of Fe(III, however, have remained either uninvestigated or controversial. Here, we showed that replacements of ombB, omaB, omcB and ombB-omaB with an antibiotic gene in the presence of ombC-omaC-omcC had no impact on reduction of Fe(III-citrate by G. sulfurreducens PCA. Disruption of ombB, omaB, omcB and ombB-omaB in the absence of ombC-omaC-omcC, however, severely impaired the bacterial ability to reduce Fe(III-citrate as well as ferrihydrite. These results unequivocally demonstrate an overlapping role of ombB-omaB-omcB and ombC-omaC-omcC in extracellular Fe(III reduction by G. sulfurreducens PCA. Involvement of both ombB-omaB-omcB and ombC-omaC-omcC in extracellular Fe(III reduction reflects the importance of these trans-outer membrane protein complexes in the physiology of this bacterium. Moreover, the kinetics of Fe(III-citrate and ferrihydrite reduction by these mutants in the absence of ombC-omaC-omcC were nearly identical, which suggests that absence of any protein subunit eliminates function of OmaB/OmbB/OmcB protein complex. Finally, orfS was found to have a negative impact on the extracellular reduction of Fe(III-citrate and ferrihydrite in G. sulfurreducens PCA probably by serving as a transcriptional repressor.

  8. The Moessbauer effect in Fe(III) HEDTA, Fe(III) EDTA, and Fe(III) CDTA compounds

    International Nuclear Information System (INIS)

    Prado, F.R.

    1989-01-01

    The dependence of Moessbauer spectra with pH value of Fe(III)HEDTA and Fe(III)CDTA compounds is studied. Informations on formation processes of LFe-O-FeL (L=ligand) type dimers by the relation of titration curves of Fe(III)EDTA, Fe(III)HEDTA and Fe(III)CDTA compounds with the series of Moessbauer spectra, are obtained. Some informations on Fe-O-Fe bond structure are also obtained. Comparing the titration curves with the series of Moessbauer spectra, it is concluded that the dimerization process begins when a specie of the form FeXOH α (X = EDTA, HEDTA, CDTA; α = -1, -2) arises. (M.C.K.) [pt

  9. A hydrogen-oxidizing, Fe(III)-reducing microorganism from the Great Bay estuary, New Hampshire

    Science.gov (United States)

    Caccavo, F.; Blakemore, R.P.; Lovley, D.R.

    1992-01-01

    A dissimilatory Fe(III)- and Mn(IV)-reducing bacterium was isolated from bottom sediments of the Great Bay estuary, New Hampshire. The isolate was a facultatively anaerobic gram-negative rod which did not appear to fit into any previously described genus. It was temporarily designated strain BrY. BrY grew anaerobically in a defined medium with hydrogen or lactate as the electron donor and Fe(III) as the electron acceptor. BrY required citrate, fumarate, or malate as a carbon source for growth on H2 and Fe(III). With Fe(III) as the sole electron acceptor, BrY metabolized hydrogen to a minimum threshold at least 60-fold lower than the threshold reported for pure cultures of sulfate reducers. This finding supports the hypothesis that when Fe(III) is available, Fe(III) reducers can outcompete sulfate reducers for electron donors. Lactate was incompletely oxidized to acetate and carbon dioxide with Fe(III) as the electron acceptor. Lactate oxidation was also coupled to the reduction of Mn(IV), U(VI), fumarate, thiosulfate, or trimethylamine n-oxide under anaerobic conditions. BrY provides a model for how enzymatic metal reduction by respiratory metal-reducing microorganisms has the potential to contribute to the mobilization of iron and trace metals and to the immobilization of uranium in sediments of Great Bay Estuary.

  10. Microbial Reduction of Fe(III) in Acidic Sediments: Isolation of Acidiphilium cryptum JF-5 Capable of Coupling the Reduction of Fe(III) to the Oxidation of Glucose

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    Küsel, Kirsten; Dorsch, Tanja; Acker, Georg; Stackebrandt, Erko

    1999-01-01

    To evaluate the microbial populations involved in the reduction of Fe(III) in an acidic, iron-rich sediment, the anaerobic flow of supplemental carbon and reductant was evaluated in sediment microcosms at the in situ temperature of 12°C. Supplemental glucose and cellobiose stimulated the formation of Fe(II); 42 and 21% of the reducing equivalents that were theoretically obtained from glucose and cellobiose, respectively, were recovered in Fe(II). Likewise, supplemental H2 was consumed by acidic sediments and yielded additional amounts of Fe(II) in a ratio of approximately 1:2. In contrast, supplemental lactate did not stimulate the formation of Fe(II). Supplemental acetate was not consumed and inhibited the formation of Fe(II). Most-probable-number estimates demonstrated that glucose-utilizing acidophilic Fe(III)-reducing bacteria approximated to 1% of the total direct counts of 4′,6-diamidino-2-phenylindole-stained bacteria. From the highest growth-positive dilution of the most-probable-number series at pH 2.3 supplemented with glucose, an isolate, JF-5, that could dissimilate Fe(III) was obtained. JF-5 was an acidophilic, gram-negative, facultative anaerobe that completely oxidized the following substrates via the dissimilation of Fe(III): glucose, fructose, xylose, ethanol, glycerol, malate, glutamate, fumarate, citrate, succinate, and H2. Growth and the reduction of Fe(III) did not occur in the presence of acetate. Cells of JF-5 grown under Fe(III)-reducing conditions formed blebs, i.e., protrusions that were still in contact with the cytoplasmic membrane. Analysis of the 16S rRNA gene sequence of JF-5 demonstrated that it was closely related to an Australian isolate of Acidiphilium cryptum (99.6% sequence similarity), an organism not previously shown to couple the complete oxidation of sugars to the reduction of Fe(III). These collective results indicate that the in situ reduction of Fe(III) in acidic sediments can be mediated by heterotrophic Acidiphilium

  11. Microbial reduction of Fe(III) in acidic sediments: isolation of Acidiphilium cryptum JF-5 capable of coupling the reduction of Fe(III) to the oxidation of glucose.

    Science.gov (United States)

    Küsel, K; Dorsch, T; Acker, G; Stackebrandt, E

    1999-08-01

    To evaluate the microbial populations involved in the reduction of Fe(III) in an acidic, iron-rich sediment, the anaerobic flow of supplemental carbon and reductant was evaluated in sediment microcosms at the in situ temperature of 12 degrees C. Supplemental glucose and cellobiose stimulated the formation of Fe(II); 42 and 21% of the reducing equivalents that were theoretically obtained from glucose and cellobiose, respectively, were recovered in Fe(II). Likewise, supplemental H(2) was consumed by acidic sediments and yielded additional amounts of Fe(II) in a ratio of approximately 1:2. In contrast, supplemental lactate did not stimulate the formation of Fe(II). Supplemental acetate was not consumed and inhibited the formation of Fe(II). Most-probable-number estimates demonstrated that glucose-utilizing acidophilic Fe(III)-reducing bacteria approximated to 1% of the total direct counts of 4', 6-diamidino-2-phenylindole-stained bacteria. From the highest growth-positive dilution of the most-probable-number series at pH 2. 3 supplemented with glucose, an isolate, JF-5, that could dissimilate Fe(III) was obtained. JF-5 was an acidophilic, gram-negative, facultative anaerobe that completely oxidized the following substrates via the dissimilation of Fe(III): glucose, fructose, xylose, ethanol, glycerol, malate, glutamate, fumarate, citrate, succinate, and H(2). Growth and the reduction of Fe(III) did not occur in the presence of acetate. Cells of JF-5 grown under Fe(III)-reducing conditions formed blebs, i.e., protrusions that were still in contact with the cytoplasmic membrane. Analysis of the 16S rRNA gene sequence of JF-5 demonstrated that it was closely related to an Australian isolate of Acidiphilium cryptum (99.6% sequence similarity), an organism not previously shown to couple the complete oxidation of sugars to the reduction of Fe(III). These collective results indicate that the in situ reduction of Fe(III) in acidic sediments can be mediated by heterotrophic

  12. Alkaline Fe(III) reduction by a novel alkali-tolerant Serratia sp. isolated from surface sediments close to Sellafield nuclear facility, UK.

    Science.gov (United States)

    Thorpe, Clare L; Morris, Katherine; Boothman, Christopher; Lloyd, Jonathan R

    2012-02-01

    Extensive denitrification resulted in a dramatic increase in pH (from 6.8 to 9.5) in nitrate-impacted, acetate-amended sediment microcosms containing sediment representative of the Sellafield nuclear facility, UK. Denitrification was followed by Fe(III) reduction, indicating the presence of alkali-tolerant, metal-reducing bacteria. A close relative (99% 16S rRNA gene sequence homology) to Serratia liquefaciens dominated progressive enrichment cultures containing Fe(III)-citrate as the sole electron acceptor at pH 9 and was isolated aerobically using solid media. The optimum growth conditions for this facultatively anaerobic Serratia species were investigated, and it was capable of metabolizing a wide range of electron acceptors including oxygen, nitrate, FeGel, Fe-NTA and Fe-citrate and electron donors including acetate, lactate, formate, ethanol, glucose, glycerol and yeast extract at an optimum pH of c. 6.5 at 20 °C. The alkali tolerance of this strain extends the pH range of highly adaptable Fe(III)-reducing Serratia species from mildly acidic pH values associated with acid mine drainage conditions to alkali conditions representative of subsurface sediments stimulated for extensive denitrification and metal reduction. © 2011 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

  13. Mangifera indica L. extract (Vimang) inhibits Fe2+-citrate-induced lipoperoxidation in isolated rat liver mitochondria.

    Science.gov (United States)

    Pardo Andreu, Gilberto; Delgado, René; Velho, Jesus; Inada, Natalia M; Curti, Carlos; Vercesi, Anibal E

    2005-05-01

    The extract of Mangifera indica L. (Vimang) is able to prevent iron mediated mitochondrial damage by means of oxidation of reduced transition metals required for the production of superoxide and hydroxyl radicals and direct free radical scavenging activity. In this study we report for the first time the iron-complexing ability of Vimang as a primary mechanism for protection of rat liver mitochondria against Fe2+ -citrate-induced lipoperoxidation. Thiobarbituric acid reactive substances (TBARS) and antimycin A-insensitive oxygen consumption were used as quantitative measures of lipoperoxidation. Vimang at 10 microM mangiferin concentration equivalent induced near-full protection against 50 microM Fe2+ -citrate-induced mitochondrial swelling and loss of mitochondrial transmembrane potential (DeltaPsi). The IC50 value for Vimang protection against Fe2+ -citrate-induced mitochondrial TBARS formation (7.89+/-1.19 microM) was around 10 times lower than that for tert-butylhydroperoxide mitochondrial induction of TBARS formation. The extract also inhibited the iron citrate induction of mitochondrial antimycin A-insensitive oxygen consumption, stimulated oxygen consumption due to Fe2+ autoxidation and prevented Fe3+ ascorbate reduction. The extracted polyphenolic compound, mainly mangiferin, could form a complex with Fe2+, accelerating Fe2+ oxidation and the formation of more stable Fe3+ -polyphenol complexes, unable to participate in Fenton-type reactions and lipoperoxidation propagation phase. The strong DPPH radical scavenging activity with an apparent IC50 of 2.45+/-0.08 microM suggests that besides its iron-complexing capacity, Vimang could also protect mitochondria from Fe2+ -citrate lipoperoxidation through direct free radical scavenging ability, mainly lipoperoxyl and alcoxyl radicals, acting as both a chain-breaking and iron-complexing antioxidant. These results are of pharmacological relevance since Vimang could be a potential candidate for antioxidant therapy in

  14. Use of Fe(III) oxalate for oxidativewastewater treatment; Einsatz von Fe(III)-Oxalat zur chemisch-oxidativen Abwasserbehandlung

    Energy Technology Data Exchange (ETDEWEB)

    Kim, S.M.; Vogelpohl, A. [Clausthal Univ., Clausthal-Zellerfeld (Germany). Inst. fuer Thermische Verfahrenstechnik

    1998-08-01

    Iron(III)-oxalate was used as an iron catalyst for the Photo Fenton reaction. Iron(III) oxalations ([Fe(C{sub 2}O{sub 4}){sub 3}]{sup 3-}) are reduced to Fe(II) by irradiation using near UV-light ({lambda} = 300 - 400 nm) or visible light ({lambda} > 400 nm). At the same time, CO{sub 2}{sup -} or C{sub 2}O{sub 4}{sup -}-radicals originate, which cause the secondary reduction of Fe(III) to Fe(II). By means of the photolytically regenerated Fe(II) ions, hydroxyl radicals are increasingly formed, so that the degradation of organic substances is accelerated. The work aimed to assess the catalytic effect of Fe(III) oxalate for photochemical oxidation processes and to establish the parameters influencing further treatment of leachate from a municipal waste sanitary landfill by means of technical-scale experiments. (orig.) [Deutsch] In der vorliegenden Arbeit wurde Eisen(III)-Oxalat als Eisenkatalysator fuer die Photo-Fenton-Reaktion eingesetzt. Eisen(III)-Oxalationen ([Fe(C{sub 2}O{sub 4}){sub 3}]{sup 3-}) werden durch Strahlung mit nahem UV-Licht ({lambda}=300 bis 400 nm) oder mit sichtbarem Licht ({lambda}>400 nm) zu Fe(II) reduziert. Gleichzeitig entstehen CO{sub 2}{sup .-} oder C{sub 2}O{sub 4}{sup .-}-Radikale, die eine sekundaere Reduktion von Fe(III) zu Fe(II) bewirken. Mit Hilfe der photolytiisch regenerierten Fe(II)-Ionen werden vermehrt Hydroxylradikale gebildet und damit die Abbaugeschwindigkeit der organischen Substanzen beschleunigt. Ziel der hier vorgestellten Arbeit war es, die katalytische Wirkung von Fe(III)-Oxalat fuer photochemische Oxidationsverfahren abzuschaetzen und die Einflussparameter zur weitergehenden Behandlung eines Deponiesickerwassers aus Hausmuelldeponie anhand von Technikumsversuchen zu ermitteln. (orig.)

  15. Equilibrium Fe isotope fractionation between inorganic aqueous Fe(III) and the siderophore complex, Fe(III)-desferrioxamine B

    DEFF Research Database (Denmark)

    Dideriksen, Knud; Baker, Joel A.; Stipp, Susan Louise Svane

    2008-01-01

    be controlled by isotope fractionation between the free and complexed iron.We have determined the equilibrium Fe isotope fractionation induced by organic ligand activity in experiments with solutions having co-existing inorganic Fe(III) species and siderophore complexes, Fedesferrioxamine B (at pH 2). The two......-type fractionation during precipitation, this experiment yielded an isotope fractionation factor of a56Fesolution-solid=1.00027. Calculations based on these results indicate that isotopic re-equilibration is unlikely to significantly affect our determined equilibrium Fe isotope fractionation between inorganically...... and organically complexed Fe. To determine the equilibrium Fe isotope fractionation between inorganically and organically bound Fe(III), experiments with variable proportions of inorganic Fe were carried out at 25 °C. Irrespective of the proportion of inorganic Fe, equilibrium fractionation factors were within...

  16. Characterization of Fe (III)-reducing enrichment culture and isolation of Fe (III)-reducing bacterium Enterobacter sp. L6 from marine sediment.

    Science.gov (United States)

    Liu, Hongyan; Wang, Hongyu

    2016-07-01

    To enrich the Fe (III)-reducing bacteria, sludge from marine sediment was inoculated into the medium using Fe (OH)3 as the sole electron acceptor. Efficiency of Fe (III) reduction and composition of Fe (III)-reducing enrichment culture were analyzed. The results indicated that the Fe (III)-reducing enrichment culture with the dominant bacteria relating to Clostridium and Enterobacter sp. had high Fe (III) reduction of (2.73 ± 0.13) mmol/L-Fe (II). A new Fe (III)-reducing bacterium was isolated from the Fe (III)-reducing enrichment culture and identified as Enterobacter sp. L6 by 16S rRNA gene sequence analysis. The Fe (III)-reducing ability of strain L6 under different culture conditions was investigated. The results indicated that strain L6 had high Fe (III)-reducing activity using glucose and pyruvate as carbon sources. Strain L6 could reduce Fe (III) at the range of NaCl concentrations tested and had the highest Fe (III) reduction of (4.63 ± 0.27) mmol/L Fe (II) at the NaCl concentration of 4 g/L. This strain L6 could reduce Fe (III) with unique properties in adaptability to salt variation, which indicated that it can be used as a model organism to study Fe (III)-reducing activity isolated from marine environment. Copyright © 2015 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  17. Impact of Fe(III)-OM complexes and Fe(III) polymerization on SOM pools reactivity under different land uses

    Science.gov (United States)

    Giannetta, B.; Plaza, C.; Zaccone, C.; Siebecker, M. G.; Rovira, P.; Vischetti, C.; Sparks, D. L.

    2017-12-01

    Soil organic matter (SOM) protection and long-term accumulation are controlled by adsorption to mineral surfaces in different ways, depending on its molecular structure and pedo-climatic conditions. Iron (Fe) oxides are known to be key regulators of the soil carbon (C) cycle, and Fe speciation in soils is highly dependent on environmental conditions and chemical interactions with SOM. However, the molecular structure and hydrolysis of Fe species formed in association with SOM is still poorly described. We hypothesize the existence of two pools of Fe which interact with SOM: mononuclear Fe(III)-SOM complexes and precipitated Fe(III) hydroxides. To verify our hypothesis, we investigated the interactions between Fe(III) and physically isolated soil fractions by means of batch experiments at pH 7. Specifically, we examined the fine silt plus clay (FSi+C) fraction, obtained by ultrasonic dispersion and wet sieving. The soil samples spanned several land uses, including coniferous forest (CFS), grassland (GS), technosols (TS) and agricultural (AS) soils. Solid phase products and supernatants were analyzed for C and Fe content. X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) analysis were also performed. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) was used to assess the main C functional groups involved in C complexation and desorption experiments. Preliminary linear combination fitting (LCF) of Fe K-edge extended X-ray absorption fine structure (EXAFS) spectra suggested the formation of ferrihydrite-like polymeric Fe(III) oxides in reacted CFS and GS samples, with higher C and Fe concentration. Conversely, mononuclear Fe(III) OM complexes dominated the speciation for TS and AS samples, characterized by lower C and Fe concentration, inhibiting the hydrolysis and polymerization of Fe (III). This approach will help revealing the mechanisms by which SOM pools can control Fe(III) speciation, and will elucidate how both Fe(III

  18. Mechanisms for Fe(III) oxide reduction in sedimentary environments

    Science.gov (United States)

    Nevin, Kelly P.; Lovely, Derek R.

    2002-01-01

    Although it was previously considered that Fe(III)-reducing microorganisms must come into direct contact with Fe(III) oxides in order to reduce them, recent studies have suggested that electron-shuttling compounds and/or Fe(III) chelators, either naturally present or produced by the Fe(III)-reducing microorganisms themselves, may alleviate the need for the Fe(III) reducers to establish direct contact with Fe(III) oxides. Studies with Shewanella alga strain BrY and Fe(III) oxides sequestered within microporous beads demonstrated for the first time that this organism releases a compound(s) that permits electron transfer to Fe(III) oxides which the organism cannot directly contact. Furthermore, as much as 450 w M dissolved Fe(III) was detected in cultures of S. alga growing in Fe(III) oxide medium, suggesting that this organism releases compounds that can solublize Fe(III) from Fe(III) oxide. These results contrast with previous studies, which demonstrated that Geobacter metallireducens does not produce electron-shuttles or Fe(III) chelators. Some freshwater aquatic sediments and groundwaters contained compounds, which could act as electron shuttles by accepting electrons from G. metallireducens and then transferring the electrons to Fe(III). However, other samples lacked significant electron-shuttling capacity. Spectroscopic studies indicated that the electron-shuttling capacity of the waters was not only associated with the presence of humic substances, but water extracts of walnut, oak, and maple leaves contained electron-shuttling compounds did not appear to be humic substances. Porewater from a freshwater aquatic sediment and groundwater from a petroleum-contaminated aquifer contained dissolved Fe(III) (4-16 w M), suggesting that soluble Fe(III) may be available as an electron acceptor in some sedimentary environments. These results demonstrate that in order to accurately model the mechanisms for Fe(III) reduction in sedimentary environments it will be necessary

  19. Aspergillus niger Secretes Citrate to Increase Iron Bioavailability

    Science.gov (United States)

    Odoni, Dorett I.; van Gaal, Merlijn P.; Schonewille, Tom; Tamayo-Ramos, Juan A.; Martins dos Santos, Vitor A. P.; Suarez-Diez, Maria; Schaap, Peter J.

    2017-01-01

    Aspergillus niger has an innate ability to secrete various organic acids, including citrate. The conditions required for A. niger citrate overproduction are well described, but the physiological reasons underlying extracellular citrate accumulation are not yet fully understood. One of the less understood culture conditions is the requirement of growth-limiting iron concentrations. While this has been attributed to iron-dependent citrate metabolizing enzymes, this straightforward relationship does not always hold true. Here, we show that an increase in citrate secretion under iron limited conditions is a physiological response consistent with a role of citrate as A. niger iron siderophore. We found that A. niger citrate secretion increases with decreasing amounts of iron added to the culture medium and, in contrast to previous findings, this response is independent of the nitrogen source. Differential transcriptomics analyses of the two A. niger mutants NW305 (gluconate non-producer) and NW186 (gluconate and oxalate non-producer) revealed up-regulation of the citrate biosynthesis gene citA under iron limited conditions compared to iron replete conditions. In addition, we show that A. niger can utilize Fe(III) citrate as iron source. Finally, we discuss our findings in the general context of the pH-dependency of A. niger organic acid production, offering an explanation, besides competition, for why A. niger organic acid production is a sequential process influenced by the external pH of the culture medium. PMID:28824560

  20. Dissimilatory Fe(III) and Mn(IV) reduction.

    Science.gov (United States)

    Lovley, D R

    1991-06-01

    The oxidation of organic matter coupled to the reduction of Fe(III) or Mn(IV) is one of the most important biogeochemical reactions in aquatic sediments, soils, and groundwater. This process, which may have been the first globally significant mechanism for the oxidation of organic matter to carbon dioxide, plays an important role in the oxidation of natural and contaminant organic compounds in a variety of environments and contributes to other phenomena of widespread significance such as the release of metals and nutrients into water supplies, the magnetization of sediments, and the corrosion of metal. Until recently, much of the Fe(III) and Mn(IV) reduction in sedimentary environments was considered to be the result of nonenzymatic processes. However, microorganisms which can effectively couple the oxidation of organic compounds to the reduction of Fe(III) or Mn(IV) have recently been discovered. With Fe(III) or Mn(IV) as the sole electron acceptor, these organisms can completely oxidize fatty acids, hydrogen, or a variety of monoaromatic compounds. This metabolism provides energy to support growth. Sugars and amino acids can be completely oxidized by the cooperative activity of fermentative microorganisms and hydrogen- and fatty-acid-oxidizing Fe(III) and Mn(IV) reducers. This provides a microbial mechanism for the oxidation of the complex assemblage of sedimentary organic matter in Fe(III)- or Mn(IV)-reducing environments. The available evidence indicates that this enzymatic reduction of Fe(III) or Mn(IV) accounts for most of the oxidation of organic matter coupled to reduction of Fe(III) and Mn(IV) in sedimentary environments. Little is known about the diversity and ecology of the microorganisms responsible for Fe(III) and Mn(IV) reduction, and only preliminary studies have been conducted on the physiology and biochemistry of this process.

  1. Mangifera indica L. extract (Vimang) inhibits 2-deoxyribose damage induced by Fe (III) plus ascorbate.

    Science.gov (United States)

    Pardo-Andreu, Gilberto Lázaro; Delgado, René; Núñez-Sellés, Alberto J; Vercesi, Anibal E

    2006-02-01

    Vimang is an aqueous extract of selected species of Mangifera indica L, used in Cuba as a nutritional antioxidant supplement. Many in vitro and in vivo models of oxidative stress have been used to elucidate the antioxidant mechanisms of this extract. To further characterize the mechanism of Vimang action, its effect on the degradation of 2-deoxyribose induced by Fe (III)-EDTA plus ascorbate or plus hypoxanthine/xanthine oxidase was studied. Vimang was shown to be a potent inhibitor of 2-deoxyribose degradation mediated by Fe (III)-EDTA plus ascorbate or superoxide (O2-). The results revealed that Vimang, at concentrations higher than 50 microM mangiferin equivalent, was equally effective in preventing degradation of both 15 mM and 1.5 mM 2-deoxyribose. At a fixed Fe (III) concentration, increasing the concentration of ligands (either EDTA or citrate) caused a significant reduction in the protective effects of Vimang. When ascorbate was replaced by O2- (formed by hypoxanthine and xanthine oxidase) the protective efficiency of Vimang was also inversely related to EDTA concentration. The results strongly indicate that Vimang does not block 2-deoxyribose degradation by simply trapping *OH radicals. Rather, Vimang seems to act as an antioxidant by complexing iron ions, rendering them inactive or poorly active in the Fenton reaction. Copyright 2006 John Wiley & Sons, Ltd.

  2. Biodegradation of metal citrate complexes and implications for toxic-metal mobility

    International Nuclear Information System (INIS)

    Francis, A.J.; Dodge, C.J.; Gillow, J.B.

    1992-01-01

    The presence of synthetic and naturally occurring chelating agents in nuclear and toxic-metal wastes is a major concern because of their potential to enhance mobilization of metal ions away from the disposal sites. Of particular interest is citric acid, which is present in low-level and transuranic radioactive wastes and in domestic and industrial wastes (as washing fluids, for instance), as well as being found naturally. Citrate ions form multidentate, stable complexes with a variety of toxic metals and radionuclides; but biodegradation of these complexes, precipitating the metal ions as insoluble hydroxides, oxides or other salts, may retard migration. Here we report a study of the biodegradation of citrate complexes of Ca, Fe(II), Fe(III), Cd, Cu, Ni, Pb and U. Several of these complexes were not readily degraded by bacteria, and the biodegradability depended on the chemical nature of the complex, not on the toxicity of the metal to the bacteria. This resistance to biodegradation implies that citrate complexation may play an important part in migration of these hazardous wastes. (author)

  3. Colorimeter determination of Fe(II)/Fe(III) ratio in glass

    International Nuclear Information System (INIS)

    Baumann, E.W.; Coleman, C.J.; Karraker, D.G.; Scott, W.H.

    1987-01-01

    A colorimetric method has been developed to determine the Fe(II)/Fe(III) ratio in glass containing nuclear waste. Fe(II) is stabilized with pentavalent vanadium during dissolution in sulfuric and hydrofluoric acids. The chromogen is FerroZine (Hach Chemical Company), which forms a magenta complex with Fe(II). The two-step color development consists of determining the Fe(II) by adding FerroZine, followed by determining total Fe after the Fe(III) present is reduced with ascorbic acid. The method was validated by analyzing mixtures of ferrous/ferric solutions and nonferrous glass frit, and by comparison with Moessbauer spectroscopy. The effect of gamma radiation was established. The procedure is generally applicable to nonradioactive materials such as minerals and other glasses

  4. Spectrophotometric speciation of Fe(II) and Fe(III) using hydrazone-micelle systems and flow injections

    International Nuclear Information System (INIS)

    Khojali, Inas Osman

    1999-04-01

    Two hydrazones were synthesised, namely salicylhyrazone (SH) and trihydroxyacetophenone (THAPH) were synthesised with the objective of developing a method for determining of Fe(II) and Fe(III) in the presence of each other and hence the total iron.those hydrazones were selected so as to combine the ability of phenolic compounds to complex Fe(III) ions and the complexing characteristics of hydrazones. The complexes of Fe(II) S H and Fe(III) S H as well those of Fe(II)-THAPH and Fe(III)-THAPH had shown maximum absorbance at λ=412 nm which was not not modified by presence of micelles i.e. sodium n-dodecyl sulphate (SDS) and n-hexa dodecyl pyridinium bromide. The maximum absorbance for all complexes takes place around a neutral pH. Generally, in addition, of n-hexa dodecylpyridinium bromide to fe(II)-SH and Fe(III)-SH absorbance of the complexes increases with increasing the concentration of the micelle. The effects of the addition of sodium n-dodecyle sulphate (SDS) to Fe(III)-SH is also studied. Generally, increasing the concentration of the micelle decrease the absorbance of the complexes. To study the effect of the presence of Fe(II) and Fe(III) on the determination of each other,mixtures of Fe(II)-SH and Fe(III)-SH are studied. However, the use of ascorbic acid as a reducing reagent for Fe(III) did not produce the needed results but non reducible results, which may be due to the masking effect of ascorbic acid and thus making the metal not available to the ligand. However, conversion of Fe(II) to Fe(III) prior to the determination was avoided as this requires the use of oxidant, which will oxidise the ligand as well. To establish the condition for the maximum absorbance of THAPH complexes, the effect of the base was investigated by using sodium and ammonium hydroxide. Generally, increasing the concentration of the base decreases the abosrbance. as expected, ammonium hydroxide produced positive results than sodium hydroxide. After establishing the optimum Fi

  5. Impact of two iron(III) chelators on the iron, cadmium, lead and nickel accumulation in poplar grown under heavy metal stress in hydroponics.

    Science.gov (United States)

    Mihucz, Victor G; Csog, Árpád; Fodor, Ferenc; Tatár, Enikő; Szoboszlai, Norbert; Silaghi-Dumitrescu, Luminiţa; Záray, Gyula

    2012-04-15

    Poplar (Populus jacquemontiana var. glauca cv. Kopeczkii) was grown in hydroponics containing 10 μM Cd(II), Ni(II) or Pb(II), and Fe as Fe(III) EDTA or Fe(III) citrate in identical concentrations. The present study was designed to compare the accumulation and distribution of Fe, Cd, Ni and Pb within the different plant compartments. Generally, Fe and heavy-metal accumulation were higher by factor 2-7 and 1.6-3.3, respectively, when Fe(III) citrate was used. Iron transport towards the shoot depended on the Fe(III) chelate and, generally, on the heavy metal used. Lead was accumulated only in the root. The amounts of Fe and heavy metals accumulated by poplar were very similar to those of cucumber grown in an identical way, indicating strong Fe uptake regulation of these two Strategy I plants: a cultivar and a woody plant. The Strategy I Fe uptake mechanism (i.e. reducing Fe(III) followed by Fe(II) uptake), together with the Fe(III) chelate form in the nutrient solution had significant effects on Fe and heavy metal uptake. Poplar appears to show phytoremediation potential for Cd and Ni, as their transport towards the shoot was characterized by 51-54% and 26-48% depending on the Fe(III) supply in the nutrient solution. Copyright © 2012 Elsevier GmbH. All rights reserved.

  6. Gas response properties of citrate gel synthesized nanocrystalline MgFe2O4: Effect of sintering temperature

    International Nuclear Information System (INIS)

    Patil, J.Y.; Mulla, I.S.; Suryavanshi, S.S.

    2013-01-01

    Graphical abstract: Display Omitted Highlights: ► Synthesis of nanocrystalline MgFe 2 O 4 by economical citrate gel combustion method. ► Structural, morphological, and gas response properties of MgFe 2 O 4 . ► Enhancement in selectivity of MgFe 2 O 4 towards LPG with sintering temperature. ► Use of MgFe 2 O 4 to detect different gases at different operating temperatures. -- Abstract: Spinel type MgFe 2 O 4 material was synthesized by citrate gel combustion method. The effect of sintering temperature on structural, morphological, and gas response properties was studied. The powder X-ray diffraction pattern and transmission electron microscope study confirms nanocrystalline spinel structure of the synthesized powder. The material was tested for response properties to various reducing gases like liquid petroleum gas (LPG), acetone, ethanol, and ammonia. The results demonstrated n-type semiconducting behavior of MgFe 2 O 4 material. It was revealed that MgFe 2 O 4 sintered at 973 K was most sensitive to LPG at 648 K and to acetone at 498 K. However MgFe 2 O 4 sintered at 1173 K exhibited higher response and selectivity to LPG with marginal increase in the operating temperature. Furthermore, the sensor exhibited a fast response and a good recovery. It was observed that the particles size, porosity, and surface activity of the sensor material is affected by the sintering temperature.

  7. Synthesis, characterization and stability of Cr(III) and Fe(III) hydroxides

    International Nuclear Information System (INIS)

    Papassiopi, N.; Vaxevanidou, K.; Christou, C.; Karagianni, E.; Antipas, G.S.E.

    2014-01-01

    Highlights: • Fe(III)–Cr(III) hydroxides enhance groundwater quality better than pure Cr(III) compounds. • Crystalline Cr(OH) 3 ·3H 2 O was unstable, with a solubility higher than 50 μg/l. • Amorphous Cr(OH) 3 (am) was stable with a solubility lower than 50 μg/l in the range 5.7 0.75 Cr 0.25 (OH) 3 , the stability region was extended to 4.8 3 ·xH 2 O whereas in the presence of iron the precipitate is a mixed Fe (1−x) Cr x (OH) 3 phase. In this study, we report on the synthesis, characterisation and stability of mixed (Fe x ,Cr 1−x )(OH) 3 hydroxides as compared to the stability of Cr(OH) 3 . We established that the plain Cr(III) hydroxide, abiding to the approximate molecular formula Cr(OH) 3 ·3H 2 O, was crystalline, highly soluble, i.e. unstable, with a tendency to transform into the stable amorphous hydroxide Cr(OH) 3 (am) phase. Mixed Fe 0.75 Cr 0.25 (OH) 3 hydroxides were found to be of the ferrihydrite structure, Fe(OH) 3 , and we correlated their solubility to that of a solid solution formed by plain ferrihydrite and the amorphous Cr(III) hydroxide. Both our experimental results and thermodynamic calculations indicated that mixed Fe(III)–Cr(III) hydroxides are more effective enhancers of groundwater quality, in comparison to the plain amorphous or crystalline Cr(III) hydroxides, the latter found to have a solubility typically higher than 50 μg/l (maximum EU permitted Cr level in drinking water), while the amorphous Cr(OH) 3 (am) phase was within the drinking water threshold in the range 5.7 0.75 Cr 0.25 (OH) 3 hydroxides studied were of extended stability in the 4.8 < pH < 13.5 range

  8. Fe(II)/Fe(III)-Catalyzed Intramolecular Didehydro-Diels-Alder Reaction of Styrene-ynes.

    Science.gov (United States)

    Mun, Hyeon Jin; Seong, Eun Young; Ahn, Kwang-Hyun; Kang, Eun Joo

    2018-02-02

    The intramolecular didehydro-Diels-Alder reaction of styrene-ynes was catalyzed by Fe(II) and Fe(III) to produce various naphthalene derivatives under microwave heating conditions. Mechanistic calculations found that the Fe(II) catalyst activates the styrenyl diene in an inverse-electron-demand Diels-Alder reaction, and the consecutive dehydrogenation reaction can be promoted by either Fe(II)-catalyzed direct dehydrogenation or an Fe(III)-catalyzed rearomatization/dehydrogenation pathway.

  9. Synthesis, characterization and stability of Cr(III) and Fe(III) hydroxides

    Energy Technology Data Exchange (ETDEWEB)

    Papassiopi, N.; Vaxevanidou, K.; Christou, C.; Karagianni, E.; Antipas, G.S.E., E-mail: gantipas@metal.ntua.gr

    2014-01-15

    Highlights: • Fe(III)–Cr(III) hydroxides enhance groundwater quality better than pure Cr(III) compounds. • Crystalline Cr(OH){sub 3}·3H{sub 2}O was unstable, with a solubility higher than 50 μg/l. • Amorphous Cr(OH){sub 3}(am) was stable with a solubility lower than 50 μg/l in the range 5.7 < pH < 11. • For mixed Fe{sub 0.75}Cr{sub 0.25}(OH){sub 3}, the stability region was extended to 4.8 < pH < 13.5. -- Abstract: Chromium is a common contaminant of soils and aquifers and constitutes a major environmental problem. In nature, chromium usually exists in the form of two oxidation states, trivalent, Cr(III), which is relatively innocuous for biota and for the aquatic environment, and hexavalent, Cr(VI) which is toxic, carcinogenic and very soluble. Accordingly, the majority of wastewater and groundwater treatment technologies, include a stage where Cr(VI) is reduced to Cr(III), in order to remove chromium from the aqueous phase and bind the element in the form of environmentally stable solid compounds. In the absence of iron the final product is typically of the form Cr(OH){sub 3}·xH{sub 2}O whereas in the presence of iron the precipitate is a mixed Fe{sub (1−x)}Cr{sub x}(OH){sub 3} phase. In this study, we report on the synthesis, characterisation and stability of mixed (Fe{sub x},Cr{sub 1−x})(OH){sub 3} hydroxides as compared to the stability of Cr(OH){sub 3}. We established that the plain Cr(III) hydroxide, abiding to the approximate molecular formula Cr(OH){sub 3}·3H{sub 2}O, was crystalline, highly soluble, i.e. unstable, with a tendency to transform into the stable amorphous hydroxide Cr(OH){sub 3}(am) phase. Mixed Fe{sub 0.75}Cr{sub 0.25}(OH){sub 3} hydroxides were found to be of the ferrihydrite structure, Fe(OH){sub 3}, and we correlated their solubility to that of a solid solution formed by plain ferrihydrite and the amorphous Cr(III) hydroxide. Both our experimental results and thermodynamic calculations indicated that mixed Fe(III)–Cr(III

  10. Characterisation of citrate and iron citrate uptake by cultured rat hepatocytes

    International Nuclear Information System (INIS)

    Graham, R.M.; Morgan, E.H.; Baker, E.

    1998-01-01

    Background/Aims: the endogenous low molecular weight iron chelator, citrate, is considered to be an important contributor to iron transport and the liver the main site of uptake of iron citrate in subjects suffering from diseases of iron overload. Moreover, the citrate-metabolising enzyme, aconitase, is implicated in the regulation of cellular iron metabolism. This study was undertaken to determine the role of citrate and ferric citrate in the uptake of iron by rat hepatocytes. Methods: Cultured rat hepatocytes were incubated (37 deg. C, 15 min) with 100 μM [ 14 C]-citrate in the presence or absence of 1.0 μM 55 Fe. Membrane-bound and intracellular radiolabel were separated by incubation with the general protease, Pronase. Results: Our results suggest that ferric citrate uptake is mediated by a specific citrate binding site which exhibits a higher affinity for citrate in the presence of iron than in its absence. Citrate was internalised by hepatocytes, with at least 70% being oxidised to CO 2 within 15 min. Citrate uptake was pH-dependent, did not require the presence of sodium and increased with increasing iron concentration. Metabolic energy, anion channels, the Na + , K + -ATPase and vesicle acidification do not appear to play a role in uptake of ferric citrate, but functional sulphydryl groups may be involved. Conclusions: The data suggest either that ferric citrate complexes with higher molar ratios of iron to citrate relative to the incubation medium are bound preferentially to the membrane, or that once citrate has delivered its iron to the membrane, the complex dissociates and the components are internalised separately. (au)

  11. Effect of the oxidation rate and Fe(II) state on microbial nitrate-dependent Fe(III) mineral formation

    Science.gov (United States)

    Senko, John M.; Dewers , Thomas A.; Krumholz, Lee R.

    2005-01-01

    A nitrate-dependent Fe(II)-oxidizing bacterium was isolated and used to evaluate whether Fe(II) chemical form or oxidation rate had an effect on the mineralogy of biogenic Fe(III) (hydr)oxides resulting from nitrate-dependent Fe(II) oxidation. The isolate (designated FW33AN) had 99% 16S rRNA sequence similarity to Klebsiella oxytoca. FW33AN produced Fe(III) (hydr)oxides by oxidation of soluble Fe(II) [Fe(II)sol] or FeS under nitrate-reducing conditions. Based on X-ray diffraction (XRD) analysis, Fe(III) (hydr)oxide produced by oxidation of FeS was shown to be amorphous, while oxidation of Fe(II)sol yielded goethite. The rate of Fe(II) oxidation was then manipulated by incubating various cell concentrations of FW33AN with Fe(II)sol and nitrate. Characterization of products revealed that as Fe(II) oxidation rates slowed, a stronger goethite signal was observed by XRD and a larger proportion of Fe(III) was in the crystalline fraction. Since the mineralogy of Fe(III) (hydr)oxides may control the extent of subsequent Fe(III) reduction, the variables we identify here may have an effect on the biogeochemical cycling of Fe in anoxic ecosystems.

  12. Particle Aggregation During Fe(III) Bioreduction in Nontronite

    Science.gov (United States)

    Jaisi, D. P.; Dong, H.; Hi, Z.; Kim, J.

    2005-12-01

    This study was performed to evaluate the rate and mechanism of particle aggregation during bacterial Fe (III) reduction in different size fractions of nontronite and to investigate the role of different factors contributing to particle aggregation. To achieve this goal, microbial Fe(III) reduction experiments were performed with lactate as an electron donor, Fe(III) in nontronite as an electron acceptor, and AQDS as an electron shuttle in bicarbonate buffer using Shewanella putrefaceins CN32. These experiments were performed with and without Na- pyrophosphate as a dispersant in four size fractions of nontronite (0.12-0.22, 0.41-0.69, 0.73-0.96 and 1.42-1.8 mm). The rate of nontronite aggregation during the Fe(III) bioreduction was measured by analyzing particle size distribution using photon correlation spectroscopy (PCS) and SEM images analysis. Similarly, the changes in particle morphology during particle aggregation were determined by analyses of SEM images. Changes in particle surface charge were measured with electrophoretic mobility analyzer. The protein and carbohydrate fraction of EPS produced by cells during Fe(III) bioreduction was measured using Bradford and phenol-sulfuric acid extraction method, respectively. In the presence of the dispersant, the extent of Fe(III) bioreduction was 11.5-12.2% within the first 56 hours of the experiment. There was no measurable particle aggregation in control experiments. The PCS measurements showed that the increase in the effective diameter (95% percentile) was by a factor of 3.1 and 1.9 for particle size of 0.12-0.22 mm and 1.42-1.80 mm, respectively. The SEM image analyses also gave the similar magnitude of increase in particle size. In the absence of the dispersant, the extent of Fe(III) bioreduction was 13.4-14.5% in 56 hours of the experiment. The rate of aggregation was higher than that in the presence of the dispersant. The increase in the effective diameter (95% percentile) was by a factor of 13.6 and 4.1 for

  13. Ion-Selective Electrode for the Determination of Iron(III in Vitamin Formulations

    Directory of Open Access Journals (Sweden)

    Teixeira Marcos Fernando de S.

    1998-01-01

    Full Text Available A coated graphite-epoxy ion-selective electrode for iron(III, based on the ion-pair formed between [Fe(citrate2]3- and the tricaprylylmethylammonium cation (Aliquat 336 in a poly(vinylchloride (PVC matrix has been constructed. A thin membrane film of this ion-pair, dibutylphthalate (DBPh in PVC was deposited directly onto a Perspex® tube, which contained a graphite-epoxy conductor substrate. The coating solution was prepared by dissolving 30% (w/w of PVC in 10 mL of tetrahydrofuran following addition of 65% (w/w DBPh and 5% (w/w of the ionic pair. The effect of pH, citrate concentration and some cations on the electrode response has been investigated. The E(mV vs. log [Fe(citrate2]3- electrode response was linear for iron(III concentration from 1.0 x 10-3 mol/L to 1.0 x 10-1 mol/L in 1.0 mol/L citrate medium, with a slope of 19.3 ± 0.5 mV/decade and a useful lifetime of at least six months (more than 800 determinations for each polymeric membrane used. The detection limit was 7.5 x 10-4 mol/L and the relative standard deviation was less than 3% for a solution containing 5.0 x 10-3 mol/L of iron(III (n = 10. The application of this electrode for iron(III determination in samples of vitamin formulations is described. The results obtained with this procedure are in close agreement with those obtained using AA spectrophotometry (r = 0.9999.

  14. Microbiological evidence for Fe(III) reduction on early Earth

    Science.gov (United States)

    Vargas, Madeline; Kashefi, Kazem; Blunt-Harris, Elizabeth L.; Lovley, Derek R.

    1998-09-01

    It is generally considered that sulphur reduction was one of the earliest forms of microbial respiration, because the known microorganisms that are most closely related to the last common ancestor of modern life are primarily anaerobic, sulphur-reducing hyperthermophiles. However, geochemical evidence indicates that Fe(III) is more likely than sulphur to have been the first external electron acceptor of global significance in microbial metabolism. Here we show that Archaea and Bacteria that are most closely related to the last common ancestor can reduce Fe(III) to Fe(II) and conserve energy to support growth from this respiration. Surprisingly, even Thermotoga maritima, previously considered to have only a fermentative metabolism, could grow as a respiratory organism when Fe(III) was provided as an electron acceptor. These results provide microbiological evidence that Fe(III) reduction could have been an important process on early Earth and suggest that microorganisms might contribute to Fe(III) reduction in modern hot biospheres. Furthermore, our discovery that hyperthermophiles that had previously been thought to require sulphur for cultivation can instead be grown without the production of toxic and corrosive sulphide, should aid biochemical investigations of these poorly understood organisms.

  15. Gas response properties of citrate gel synthesized nanocrystalline MgFe{sub 2}O{sub 4}: Effect of sintering temperature

    Energy Technology Data Exchange (ETDEWEB)

    Patil, J.Y. [School of Physical Sciences, Solapur University Solapur-413255 (India); Mulla, I.S. [Emeritus Scientist (CSIR), Centre for Materials for Electronic Technology(C-MET) Pune-411 008 (India); Suryavanshi, S.S., E-mail: sssuryavanshi@rediffmail.com [School of Physical Sciences, Solapur University Solapur-413255 (India)

    2013-02-15

    Graphical abstract: Display Omitted Highlights: ► Synthesis of nanocrystalline MgFe{sub 2}O{sub 4} by economical citrate gel combustion method. ► Structural, morphological, and gas response properties of MgFe{sub 2}O{sub 4}. ► Enhancement in selectivity of MgFe{sub 2}O{sub 4} towards LPG with sintering temperature. ► Use of MgFe{sub 2}O{sub 4} to detect different gases at different operating temperatures. -- Abstract: Spinel type MgFe{sub 2}O{sub 4} material was synthesized by citrate gel combustion method. The effect of sintering temperature on structural, morphological, and gas response properties was studied. The powder X-ray diffraction pattern and transmission electron microscope study confirms nanocrystalline spinel structure of the synthesized powder. The material was tested for response properties to various reducing gases like liquid petroleum gas (LPG), acetone, ethanol, and ammonia. The results demonstrated n-type semiconducting behavior of MgFe{sub 2}O{sub 4} material. It was revealed that MgFe{sub 2}O{sub 4} sintered at 973 K was most sensitive to LPG at 648 K and to acetone at 498 K. However MgFe{sub 2}O{sub 4} sintered at 1173 K exhibited higher response and selectivity to LPG with marginal increase in the operating temperature. Furthermore, the sensor exhibited a fast response and a good recovery. It was observed that the particles size, porosity, and surface activity of the sensor material is affected by the sintering temperature.

  16. Low temperature {sup 57}Fe Moessbauer study of cucumber root

    Energy Technology Data Exchange (ETDEWEB)

    Kovacs, K; Kuzmann, E; Homonnay, Z; Vertes, A [Institute of Chemistry, Eoetvoes Lorand University, PO Box 32, 1512 Budapest (Hungary); Fodor, F [Department of Plant Physiology and Molecular Plant Biology, Eoetvoes Lorand University, PO Box 32, 1512 Budapest (Hungary); Machala, L, E-mail: kkriszti@chem.elte.h [Centre for Nanomaterial Research, Palacky University, Svobody 26, Olomouc 771 46 (Czech Republic)

    2010-03-01

    Iron uptake and distribution in cucumber root were studied with the help of {sup 57}Fe Moessbauer spectroscopy at low temperature applying external magnetic field. Cucumber was grown in iron sufficient modified Hoagland nutrient solution. Moessbauer spectra of the frozen roots taken at 4.2 and 1.5 K, at 5 T external magnetic field support the identification of the main iron species (Fe{sup III}-carboxylates, hydrous ferric oxides, Fe{sup III}-sulfate-hydroxide) suggested according to its Moessbauer spectra taken between 35-200 K [1]. The magnetic ordering temperature of the hydrous ferric oxide and Fe{sup III}-sulfate-hydroxide was found to be in the range of 4.2-1.5 K, which suggests the incorporation of H{sub 3}O{sup +}, PO{sub 4}{sup 3-} and citrate into these minerals.

  17. A study of the Fe(III)/Fe(II)-triethanolamine complex redox couple for redox flow battery application

    International Nuclear Information System (INIS)

    Wen, Y.H.; Zhang, H.M.; Qian, P.; Zhou, H.T.; Zhao, P.; Yi, B.L.; Yang, Y.S.

    2006-01-01

    The electrochemical behavior of the Fe(III)/Fe(II)-triethanolamine(TEA) complex redox couple in alkaline medium and influence of the concentration of TEA were investigated. A change of the concentration of TEA mainly produces the following two results. (1) With an increase of the concentration of TEA, the solubility of the Fe(III)-TEA can be increased to 0.6 M, and the solubility of the Fe(II)-TEA is up to 0.4 M. (2) In high concentration of TEA with the ratio of TEA to NaOH ranging from 1 to 6, side reaction peaks on the cathodic main reaction of the Fe(III)-TEA complex at low scan rate can be minimized. The electrode process of Fe(III)-TEA/Fe(II)-TEA is electrochemically reversible with higher reaction rate constant than the uncomplexed species. Constant current charge-discharge shows that applying anodic active materials of relatively high concentrations facilitates the improvement of cell performance. The open-circuit voltage of the Fe-TEA/Br 2 cell with the Fe(III)-TEA of 0.4 M, after full charging, is nearly 2.0 V and is about 32% higher than that of the all-vanadium batteries, together with the energy efficiency of approximately 70%. The preliminary exploration shows that the Fe(III)-TEA/Fe(II)-TEA couple is electrochemically promising as negative redox couple for redox flow battery (RFB) application

  18. Molecular magnetism of a linear Fe(III)-Mn(II)-Fe(III) complex. Influence of long-range exchange interaction

    International Nuclear Information System (INIS)

    Lengen, M.; Chaudhuri, P.

    1994-01-01

    The magnetic properties of [L-Fe(III)-dmg 3 Mn(II)-Fe(III)-L] (ClO 4 ) 2 have been characterized by magnetic susceptibility, EPR, and Moessbauer studies. L represents 1,4,7-trimethyl-,1,4,7-triazacyclononane and dmg represents dimethylglyoxime. X-ray diffraction measurements yield that the arrangement of the three metal centers is strictly linear with atomic distances d Fe-Mn 0.35 nm and d Fe-Fe = 0.7 nm. Magnetic susceptibility measurements (3-295 K) were analyzed in the framework of the spin-Hamiltonian formalism considering Heisenberg exchange and Zeeman interaction: H = J Fe-Mn (S Fe1 + S Fe2 )S Mn + J Fe-Fe S Fe1 S Fe2 + gμ B S total B. The spins S Fe1 = S Fe2 = S Mn = 5/2 of the complex are antiferromagnetically coupled, yielding a total spin of S total = 5/2 with exchange coupling constants F Fe-Mn = 13.4 cm -1 and J Fe-Fe = 4.5 cm -1 . Magnetically split Moessbauer spectra were recorded at 1.5 K under various applied fields (20 mT, 170 mT, 4 T). The spin-Hamiltonian analysis of these spectra yields isotropic magnetic hyperfine coupling with A total /(g N μ N ) = -18.5 T. The corresponding local component A Fe is related to A total via spin-projection: A total = (6/7)A Fe . The resulting A Fe /(g N μ N ) -21.6 T is in agreement with standard values of ferric high-spin complexes. Spin-Hamiltonian parameters as obtained from Moessbauer studies and exchange coupling constants as derived from susceptibility measurements are corroborated by temperature-dependent EPR studies. (orig.)

  19. A binuclear Fe(III)Dy(III) single molecule magnet. Quantum effects and models.

    Science.gov (United States)

    Ferbinteanu, Marilena; Kajiwara, Takashi; Choi, Kwang-Yong; Nojiri, Hiroyuki; Nakamoto, Akio; Kojima, Norimichi; Cimpoesu, Fanica; Fujimura, Yuichi; Takaishi, Shinya; Yamashita, Masahiro

    2006-07-19

    The binuclear [FeIII(bpca)(mu-bpca)Dy(NO3)4], having Single Molecule Magnet (SMM) properties, belonging to a series of isostructural FeIIILnIII complexes (Ln = Eu, Gd, Tb, Dy, Ho) and closely related FeIILnIII chain structures, was characterized in concise experimental and theoretical respects. The low temperature magnetization data showed hysteresis and tunneling. The anomalous temperature dependence of Mössbauer spectra is related to the onset of magnetic order, consistent with the magnetization relaxation time scale resulting from AC susceptibility measurements. The advanced ab initio calculations (CASSCF and spin-orbit) revealed the interplay of ligand field, spin-orbit, and exchange effects and probed the effective Ising nature of the lowest states, involved in the SMM and tunneling effects.

  20. Fe(III) mobilisation by carbonate in low temperature environments: Study of the solubility of ferrihydrite in carbonate media and the formation of Fe(III) carbonate complexes

    International Nuclear Information System (INIS)

    Grivé, Mireia; Duro, Lara; Bruno, Jordi

    2014-01-01

    Graphical abstract: - Highlights: • We have determined thermodynamic stabilities of Fe(III)-carbonate species. • We have determined the effect of those species on the solubility of ferrihydrite. • Results. • Highlight the importance of two Fe(III)-carbonate: FeOHCO 3 and Fe(CO 3 ) 3 3− . - Abstract: The linkage between the iron and the carbon cycles is of paramount importance to understand and quantify the effect of increased CO 2 concentrations in natural waters on the mobility of iron and associated trace elements. In this context, we have quantified the thermodynamic stability of mixed Fe(III) hydroxo-carbonate complexes and their effect on the solubility of Fe(III) oxihydroxides. We present the results of carefully performed solubility measurements of 2-line ferrihydrite in the slightly acidic to neutral–alkaline pH ranges (3.8–8.7) under constant pCO 2 varying between (0.982–98.154 kPa) at 25 °C. The outcome of the work indicates the predominance of two Fe(III) hydroxo carbonate complexes FeOHCO 3 and Fe(CO 3 ) 3 3− , with formation constants log * β° 1,1,1 = 10.76 ± 0.38 and log β° 1,0,3 = 24.24 ± 0.42, respectively. The solubility constant for the ferrihydrite used in this study was determined in acid conditions (pH: 1.8–3.2) in the absence of CO 2 and at T = (25 ± 1) °C, as log * K s,0 = 1.19 ± 0.41. The relative stability of the Fe(III)-carbonate complexes in alkaline pH conditions has implications for the solubility of Fe(III) in CO 2 -rich environments and the subsequent mobilisation of associated trace metals that will be explored in subsequent papers

  1. The reduction of 4-chloronitrobenzene by Fe(II)-Fe(III) oxide systems - correlations with reduction potential and inhibition by silicate

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Adele M., E-mail: adele.jones1@unsw.edu.au; Kinsela, Andrew S.; Collins, Richard N.; Waite, T. David, E-mail: d.waite@unsw.edu.au

    2016-12-15

    Recent studies have demonstrated that the rate at which Fe(II)-Fe(III) oxyhydroxide systems catalyze the reduction of reducible contaminants, such as 4-chloronitrobenzene, is well correlated to their thermodynamic reduction potential. Here we confirm this effect in the presence of Fe(III) oxyhydroxide phases not previously assessed, namely ferrihydrite and nano-goethite, as well as Fe(III) oxyhydroxide phases previously examined. In addition, silicate is found to decrease the extent of Fe(II) sorption to the Fe(III) oxyhydroxide surface, increasing the reduction potential of the Fe(II)-Fe(III) oxyhydroxide suspension and, accordingly, decreasing the rate of 4-chloronitrobenzene reduction. A linear relationship between the reduction potential of the Fe(II)-Fe(III) oxyhydroxide suspensions and the reduction rate of 4-chloronitrobenzene (normalized to surface area and concentration of sorbed Fe(II)) was obtained in the presence and absence of silicate. However, when ferrihydrite was doped with Si (through co-precipitation) the reduction of 4-chloronitrobenzene was much slower than predicted from its reduction potential. The results obtained have significant implications to the likely effectiveness of naturally occurring contaminant degradation processes involving Fe(II) and Fe(III) oxyhydroxides in groundwater environments containing high concentrations of silicate, or other species which compete with Fe(II) for sorption sites.

  2. Selective transport of Fe(III) using ionic imprinted polymer (IIP) membrane particle

    Science.gov (United States)

    Djunaidi, Muhammad Cholid; Jumina, Siswanta, Dwi; Ulbricht, Mathias

    2015-12-01

    The membrane particles was prepared from polyvinyl alcohol (PVA) and polymer IIP with weight ratios of 1: 2 and 1: 1 using different adsorbent templates and casting thickness. The permeability of membrane towards Fe(III) and also mecanism of transport were studied. The selectivity of the membrane for Fe(III) was studied by performing adsorption experiments also with Cr(III) separately. In this study, the preparation of Ionic Imprinted Polymer (IIP) membrane particles for selective transport of Fe (III) had been done using polyeugenol as functional polymer. Polyeugenol was then imprinted with Fe (III) and then crosslinked with PEGDE under alkaline condition to produce polyeugenol-Fe-PEGDE polymer aggregates. The agrregates was then crushed and sieved using mesh size of 80 and the powder was then used to prepare the membrane particles by mixing it with PVA (Mr 125,000) solution in 1-Methyl-2-pyrrolidone (NMP) solvent. The membrane was obtained after casting at a speed of 25 m/s and soaking in NaOH solution overnight. The membrane sheet was then cut and Fe(III) was removed by acid to produce IIP membrane particles. Analysis of the membrane and its constituent was done by XRD, SEM and size selectivity test. Experimental results showed the transport of Fe(III) was faster with the decrease of membrane thickness, while the higher concentration of template ion correlates with higher Fe(III) being transported. However, the transport of Fe(III) was slower for higher concentration of PVA in the membrane. IImparticles works through retarded permeation mechanism, where Fe(III) was bind to the active side of IIP. The active side of IIP membrane was dominated by the -OH groups. The selectivity of all IIP membranes was confirmed as they were all unable to transport Cr (III), while NIP (Non-imprinted Polymer) membrane was able transport Cr (III).

  3. Structure and dynamics of hydrated Fe(II) and Fe(III) ions. Quantum mechanical and molecular mechanical simulations

    International Nuclear Information System (INIS)

    Remsungnen, T.

    2002-11-01

    Classical molecular dynamics (MD) and combined em ab initio quantum mechanical/molecular mechanical molecular dynamics (QM/MM-MD) simulations have been performed to investigate structural, dynamical and energetical properties of Fe(II), and Fe(III) transition metal ions in aqueous solution. In the QM/MM-MD simulations the ion and its first hydration sphere were treated at the Hartree-Fock ab initio quantum mechanical level, while ab initio generated pair plus three-body potentials were employed for the remaining system. For the classical MD simulation the pair plus three-body potential were employed for all ion-water interactions. The coordination number of the first hydration shell is 100 % of 6 in both cases. The number of waters in the second hydration shell obtained from classical simulations are 13.4 and 15.1 for Fe(II) and Fe(III), respectively, while QM/MM-MD gives the values of 12.4 and 13.4 for Fe(II) and Fe(III). The energies of hydration obtained from MD and QM/MM-MD for Fe(II) are 520 and 500 kcal/mol, and for Fe(III) 1160 and 1100 kcal/mol respectively. The mean residence times of water in the second shell obtained from QM/MM-MD are 24 and 48 ps for Fe(II) and Fe(III), respectively. In contrast to the data obtained from classical MD simulation, the QM/MM-MD values are all in good agreement with the experimental data available. These investigations and results clearly indicate that many-body effects are essential for the proper description of all properties of the aqueous solution of both Fe(II) and Fe(III) ions. (author)

  4. Study on the extraction characteristics of Fe(III) with trialkylphosphine oxide

    International Nuclear Information System (INIS)

    Zhang Qiwei; Jiao Rongzhou; Song Chongli

    1994-08-01

    The extractive properties of TRPO (trialkyephosphine oxide) as the extractant for the Fe(III) have been studied. Under this experiment condition, the distribution ratio D of Fe (III) with the changes of extraction equilibrium time, temperature, nitric acid concentration and Fe 3+ concentration in aqueous solution have been determined. The ΔH degree, ΔS degree and apparent equilibrium constant K of the reaction in which Fe (III) is extracted by TRPO have been calculated. The experiment results show that the third phase appearance in 30% TRPO extractive system has close relations with Fe 3+ concentration in aqueous solution. When nitric acid concentration is 1.5 mol/L and Fe 3+ initial concentration is higher than 8.0 g/L in aqueous solution, the extractant system appears third phase. Two organic phase volume ratio and Fe(III) concentration ratio in the organic phases have been determined respectively, and they vary with the Fe 3+ concentration in aqueous solution

  5. Preparation and characterisation of mixed ligand complexes of Co(III), Fe(III) and Cr(III) containing phthalimide and phenols

    International Nuclear Information System (INIS)

    Miah, M.A.J.; Islam, M.S.; Pal, S.C.; Barma, T.K.

    1996-01-01

    Some novel mixed ligand complexes of Co(III), Fe(III) and Cr(III) containing phthalimide as primary and 2-aminophenol and 3-aminophenol as secondary ligands have been synthesized and characterised on the basis of elemental analyses, conductivity and magnetic measurements and infrared and electronic spectral studies. Complexes containing 2-aminophenol are 1:1 electrolyte in N,N dimethylformamide. Spectral studies indicate that all the complexes exhibit octahedral geometry. The complexes have the general composition; K[M(pim)/sub 2/(L)/sub 2/]; where m=Co(III), Fe(III) and Cr(III), pim-anion of phthalimamide and L=anion of 2-aminophenol and 3-aminophenol. (author)

  6. Single peak parameters technique for simultaneous measurements: Spectrophotometric sequential injection determination of Fe(II) and Fe(III).

    Science.gov (United States)

    Kozak, J; Paluch, J; Węgrzecka, A; Kozak, M; Wieczorek, M; Kochana, J; Kościelniak, P

    2016-02-01

    Spectrophotometric sequential injection system (SI) is proposed to automate the method of simultaneous determination of Fe(II) and Fe(III) on the basis of parameters of a single peak. In the developed SI system, sample and mixture of reagents (1,10-phenanthroline and sulfosalicylic acid) are introduced into a vessel, where in an acid environment (pH≅3) appropriate compounds of Fe(II) and Fe(III) with 1,10-phenanthroline and sulfosalicylic acid are formed, respectively. Then, in turn, air, sample, EDTA and sample again, are introduced into a holding coil. After the flow reversal, a segment of air is removed from the system by an additional valve and as EDTA replaces sulfosalicylic acid forming a more stable colorless compound with Fe(III), a complex signal is registered. Measurements are performed at wavelength 530 nm. The absorbance measured at minimum of the negative peak and the area or the absorbance measured at maximum of the signal can be used as measures corresponding to Fe(II) and Fe(III) concentrations, respectively. The time of the peak registration is about 2 min. Two-component calibration has been applied to analysis. Fe(II) and Fe(III) can be determined within the concentration ranges of 0.04-4.00 and 0.1-5.00 mg L(-1), with precision less than 2.8% and 1.7% (RSD), respectively and accuracy better than 7% (RE). The detection limit is 0.04 and 0.09 mg L(-1) for Fe(II) and Fe(III), respectively. The method was applied to analysis of artesian water samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Cd Mobility in Anoxic Fe-Mineral-Rich Environments - Potential Use of Fe(III)-Reducing Bacteria in Soil Remediation

    Science.gov (United States)

    Muehe, E. M.; Adaktylou, I. J.; Obst, M.; Schröder, C.; Behrens, S.; Hitchcock, A. P.; Tylsizczak, T.; Michel, F. M.; Krämer, U.; Kappler, A.

    2014-12-01

    Agricultural soils are increasingly burdened with heavy metals such as Cd from industrial sources and impure fertilizers. Metal contaminants enter the food chain via plant uptake from soil and negatively affect human and environmental health. New remediation approaches are needed to lower soil metal contents. To apply these remediation techniques successfully, it is necessary to understand how soil microbes and minerals interact with toxic metals. Here we show that microbial Fe(III) reduction initially mobilizes Cd before its immobilization under anoxic conditions. To study how microbial Fe(III) reduction influences Cd mobility, we isolated a new Cd-tolerant, Fe(III)-reducing Geobacter sp. from a heavily Cd-contaminated soil. In lab experiments, this Geobacter strain first mobilized Cd from Cd-loaded Fe(III) hydroxides followed by precipitation of Cd-bearing mineral phases. Using Mössbauer spectroscopy and scanning electron microscopy, the original and newly formed Cd-containing Fe(II) and Fe(III) mineral phases, including Cd-Fe-carbonates, Fe-phosphates and Fe-(oxyhydr)oxides, were identified and characterized. Using energy-dispersive X-ray spectroscopy and synchrotron-based scanning transmission X-ray microscopy, Cd was mapped in the Fe(II) mineral aggregates formed during microbial Fe(III) reduction. Microbial Fe(III) reduction mobilizes Cd prior to its precipitation in Cd-bearing mineral phases. The mobilized Cd could be taken up by phytoremediating plants, resulting in a net removal of Cd from contaminated sites. Alternatively, Cd precipitation could reduce Cd bioavailability in the environment, causing less toxic effects to crops and soil microbiota. However, the stability and thus bioavailability of these newly formed Fe-Cd mineral phases needs to be assessed thoroughly. Whether phytoremediation or immobilization of Cd in a mineral with reduced Cd bioavailability are feasible mechanisms to reduce toxic effects of Cd in the environment remains to be

  8. Application of UV-irradiated Fe(III)-nitrilotriacetic acid (UV-Fe(III)NTA) and UV-NTA-Fenton systems to degrade model and natural occurring naphthenic acids.

    Science.gov (United States)

    Zhang, Ying; Chelme-Ayala, Pamela; Klamerth, Nikolaus; Gamal El-Din, Mohamed

    2017-07-01

    Naphthenic acids (NAs) are a highly complex mixture of organic compounds naturally present in bitumen and identified as the primary toxic constituent of oil sands process-affected water (OSPW). This work investigated the degradation of cyclohexanoic acid (CHA), a model NA compound, and natural occurring NAs during the UV photolysis of Fe(III)-nitrilotriacetic acid (UV-Fe(III)NTA) and UV-NTA-Fenton processes. The results indicated that in the UV-Fe(III)NTA process at pH 8, the CHA removal increased with increasing NTA dose (0.18, 0.36 and 0.72 mM), while it was independent of the Fe(III) dose (0.09, 0.18 and 0.36 mM). Moreover, the three Fe concentrations had no influence on the photolysis of the Fe(III)NTA complex. The main responsible species for the CHA degradation was hydroxyl radical (OH), and the role of dissolved O 2 in the OH generation was found to be negligible. Real OSPW was treated with the UV-Fe(III)NTA and UV-NTA-Fenton advanced oxidation processes (AOPs). The removals of classical NAs (O 2 -NAs), oxidized NAs with one additional oxygen atom (O 3 -NAs) and with two additional oxygen atoms (O 4 -NAs) were 44.5%, 21.3%, and 25.2% in the UV-Fe(III)NTA process, respectively, and 98.4%, 86.0%, and 81.0% in the UV-NTA-Fenton process, respectively. There was no influence of O 2 on the NA removal in these two processes. The results also confirmed the high reactivity of the O 2 -NA species with more carbons and increasing number of rings or double bond equivalents. This work opens a new window for the possible treatment of OSPW at natural pH using these AOPs. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. New method for simultaneous determination of Fe(II) and Fe(III) in water using flow injection technique

    International Nuclear Information System (INIS)

    Kozak, J.; Gutowski, J.; Kozak, M.; Wieczorek, M.; Koscielniak, P.

    2010-01-01

    The method exploits the possibilities of flow injection gradient titration in a system of reversed flow with spectrophotometric detection. In the developed approach a small amount of titrant (EDTA) is injected into a stream of sample containing a mixture of indicators (sulfosalicylic acid and 1,10-phenanthroline). In acid environment sulfosalicylic acid forms a complex with Fe(III), whereas 1,10-phenanthroline forms a complex with Fe(II). Measurements are performed at wavelength λ = 530 nm when radiation is absorbed by both complexes. After injection EDTA replaces sulfosalicylic acid and forms with Fe(III) more stable colourless complex. As a result, a characteristic 'cut off' peak is registered with a width corresponding to the Fe(III) concentration and with a height corresponding to the Fe(II) concentration. Calibration was performed by titration of four two-component standard solutions of the Fe(II)/Fe(III) concentrations established in accordance with 2 2 factorial plan. The method was tested with the use of synthetic samples and then it was applied to the analysis of water samples taken from artesian wells. Under optimized experimental conditions Fe(II) and Fe(III) were determined with precision less than 0.8 and 2.5% (RSD) and accuracy less than 3.2 and 5.1% (relative error) within the concentration ranges of 0.1-3.0 and 0.9-3.5 mg L -1 of both analytes, respectively.

  10. Cr(VI) retention and transport through Fe(III)-coated natural zeolite

    Energy Technology Data Exchange (ETDEWEB)

    Du, Gaoxiang [School of Materials Science and Technology, China University of Geosciences, Beijing 100083 (China); Li, Zhaohui, E-mail: li@uwp.edu [School of Materials Science and Technology, China University of Geosciences, Beijing 100083 (China); Geosciences Department, University of Wisconsin-Parkside, Kenosha, WI 53144 (United States); Department of Earth Sciences, National Cheng Kung University, 1 University Road, Tainan 70101, Taiwan (China); Liao, Libing [School of Materials Science and Technology, China University of Geosciences, Beijing 100083 (China); Hanson, Renee; Leick, Samantha; Hoeppner, Nicole [Geosciences Department, University of Wisconsin-Parkside, Kenosha, WI 53144 (United States); Jiang, Wei-Teh [Department of Earth Sciences, National Cheng Kung University, 1 University Road, Tainan 70101, Taiwan (China)

    2012-06-30

    Graphical abstract: Breakthrough curves of Cr(VI) from columns packed with raw zeolite (a) and Fe(III)-zeolite (b). The solid line in (b) is the HYDRUS-1D fit to the observed data with adsorption term only, while the dashed line in (b) includes a reduction term in the HYDRUS-1D fit. Highlights: Black-Right-Pointing-Pointer Zeolite modified with Fe(III) could be used for adsorption and retention of Cr(VI). Black-Right-Pointing-Pointer The Fe present on zeolite was in an amorphous Fe(OH){sub 3} form. Black-Right-Pointing-Pointer A Cr(VI) adsorption capacity of 82 mg/kg was found on Fe(III)-zeolite. Black-Right-Pointing-Pointer A Cr(VI) retardation factor of 3 or 5 was determined from column and batch studies. - Abstract: Cr(VI) is a group A chemical based on the weight of evidence of carcinogenicity. Its transport and retention in soils and groundwater have been studied extensively. Zeolite is a major component in deposits originated from volcanic ash and tuff after alteration. In this study, zeolite aggregates with the particle size of 1.4-2.4 mm were preloaded with Fe(III). The influence of present Fe(III) on Cr(VI) retention by and transport through zeolite was studied under batch and column experiments. The added Fe(III) resulted in an enhanced Cr(VI) retention by the zeolite with a capacity of 82 mg/kg. The Cr(VI) adsorption on Fe(III)-zeolite followed a pseudo-second order kinetically and the Freundlich adsorption isotherm thermodynamically. Fitting the column experimental data to HYDRUS-1D resulted in a retardation factor of 3 in comparison to 5 calculated from batch tests at an initial Cr(VI) concentration of 3 mg/L. The results from this study showed that enhanced adsorption and retention of Cr(VI) may happen in soils derived from volcanic ash and tuff that contains significant amounts of zeolite with extensive Fe(III) coating.

  11. Microbial removal of Fe(III) impurities from clay using dissimilatory iron reducers.

    Science.gov (United States)

    Lee, E Y; Cho, K S; Ryu, H W; Chang, Y K

    1999-01-01

    Fe(III) impurities, which detract refractoriness and whiteness from porcelain and pottery, could be biologically removed from low-quality clay by indigenous dissimilatory Fe(III)-reducing microorganisms. Insoluble Fe(III) in clay particles was leached out as soluble Fe(II), and the Fe(III) reduction reaction was coupled to the oxidation of sugars such as glucose, maltose and sucrose. A maximum removal of 44-45% was obtained when the relative amount of sugar was 5% (w/w; sugar/clay). By the microbial treatment, the whiteness of the clay was increased from 63.20 to 79.64, whereas the redness was clearly decreased from 13.47 to 3.55.

  12. Thermometric studies on the Fe(III)-EDTA chelate.

    Science.gov (United States)

    Dot, K

    1978-02-01

    A DeltaH of -11.5 +/- 0.5 kJ/mole has been determined for the formation of the Fe(III)-EDTA chelate at 25.0 degrees and mu = 0.1(= [HClO(4)] + [NaClO(4)]) by a direct thermometric titration procedure. The entropy change, DeltaS, has been calculated to be 440 J.mole(-1) .deg(-1) by combining the result of the heat measurements with the free energy change obtained from the stability constant previously determined. A relationship between the DeltaS values and the standard partial molal entropies of the tervalent metal ions is discussed. In addition, conditions for the thermometric titration of Fe(III) with NA(4)EDTA at room temperature have been investigated. Iron(III) can be determined in the presence of fairly large amounts of phosphate, Cr(III), Mn(II) and Al(III).

  13. Structural Properties of the Cr(III)-Fe(III) (Oxy)Hydroxide Compositional Series: Insights for a Nanomaterial 'Solid Solution'

    International Nuclear Information System (INIS)

    Tang, Y.; Zhang, L.; Michel, F.M.; Harrington, R.; Parise, J.B.; Reeder, R.J.

    2010-01-01

    Chromium(III) (oxy)hydroxide and mixed Cr(III)-Fe(III) (oxy)hydroxides are environmentally important compounds for controlling chromium speciation and bioaccessibility in soils and aquatic systems and are also industrially important as precursors for materials and catalyst synthesis. However, direct characterization of the atomic arrangements of these materials is complicated because of their amorphous X-ray properties. This study involves synthesis of the complete Cr(III)-Fe(III) (oxy)hydroxide compositional series, and the use of complementary thermal, microscopic, spectroscopic, and scattering techniques for the evaluation of their structural properties. Thermal analysis results show that the Cr end member has a higher hydration state than the Fe end member, likely associated with the difference in water exchange rates in the first hydration spheres of Cr(III) and Fe(III). Three stages of weight loss are observed and are likely related to the loss of surface/structural water and hydroxyl groups. As compared to the Cr end member, the intermediate composition sample shows lower dehydration temperatures and a higher exothermic transition temperature. XANES analysis shows Cr(III) and Fe(III) to be the dominant oxidation states. XANES spectra also show progressive changes in the local structure around Cr and Fe atoms over the series. Pair distribution function (PDF) analysis of synchrotron X-ray total scattering data shows that the Fe end member is nanocrystalline ferrihydrite with an intermediate-range order and average coherent domain size of ∼27 (angstrom). The Cr end member, with a coherent domain size of ∼10 (angstrom), has only short-range order. The PDFs show progressive structural changes across the compositional series. High-resolution transmission electron microscopy (HRTEM) results also show the loss of structural order with increasing Cr content. These observations provide strong structural evidence of chemical substitution and progressive structural

  14. Microbial reduction of Fe(III) and turnover of acetate in Hawaiian soils.

    Science.gov (United States)

    Küsel, Kirsten; Wagner, Christine; Trinkwalter, Tanja; Gössner, Anita S; Bäumler, Rupert; Drake, Harold L

    2002-04-01

    Soils contain anoxic microzones, and acetate is an intermediate during the turnover of soil organic carbon. Due to negligible methanogenic activities in well-drained soils, acetate accumulates under experimentally imposed short-term anoxic conditions. In contrast to forest, agricultural, and prairie soils, grassland soils from Hawaii rapidly consumed rather than formed acetate when incubated under anoxic conditions. Thus, alternative electron acceptors that might be linked to the anaerobic oxidation of soil organic carbon in Hawaiian soils were assessed. Under anoxic conditions, high amounts of Fe(II) were formed by Hawaiian soils as soon as soils were depleted of nitrate. Rates of Fe(II) formation for different soils ranged from 0.01 to 0.31 micromol (g dry weight soil)(-1) h(-1), but were not positively correlated to increasing amounts of poorly crystallized iron oxides. In general, sulfate-reducing and methanogenic activities were negligible. Supplemental acetate was rapidly oxidized to CO2 via the sequential reduction of nitrate and Fe(III) in grassland soil (obtained near Kaena State Park). Supplemental H2 stimulated the formation of Fe(II), but H2-utilizing acetogens appeared to also be involved in the consumption of H2. Approximately 270 micromol Fe(III) (g dry weight soil)(-1) was available for Fe(III)-reducing bacteria, and acetate became a stable end product when Fe(III) was depleted in long-term incubations. Most-probable-number estimates of H2- and acetate-utilizing Fe(III) reducers and of H2-utilizing acetogens were similar. These results indicate that (i) the microbial reduction of Fe(III) is an important electron-accepting process for the anaerobic oxidation of organic matter in Fe(III)-rich Hawaiian soils of volcanic origin, and (ii) acetate, formed by the combined activity of fermentative and acetogenic bacteria, is an important trophic link in anoxic microsites of these soils.

  15. Protection of Nitrate-Reducing Fe(II)-Oxidizing Bacteria from UV Radiation by Biogenic Fe(III) Minerals

    Science.gov (United States)

    Gauger, Tina; Konhauser, Kurt; Kappler, Andreas

    2016-04-01

    Due to the lack of an ozone layer in the Archean, ultraviolet radiation (UVR) reached early Earth's surface almost unattenuated; as a consequence, a terrestrial biosphere in the form of biological soil crusts would have been highly susceptible to lethal doses of irradiation. However, a self-produced external screen in the form of nanoparticular Fe(III) minerals could have effectively protected those early microorganisms. In this study, we use viability studies by quantifying colony-forming units (CFUs), as well as Fe(II) oxidation and nitrate reduction rates, to show that encrustation in biogenic and abiogenic Fe(III) minerals can protect a common soil bacteria such as the nitrate-reducing Fe(II)-oxidizing microorganisms Acidovorax sp. strain BoFeN1 and strain 2AN from harmful UVC radiation. Analysis of DNA damage by quantifying cyclobutane pyrimidine dimers (CPD) confirmed the protecting effect by Fe(III) minerals. This study suggests that Fe(II)-oxidizing microorganisms, as would have grown in association with mafic and ultramafic soils/outcrops, would have been able to produce their own UV screen, enabling them to live in terrestrial habitats on early Earth.

  16. Moessbauer study of Fe(III)-reducing sugar complexes

    International Nuclear Information System (INIS)

    Wolowiec, S.; Drabent, K.

    1985-01-01

    Iron(III) complexes with glucose, galactose, mannose and lactose were prepared. The Moessbauer and magnetic susceptibility data demonstrate the polymeric structure of the complexes. The thermal behaviour of the Fe(III)-glucose complex was monitored by Moessbauer spectroscopy. (author)

  17. Study of Stoichiometry and Stability of some Fe(III)-Amino Acid Complexes

    International Nuclear Information System (INIS)

    Latif, S.; Shirin, K.; Nisar, S.; Zahida, T. M.

    2005-01-01

    The complexation of ferric with three amino acids (Glycine, Glutamic acid and Aspartic acid) was studied spectrophotometrically and potentiometrically at pH 5.0 and in aqueous medium. The stoichiometry was calculated spectrophotometrically using mole ratio method and is found to be ML3 for Fe (III)-Glycine and ML2 for Fe (III)-Glutamate for Fe (III)-Glutamate and Aspartate complex. The stabilities of these complexes were calculated spectrophotometrically and potentiometrically. The experimental results of potentiometric titrations were treated by well known computer program B EST . The values were further refined till least sigma fit i.e. 0.03. The complexes were not formed under normal conditions. Each complex was studied at more than one wavelength and no kmax was obtained because Fe (III) solution and the complexes absorb in similar wavelength region. The formation constants of all these complexes are not very high shows weak complexation of Fe (III) with these amino acids. (author)

  18. Limiting Factors for Microbial Fe(III)-Reduction In a Landfill Leachate Polluted Aquifer (Vejen, Denmark)

    DEFF Research Database (Denmark)

    Albrechtsen, Hans-Jørgen; Heron, Gorm; Christensen, Thomas Højlund

    1995-01-01

    Aquifer sediment samples from two locations within the anaerobic leachate plume of a municipal landfill were compared with respect to microbiology (especially Fe(III)-reduction) and geochemistry. The samples close to the landfill were characterized by low contents of Fe(III), whereas samples from...... the more distant cluster were rich in Fe(III)-oxides. The active microbial population seemed to be less dense in samples more distant from the landfill (measured by ATP and phospholipid fatty acids (PLFA)), but the microbial communities were very similar in the two sample clusters according...... to the composition of PLFA. Very little, if any, Fe(III)-reduction was observed close to the landfill, but all the more distant samples showed evident microbially mediated Fe(III)-reduction. After amendment with both acetate and Fe(III), all the samples showed a potential for Fe(III)-reduction, and the in situ Fe...

  19. Simultaneous Fe(III) reduction and ammonia oxidation process in Anammox sludge.

    Science.gov (United States)

    Li, Xiang; Huang, Yong; Liu, Heng-Wei; Wu, Chuan; Bi, Wei; Yuan, Yi; Liu, Xin

    2018-02-01

    In recent years, there have been a number of reports on the phenomenon in which ferric iron (Fe(III)) is reduced to ferrous iron [Fe(II)] in anaerobic environments, accompanied by simultaneous oxidation of ammonia to NO 2 - , NO 3 - , or N 2. However, studies on the relevant reaction characteristics and mechanisms are rare. Recently, in research on the effect of Fe(III) on the activity of Anammox sludge, excess ammonia oxidization has also been found. Hence, in the present study, Fe(III) was used to serve as the electron acceptor instead of NO 2 - , and the feasibility and characteristics of Anammox coupled to Fe(III) reduction (termed Feammox) were investigated. After 160days of cultivation, the conversion rate of ammonia in the reactor was above 80%, accompanied by the production of a large amount of NO 3 - and a small amount of NO 2 - . The total nitrogen removal rate was up to 71.8%. Furthermore, quantities of Fe(II) were detected in the sludge fluorescence in situ hybridization (FISH) and denaturated gradient gel electrophoresis (DGGE) analyses further revealed that in the sludge, some Anammox bacteria were retained, and some microbes were enriched during the acclimatization process. We thus deduced that in Anammox sludge, Fe(III) reduction takes place together with ammonia oxidation to NO 2 - and NO 3 - along with the Anammox process. Copyright © 2017. Published by Elsevier B.V.

  20. Cyanide-bridged Fe(III)-Mn(III) bimetallic complexes with dimeric and chain structures constructed from a newly made mer-Fe tricyanide: structures and magnetic properties.

    Science.gov (United States)

    Kim, Jae Il; Kwak, Hyun Young; Yoon, Jung Hee; Ryu, Dae Won; Yoo, In Young; Yang, Namgeun; Cho, Beong Ki; Park, Je-Geun; Lee, Hyosug; Hong, Chang Seop

    2009-04-06

    Four cyanide-linked Fe(III)-Mn(III) complexes were prepared by reacting Mn Schiff bases with a new molecular precursor (PPh(4))[Fe(qcq)(CN)(3)] [1; qcq = 8-(2-quinolinecarboxamido)quinoline anion]. They include a dimeric molecule, [Fe(qcq)(CN)(3)][Mn(3-MeOsalen)(H(2)O)] x 2 H(2)O [2 x 2 H(2)O; 3-MeOsalen = N,N'-ethylenebis(3-methoxysalicylideneiminato) dianion], and three 1D zigzag chains, [Fe(qcq)(CN)(3)][Mn(5-Clsalen)] x 3 H(2)O [3 x 2 MeOH; 5-Clsalen = N,N'-ethylenebis(5-chlorosalicylideneiminato) dianion], [Fe(qcq)(CN)(3)][Mn(5-Brsalen)] x 2 MeOH [4 x 2 MeOH; 5-Brsalen = N,N'-ethylenebis(5-bromosalicylideneiminato) dianion], and Fe(qcq)(CN)(3)][Mn(salen)].MeCN x H(2)O [5 x MeCN; salen = N,N'-ethylenebis(salicylideneiminato) dianion]. The complexes consist of extensive hydrogen bonding and pi-pi stacking interactions, generating multidimensional structures. Magnetic studies demonstrate that antiferromagnetic couplings are operative between Fe(III) and Mn(III) centers bridged by cyanide ligands. On the basis of an infinite chain model, magnetic coupling parameters of 2-5 range from -9.3 to -14.1 cm(-1). A long-range order is observed at 2.3 K for 3 and 2.2 K for 4, while compound 5 shows spin glass behavior possibly coupled with magnetic ordering.

  1. Electrochemical Studies of Interactions Between Fe(II/Fe(III and Amino Acids Using Ferrocene-Modified Carbon Paste Electrode

    Directory of Open Access Journals (Sweden)

    Vatrál Jaroslav

    2014-12-01

    Full Text Available The electrochemical behavior of an Fe(II/Fe(III redox couple in the presence of various selected amino acids has been studied using ferrocene-modified carbon paste electrode at pH = 7.4. Because of Fe(II/Fe(III solubility issues at physiological pH, ferrocene was used as a source of iron. Anodic oxidation of iron (pH = 7.2 occurred at 0.356 V and cathodic oxidation at 0.231 V, both vs Ag|AgCl. Treatment of the voltammetric data showed that it was a purely diffusion-controlled reaction with the involvement of one electron. After addition of amino acids, potential shifts and current changes can be observed on the voltammograms. Cyclic voltammetry experiments revealed the capability of amino acids to change the electrochemical behavior of the Fe(II/Fe(III redox couple.

  2. Estudio de reacciones de oxidación catalizadas por complejos biomiméticos de Fe (II), Fe (III) y Mn (III)

    OpenAIRE

    Clemente Tejeda, David

    2015-01-01

    [ES]Se ha desarrollado una metodología económicamente asequible y medioambientalmente sostenible para la oxidación catalítica de sustratos orgánicos con interés preparativo, utilizando para ello sistemas biomiméticos de Fe(II), Fe(III) y Mn(III). En primer lugar se ha llevado a cabo la síntesis de los complejos metálicos catalizadores, optimizando los procedimientos descritos en la bibliografía precedente. Asimismo se ha llevado a cabo un análisis exhaustivo de todas las variables implicadas ...

  3. Probing Fe (III)/Fe (II) redox potential in a clayey material

    International Nuclear Information System (INIS)

    Tournassat, Christophe; Chainet, Fabien; Betelu, Stephanie; Hadi, Jebril; Gaucher, Eric C.; Ignatiadis, Ioannis; Greneche, Jean-Marc; Charlet, Laurent

    2010-01-01

    Document available in extended abstract form only. Redox is one of the main factors affecting the migration of redox-sensitive radionuclides. As a consequence reducing conditions are considered of strategic importance for the confinement properties of a clayey formation towards nuclear waste. A representative redox potential of clay formation such as Callovian- Oxfordian (COx) can be derived from thermodynamic calculations considering equilibrium between observed redox phases such as pyrite and siderite. However, there is little information on the reactivity of the different reservoirs of redox constituents in this type of complex material. The present study aims at investigating the reactivity of the Fe(III)/Fe(II) redox couple in the structure of clay minerals using different investigation methods: electrochemistry and O 2 reduction kinetic experiments. Clay modified electrodes were specifically designed to probe Fe(III)/Fe(II) redox potential in the structure of clay minerals. The clay fraction of a Callovian-Oxfordian argillite sample originating from the same level than ANDRA underground research laboratory was used after pre-treatment to remove organic matter and accessory minerals such as pyrite that could influence redox potential measurements. These electrodes were used to verify the validity of the model of Favre et al. (2006) that links the redox potential (E clay ) to the the Fe(II)/Fe tot ratio in the structure (m rel ), the pH and the sodium concentration in solution: equation 1. The good agreement between direct potential measurements and model prediction provides a strong evidence of the relevance of this model in our experimental conditions although the clay composition and its too low Fe content do not a priori fulfil the conditions set by Drits and Manceau (2000) for the calculation of K 0 parameter. Following the verification of the model, we tried to apply it to the specific case of a Callovian-Oxfordian sample that had been very well preserved

  4. Molecular and electronic structure of thin films of protoporphyrin(IX)Fe(III)Cl

    Science.gov (United States)

    Snyder, Shelly R.; White, Henry S.

    1991-11-01

    Electrochemical, scanning tunneling microscopy (STM), and tunneling spectroscopy studies of the molecular and electronic properties of thin films of protoporphyrin(IX)Fe(III)Cl (abbreviated as PP(IX)Fe(III)Cl) on highly oriented pyrolytic graphite (HOPG) electrodes are reported. PP(IX)Fe(III)Cl films are prepared by two different methods: (1) adsorption, yielding an electrochemically-active film, and (2) irreversible electrooxidative polymerization, yielding an electrochemically-inactive film. STM images, in conjunction with electro-chemical results, indicate that adsorption of PP(IX)Fe(III)Cl from aqueous solutions onto freshly cleaved HOPG results in a film comprised of molecular aggregates. In contrast, films prepared by irreversible electrooxidative polymerization of PP(IX)Fe(III)Cl have a denser, highly structured morphology, including what appear to be small pinholes (approx. 50A diameter) in an otherwise continuous film.

  5. The [Fe(III)[Fe(III)(L1)2]3] star-type single-molecule magnet.

    Science.gov (United States)

    Saalfrank, Rolf W; Scheurer, Andreas; Bernt, Ingo; Heinemann, Frank W; Postnikov, Andrei V; Schünemann, Volker; Trautwein, Alfred X; Alam, Mohammad S; Rupp, Holger; Müller, Paul

    2006-06-21

    Star-shaped complex [Fe(III)[Fe(III)(L1)2]3] (3) was synthesized starting from N-methyldiethanolamine H2L1 (1) and ferric chloride in the presence of sodium hydride. For 3, two different high-spin iron(III) ion sites were confirmed by Mössbauer spectroscopy at 77 K. Single-crystal X-ray structure determination revealed that 3 crystallizes with four molecules of chloroform, but, with only three molecules of dichloromethane. The unit cell of 3.4CHCl3 contains the enantiomers (delta)-[(S,S)(R,R)(R,R)] and (lambda)-[(R,R)(S,S)(S,S)], whereas in case of 3.3CH2Cl2 four independent molecules, forming pairs of the enantiomers [lambda-(R,R)(R,R)(R,R)]-3 and [lambda-(S,S)(S,S)(S,S)]-3, were observed in the unit cell. According to SQUID measurements, the antiferromagnetic intramolecular coupling of the iron(III) ions in 3 results in a S = 10/2 ground state multiplet. The anisotropy is of the easy-axis type. EPR measurements enabled an accurate determination of the ligand-field splitting parameters. The ferric star 3 is a single-molecule magnet (SMM) and shows hysteretic magnetization characteristics below a blocking temperature of about 1.2 K. However, weak intermolecular couplings, mediated in a chainlike fashion via solvent molecules, have a strong influence on the magnetic properties. Scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) were used to determine the structural and electronic properties of star-type tetranuclear iron(III) complex 3. The molecules were deposited onto highly ordered pyrolytic graphite (HOPG). Small, regular molecule clusters, two-dimensional monolayers as well as separated single molecules were observed. In our STS measurements we found a rather large contrast at the expected locations of the metal centers of the molecules. This direct addressing of the metal centers was confirmed by DFT calculations.

  6. Studies of Binary Complexes of Tripodal Ligand cis,cis-1,3,5-tris(methylaminocyclohexane with Cr(III and Fe(III

    Directory of Open Access Journals (Sweden)

    S. Esakki Muthu

    2005-01-01

    Full Text Available The formation of binary complexes of Cr(III and Fe(III with a tripodal ligand cis,cis-1,3,5-tris(methylaminocyclohexane (tmach (L has been investigated in solution. The overall stability constants of tmach with Cr(III and Fe(III were determined by potentiometric method at an ionic strength of 0.1 M NaClO4 at 25±1°C in aqueous medium. The formation of species like MLH25+, MLH4+, ML3+, ML(OH2+ and ML(OH3 were observed. Fe(III was found to form more stable complexes than Cr(III. Molecular mechanics calculations were performed to explain the mode of coordination in solution.

  7. Microbial reduction of Fe(III) in the presence of oxygen under low pH conditions

    Energy Technology Data Exchange (ETDEWEB)

    Kusel, K.; Roth, U.; Drake, H.L. [University of Bayreuth, Bayreuth (Germany)

    2002-07-01

    In acidic, coal mining lake sediments, facultatively anaerobic Acidiphilium species are probably involved in the reduction of Fe(III). Previous results indicate that these bacteria can co-respire O{sub 2} and Fe(III). In this study, we investigated the capacity of the sediment microbiota to reduce Fe(III) in the presence of O{sub 2} at pH 3. In sediment microcosms with 4% O{sub 2} in the headspace, the concentration of Fe(II) increased at a rate of 1.03 {mu}mol (g wet sediment){sup -1} day{sup -1} within the first 7 days of incubation which was similar to the rate obtained with controls incubated under anoxic conditions. However, in microcosms incubated under air, Fe(II) was consumed after a lag phase of 8 h with a rate of 2.66 {mu}mol (g wet sediment){sup -1} day{sup -1}. Acidiphilium cryptum JF-5, isolated from this sediment, reduced soluble Fe(III) with either 4 or 21% O{sub 2} in the headspace, and concomitantly consumed O{sub 2}. However, the rate of Fe(II) formation normalized for cell density decreased under oxic conditions. Schwertmannite, the predominant Fe(III)-mineral of this sediment, was also reduced by A. cryptum JF-5 under oxic conditions. The rate of Fe(II) formation by A. cryptum JF-5 decreased after transfer from preincubation under air in medium lacking Fe(III). Acidiphilium cryptum JF-5 did not form Fe(II) when preincubated under air and transferred to anoxic medium containing Fe(III) and chloramphenicol, an inhibitor of protein synthesis. These results indicate that: (i) the reduction of Fe(III) can occur at low O{sub 2} concentrations in acidic sediments; (ii) Fe(II) can be oxidized at O{sub 2} concentrations near saturation; and (iii) the enzyme(s) responsible for the reduction of Fe(III) in A. cryptum JF-5 are not constitutive.

  8. 2-Hydro-4-n-But oxypropiophenone Oxime as a spectrophotometric reagent for Fe (III)

    International Nuclear Information System (INIS)

    Purohit, K.; Desai, K.K.

    2006-01-01

    2-Hydro-4-n-But oxypropiophenone Oxime [Hipbone] has been synthesized and used for the spectrophotometric determination of Fe (III). The reagent gives purple coloured complex with Fe (III) in 50% alcoholic medium in pH range of 2.5-4.5. Beer's law is obeyed up to 23.1 ppm of Fe (III). Molar absorptivity and sandell's sensitivity at 500 nm of complex were found to be 7.062x 10 power2 lit.mol.cm and 0.079 ug of Fe (III)/cm respectively. Composition and stability constant have been determined. The reagent is successfully used for determination of Fe (III) in dolomite and in pharmaceutical sample. It is also used for the indirect determination of fluoride in tap water sample. (author)

  9. Fine-structure excitation of Fe II and Fe III due to collisions with electrons

    Science.gov (United States)

    Wan, Yier; Qi, Yueying; Favreau, Connor; Loch, Stuart; Stancil, P.; Ballance, Connor; McLaughlin, Brendan

    2018-06-01

    Atomic data of iron peak elements are of great importance in astronomical observations. Among all the ionization stages of iron, Fe II and Fe III are of particular importance because of the high cosmic abundance, relatively low ionization potential and complex open d-shell atomic structure. Fe II and Fe III emission are observed from nearly all classes of astronomical objects over a wide spectral range from the infrared to the ultraviolet. To meaningfully interpret these spectra, astronomers have to employ highly complex modeling codes with reliable collision data to simulate the astrophysical observations. The major aim of this work is to provide reliable atomic data for diagnostics. We present new collision strengths and effective collisions for electron impact excitation of Fe II and Fe III for the forbidden transitions among the fine-structure levels of the ground terms. A very fine energy mesh is used for the collision strengths and the effective collision strengths are calculated over a wide range of electron temperatures of astrophysical importance (10-2000 K). The configuration interaction state wave functions are generated with a scaled Thomas-Fermi-Dirac-Amaldi (TFDA) potential, while the R-matrix plus intermediate coupling frame transformation (ICFT), Breit-Pauli R-matrix and Dirac R-matrix packages are used to obtain collision strengths. Influences of the different methods and configuration expansions on the collisional data are discussed. Comparison is made with earlier theoretical work and differences are found to occur at the low temperatures considered here.This work was funded by NASA grant NNX15AE47G.

  10. Development of a C3-symmetric benzohydroxamate tripod: Trimetallic complexation with Fe(III), Cr(III) and Al(III)

    Science.gov (United States)

    Baral, Minati; Gupta, Amit; Kanungo, B. K.

    2016-06-01

    The design, synthesis and physicochemical characterization of a C3-symmetry Benzene-1,3,5-tricarbonylhydroxamate tripod, noted here as BTHA, are described. The chelator was built from a benzene as an anchor, symmetrically extended by three hydroxamate as ligating moieties, each bearing O, O donor sites. A combination of absorption spectrophotometry, potentiometry and theoretical investigations are used to explore the complexation behavior of the ligand with some trivalent metal ions: Fe(III), Cr(III), and Al(III). Three protonation constants were calculated for the ligand in a pH range of 2-11 in a highly aqueous medium (9:1 H2O: DMSO). A high rigidity in the molecular structure restricts the formation of 1:1 (M/L) metal encapsulation but shows a high binding efficiency for a 3:1 metal ligand stoichiometry giving formation constant (in β unit) 28.73, 26.13 and 19.69 for [M3L]; Mdbnd Fe(III), Al(III) and Cr(III) respectively, and may be considered as an efficient Fe-carrier. The spectrophotometric study reveals of interesting electronic transitions occurred during the complexation. BTHA exhibits a peak at 238 nm in acidic pH and with the increase of pH, a new peak appeared at 270 nm. A substantial shifting in both of the peaks in presence of the metal ions implicates a s coordination between ligand and metal ions. Moreover, complexation of BTHA with iron shows three distinct colors, violet, reddish orange and yellow in different pH, enables the ligand to be considered for the use as colorimetric sensor.

  11. Characterisation and application of the Fe(II)/Fe(III) redox reaction in an ionic liquid analogue

    International Nuclear Information System (INIS)

    Lloyd, David; Vainikka, Tuomas; Ronkainen, Markus; Kontturi, Kyösti

    2013-01-01

    Highlights: • The Fe(II)/Fe(III) reaction is shown to be facile using a wall-jet electrode and RDE. • Deposition/stripping of iron has equally slow kinetics as in aqueous systems. • An IL based all-iron RFB is reported for the first time, energy efficiency is 37%. • An Zn–Fe complex is shown to form. In an RFB this gives an energy efficiency of 78%. • Problems resulting from the use of redox probes and urea-based DES are demonstrated. -- Abstract: In this paper we report the properties of the Fe(II)/Fe(III) reaction in a deep eutectic solvent based on choline chloride and ethylene glycol. This reaction is shown to be facile using a wall-jet electrode and rotating disc electrode. The deposition and stripping of iron exhibits equally slow kinetics as in aqueous systems. Using these two reactions an all-iron redox flow battery based on ionic liquids is reported for the first time. An energy efficiency of 37% is attained at a current density of 0.5 mA cm −2 . A Zn(II)–Fe(II) complex is shown to form when zinc is oxidized by Fe(III). When this complex is applied in a redox flow battery energy efficiencies of 78% are achieved at a current density of 0.5 mA cm −2

  12. Cyclic Voltammetric Study of Complexes of Fe (III) with Saponins Isolated from Cicer aritinum and Glycyrrhizin

    International Nuclear Information System (INIS)

    Khan, S.S.; Kazmi, S.A.; Anwar, H

    2013-01-01

    Cyclic voltammetric study was used to analyze three new saponins (isolated from the seeds of Cicer aritinum) along with a known saponin soyasaponin I and beta sitosterol glycoside isolated saponins as well as glycyrrhizin. These studies were carried out in aqueous medium at Glassy carbon (GCE) electrode vs. AgCl reference electrode. Results revealed that the voltammograms of Fe(III) with isolated saponins are irreversible while that of Fe(III)-glycyrrhizin complex is reversible. Even though precise Eo values of their Fe(III) complex could not be determined, it is clearly indicated that Fe(III) forms complexes with these saponins. The ability to form strong complexes with Fe(III) therefore reduces the availability of Fe(III) by saponins. (author)

  13. Dissolution of Fe(III)(hydr)oxides by an Aerobic Bacterium

    International Nuclear Information System (INIS)

    Maurice, P.

    2004-01-01

    This project investigated the effects of an aerobic Pseudomonas mendocina bacterium on the dissolution of Fe(III)(hydr)oxides. The research is important because metals and radionuclides that adsorb to Fe(III)(hydr)oxides could potentially be remobilized by dissolving bacteria. We showed that P. mendocina is capable of dissolving Fe-bearing minerals by a variety of mechanisms, including production of siderophores, pH changes, and formation of reductants. The production of siderophores by P. mendocina was quantified under a variety of growth conditions. Finally, we demonstrated that microbial siderophores may adsorb to and enhance dissolution of clay minerals

  14. THE INFLUENCES OF Fe(III ION and Fe(OH3 COLLOID ON THE PHOTODEGRADATION of p-CHLOROPHENOL CATALYZED BY TiO2

    Directory of Open Access Journals (Sweden)

    Endang Tri Wahyuni

    2010-06-01

    Full Text Available The influences of ionic Fe(III and colloidal Fe(OH3 on the effectiveness of p-chlorophenol photodegradation catalyzed by TiO2 has been studied. Photodegradation was carried out in a batch system by irradiating a suspension of TiO2, p-chlorophenol, and Fe(III as ionic or colloidal forms, using UV lamp for a period of time accompanied by magnetic stirring. Concentration of photodegraded p-chlorophenol was calculated by subtracting the initial concentration with that of undegraded p-chlorophenol. Concentration of undegraded p-chlorophenol was determined by gas chromatography. In this study, TiO2 mass and the photodegradation time were optimized. The influences of concentration of Fe(III solution, mass of Fe(OH3, and pH of the solution have also been systematically studied. The research results showed that the presence of Fe(III ions improved the effectiveness of photocatalytical degradation of p-chlorophenol, which was proportional to the concentrations of Fe(III ion. In contrast, the increasing mass of Fe(OH3 led to a decrease in the degree of p-chlorophenol photodegradation. Furthermore, it was observed that increasing pH of the solution resulted in a decrease in the photodegradation of p-chlorophenol. This phenomena may be due to the different species of TiO2 available at the surface of photocatalyst and of ionic Fe(III and colloidal Fe(OH3 in the solution resulted from the pH alteration. The highest photodegradation degree, ca. 80 % was obtained when 20 mg of TiO2 was applied in the photodegradation of 50 mL of 100 ppm p-chlorophenol solution in the presence of 100 ppm Fe3+ irradiated by UV-light for 25 hours.    Keywords: p-chlorophenol photodegradation, TiO2, Fe(III species

  15. COMPARATIVE STUDY OF DEGRADATION OF ISOPROTURON (3-(4-isopropylphenyl-1,1dimethylurea PHOTOINDUCED BY FE(III AND FE(III-PHOTOINDUCED SONOCHEMICAL IN AQUEOUS SOLUTION

    Directory of Open Access Journals (Sweden)

    S Azizi

    2014-05-01

    Full Text Available The degradation of isoproturon 3-(4-isopropylphenyl-1,1dimethylurea photoinduced by Fe(III in aqueous solution has been investigated. The rate of degradation depends on the concentration of Fe(OH2+, the most photoreactive species in terms of .OH radical formation. These .OH radicals are able to degrade isoproturon until total mineralisation. The formation  of  Fe(II in the irradiated solution was monitored. The sonophotochemical degradation of isoproturon has been found to be dependent on the intensity of sonication. The combination of ultrasound and photochemistry has been used to degrade an aqueous solution of Isoproturon (IP. The degradation of IP in aqueous solution was investigated under sonolysis at         500 kHz and in the presence of Fe(III, as well as under simultaneous sonolysis and photoinduced Fe(III. Coupling photolysis with ultrasound for degradation of IP has been developed. The photosonochemical decomposition rate constant is greater than the additive rate constants of the two processes. Degradation products were analysed by CG/MS performed in the electron-impact (EI mode, at 70 eV potential using full scan mode. Degradation photoproducts were identified and a mechanism of degradation is proposed for two processes.

  16. Molecular Underpinnings of Fe(III Oxide Reduction by Shewanella oneidensis MR-1

    Directory of Open Access Journals (Sweden)

    Liang eShi

    2012-02-01

    Full Text Available In the absence of O2 and other electron acceptors, the Gram-negative bacterium Shewanella oneidensis MR-1 can use ferric [Fe(III] (oxy(hydroxide minerals as the terminal electron acceptors for anaerobic respiration. At circumneutral pH and in the absence of strong complexing ligands, Fe(III oxides are relatively insoluble and thus are external to the bacterial cells. S. oneidensis MR-1 has evolved the machinery (i.e., metal-reducing or Mtr pathway for transferring electrons across the entire cell envelope to the surface of extracellular Fe(III oxides. The protein components identified to date for the Mtr pathway include CymA, MtrA, MtrB, MtrC and OmcA. CymA is an inner-membrane tetraheme c-type cytochrome (c-Cyt that is proposed to oxidize the quinol in the inner-membrane and transfers the released electrons to redox proteins in the periplasm. Although the periplasmic proteins receiving electrons from CymA during Fe(III oxidation have not been identified, they are believed to relay the electrons to MtrA. A decaheme c-Cyt, MtrA is thought to be embedded in the trans outer-membrane and porin-like protein MtrB. Together, MtrAB deliver the electrons across the outer-membrane to the MtrC and OmcA on the outmost bacterial surface. Functioning as terminal reductases, the outer membrane and decaheme c-Cyts MtrC and OmcA can bind the surface of Fe(III oxides and transfer electrons directly to these minerals. To increase their reaction rates, MtrC and OmcA can use the flavins secreted by S. oneidensis MR-1 cells as diffusible co-factors for reduction of Fe(III oxides. MtrC and OmcA can also serve as the terminal reductases for soluble forms of Fe(III. Although our understanding of the Mtr pathway is still far from complete, it is the best characterized microbial pathway used for extracellular electron exchange. Characterizations of the Mtr pathway have made significant contributions to the molecular understanding of microbial reduction of Fe(III oxides.

  17. Production of 67Ga citrate injection liquid with butylacetate extraction method

    International Nuclear Information System (INIS)

    Fang Yibing; Li Bo; Liu Peng; Pan Qiyuan; Liu Peihua; Wang Han; Feng Jingling

    1995-01-01

    The distribution ratios D for Ga(III) at trace concentration in the HCl-butylacetate extraction system are measured. It showed that the D in 6 mol/l HCl is 5 x 10 2 which is maximum in 3-8 mol/l HCl. The extraction rates E in 5.5-8 mol/l HCl at phase ratio of 1 are ≥98% and ≥96% respectively when the concentration of ZnCl 2 in the solution are 0 and ≤2 mol/l. A butylacetate extraction method for the production of 67 Ga citrate injection liquid from Zn target irradiated by proton beam is developed. The optimal acidity of extraction is 6 mol/l HCl. The concentration of ZnCl 2 is adjusted to ≤2.0 mol/l and the impurity of Fe(III) in solution is reduced to Fe(II) with 10% TiCl 3 before extraction. The 67 Ga in organic phase is then stripped with water. The radionuclidic purity of the product is 100% while the radiochemical purity >90%. The amounts of Zn, Ti, Fe, Cu, Cd and Pb in the injection are below or near 1 mg/l. The test of abnormal toxicity is negative. The quality of the injection meets the requirements of both the Chinese and the United States Pharmacopoeia. The chemical yield is (92 +- 2)% while the time of operation is <3 h

  18. On the structure and spin states of Fe(III)-EDDHA complexes.

    Science.gov (United States)

    Gómez-Gallego, Mar; Fernández, Israel; Pellico, Daniel; Gutiérrez, Angel; Sierra, Miguel A; Lucena, Juan J

    2006-07-10

    DFT methods are suitable for predicting both the geometries and spin states of EDDHA-Fe(III) complexes. Thus, extensive DFT computational studies have shown that the racemic-Fe(III) EDDHA complex is more stable than the meso isomer, regardless of the spin state of the central iron atom. A comparison of the energy values obtained for the complexes under study has also shown that high-spin (S = 5/2) complexes are more stable than low-spin (S = 1/2) ones. These computational results matched the experimental results of the magnetic susceptibility values of both isomers. In both cases, their behavior has been fitted as being due to isolated high-spin Fe(III) in a distorted octahedral environment. The study of the correlation diagram also confirms the high-spin iron in complex 2b. The geometry optimization of these complexes performed with the standard 3-21G* basis set for hydrogen, carbon, oxygen, and nitrogen and the Hay-Wadt small-core effective core potential (ECP) including a double-xi valence basis set for iron, followed by single-point energy refinement with the 6-31G* basis set, is suitable for predicting both the geometries and the spin-states of EDDHA-Fe(III) complexes. The presence of a high-spin iron in Fe(III)-EDDHA complexes could be the key to understanding their lack of reactivity in electron-transfer processes, either chemically or electrochemically induced, and their resistance to photodegradation.

  19. Environmentally-relevant concentrations of Al(III) and Fe(III) cations induce aggregation of free DNA by complexation with phosphate group.

    Science.gov (United States)

    Qin, Chao; Kang, Fuxing; Zhang, Wei; Shou, Weijun; Hu, Xiaojie; Gao, Yanzheng

    2017-10-15

    Environmental persistence of free DNA is influenced by its complexation with other chemical species and its aggregation mechanisms. However, it is not well-known how naturally-abundant metal ions, e.g., Al(III) and Fe(III), influence DNA aggregation. This study investigated aggregation behaviors of model DNA from salmon testes as influenced by metal cations, and elucidated the predominant mechanism responsible for DNA aggregation. Compared to monovalent (K + and Na + ) and divalent (Ca 2+ and Mg 2+ ) cations, Al(III) and Fe(III) species in aqueous solution caused rapid DNA aggregations. The maximal DNA aggregation occurred at 0.05 mmol/L Al(III) or 0.075 mmol/L Fe(III), respectively. A combination of atomic force microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy revealed that Al(III) and Fe(III) complexed with negatively charged phosphate groups to neutralize DNA charges, resulting in decreased electrostatic repulsion and subsequent DNA aggregation. Zeta potential measurements and molecular computation further support this mechanism. Furthermore, DNA aggregation was enhanced at higher temperature and near neutral pH. Therefore, DNA aggregation is collectively determined by many environmental factors such as ion species, temperature, and solution pH. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Structure and spectroscopic study of aqueous Fe(III)-As(V) complexes using UV-Vis, XAS and DFT-TDDFT.

    Science.gov (United States)

    Chai, Liyuan; Yang, Jinqin; Zhang, Ning; Wu, Pin-Jiun; Li, Qingzhu; Wang, Qingwei; Liu, Hui; Yi, Haibo

    2017-09-01

    Aqueous complexes between ferric (Fe(III)) and arsenate (As(V)) are indispensable for understanding the mobility of arsenic (As) in Fe(III)-As(V)-rich systems. In this study, aqueous Fe(III)-As(V) complexes, FeH 2 AsO 4 2+ and FeHAsO 4 + , were postulated based on the qualitative analysis of UV-Vis spectra in both Fe(III)-As(V)-HClO 4 and Fe(III)-As(V)-H 2 SO 4 systems. Subsequently, monodentate structures were evidenced by Fe K-edge EXAFS and modeled as [FeH 2 AsO 4 (H 2 O) 5 ] 2+ and [FeHAsO 4 (H 2 O) 5 ] + by DFT. The feature band at ∼280 nm was verified as electron excitation chiefly from Fe-As-bridged O atoms to d-orbital of Fe in [FeH 2 AsO 4 (H 2 O) 5 ] 2+ and [FeHAsO 4 (H 2 O) 5 ] + . The structural and spectral information of Fe(III)-As(V) complexes will enable future speciation analysis in Fe(III)-As(V)-rich system. Copyright © 2017. Published by Elsevier Ltd.

  1. Growth of Thermophilic and Hyperthermophilic Fe(III)-Reducing Microorganisms on a Ferruginous Smectite as the Sole Electron Acceptor▿

    Science.gov (United States)

    Kashefi, Kazem; Shelobolina, Evgenya S.; Elliott, W. Crawford; Lovley, Derek R.

    2008-01-01

    Recent studies have suggested that the structural Fe(III) within phyllosilicate minerals, including smectite and illite, is an important electron acceptor for Fe(III)-reducing microorganisms in sedimentary environments at moderate temperatures. The reduction of structural Fe(III) by thermophiles, however, has not previously been described. A wide range of thermophilic and hyperthermophilic Archaea and Bacteria from marine and freshwater environments that are known to reduce poorly crystalline Fe(III) oxides were tested for their ability to reduce structural (octahedrally coordinated) Fe(III) in smectite (SWa-1) as the sole electron acceptor. Two out of the 10 organisms tested, Geoglobus ahangari and Geothermobacterium ferrireducens, were not able to conserve energy to support growth by reduction of Fe(III) in SWa-1 despite the fact that both organisms were originally isolated with solid-phase Fe(III) as the electron acceptor. The other organisms tested were able to grow on SWa-1 and reduced 6.3 to 15.1% of the Fe(III). This is 20 to 50% less than the reported amounts of Fe(III) reduced in the same smectite (SWa-1) by mesophilic Fe(III) reducers. Two organisms, Geothermobacter ehrlichii and archaeal strain 140, produced copious amounts of an exopolysaccharide material, which may have played an active role in the dissolution of the structural iron in SWa-1 smectite. The reduction of structural Fe(III) in SWa-1 by archaeal strain 140 was studied in detail. Microbial Fe(III) reduction was accompanied by an increase in interlayer and octahedral charges and some incorporation of potassium and magnesium into the smectite structure. However, these changes in the major element chemistry of SWa-1 smectite did not result in the formation of an illite-like structure, as reported for a mesophilic Fe(III) reducer. These results suggest that thermophilic Fe(III)-reducing organisms differ in their ability to reduce and solubilize structural Fe(III) in SWa-1 smectite and that SWa-1

  2. [Fe(III)(dmbpy)(CN)4]-: a new building block for designing single-chain magnets.

    Science.gov (United States)

    Toma, Luminita Marilena; Pasán, Jorge; Ruiz-Pérez, Catalina; Lloret, Francesc; Julve, Miguel

    2012-11-28

    We herein present the synthesis and magneto-structural study of a new family of heterobimetallic chains of general formula {[Fe(III)(dmbpy)(CN)(4)](2)M(II)(H(2)O)(2)}(n)·pnH(2)O [dmbpy = 4,4'-dimethyl-2,2'-bipyridine; M = Mn (2), Cu (3), Ni (4) and Co (5) with p = 4 (2), 3 (3), 9 (4) and 3.5 (5)] which were prepared by using the mononuclear PPh(4)[Fe(III)(dmbpy)(CN)(4)]·3H(2)O (1) building block (PPh(4)(+) = tetraphenylphosphonium) as a ligand toward fully solvated M(II) ions. The structure of 1 consists of discrete [Fe(III)(dmbpy)(CN)(4)](-) anions, tetraphenylphosphonium cations and noncoordinated water molecules. Complexes 2-5 are isostructural compounds whose structure consists of neutral 4,2-wave like heterobimetallic chains of formula {[Fe(III)(dmbpy)(CN)(4)](2)M(II)(H(2)O)(2)}(n) where the [Fe(III)(dmbpy)(CN)(4)](-) entity adopts a bis-monodentate coordination mode toward trans-[M(II)(H(2)O)(2)] units through two of its four cyanide groups in cis positions. 1 exhibits the magnetic behaviour of magnetically isolated six-coordinate low-spin Fe(III) complexes with an important orbital contribution. 2 behaves as ferrimagnetic Fe(III)(2)Mn(II) chains, whereas 3-5 exhibit intrachain ferromagnetic couplings between the low-spin Fe(III) and either Cu(II) (3), Ni (4) or Co(II) (5) as well as frequency-dependence of the out-of-phase ac susceptibility signals below 3.0 (3), 5.5 (4) and 5.0 K (5). The relaxation time and the energy to reverse the magnetization of 3-5 are related to the anisotropy of the M(II) center and to the intra- and interchain magnetic interactions. Unprecedentedly in the world of cyanide-bearing complexes, 5 exhibits a double slow relaxation of the magnetization.

  3. Flow injection spectrophotometric determination of Fe(III) and V(v)

    International Nuclear Information System (INIS)

    Elrahman, Azza Mohamed

    2000-01-01

    Phenylflourone was synthesized with the objective of developing a method for determining Fe(III) and V(V) in the pressence of micelles using flow injectoin technique. Phenylflourone showed a wavelength of maximum absorption at 412 nm which was not affected by the presence of miccelles i.e. n-hexadodecylpyridinum bromide and sodium n-dodecylsulphate, but they have different effects on the absorbance of PHF. The example of PHF-Fe(III) and PHF-V(V) showed the wavelength of the maximum absorption at 4428 nm and 412 nm, respectively. Presence of micelles shifted the wavelength of the two complexes to a lower one. Generally the addition of micelles increased the absorbance of phenylflourone metal ions complexes except for PHF-V(V) with hexadodecylpyridinum bromide. With flow injection technique two approaches were practiced the use of micelle as a carrier or water as a carrier. Sodium n-dodecylsulphate increased the absorbance of the two complexes when it was used as a carrier or added to the metal ions using water as carrier. On the other hand, the use of n-hexadodecylpyridinum bromide as carrieer increased the absorbance of the complexes but it decreased the absorbance when it was used in conjunction with metal ions and water as a carrier. After establishing the optimum FI conditions for PHF-Fe(III) and PHF-V(V) complexes, the calibration curves were construction and produced semiliner response in the concentration range studied. Ti(IV) III, Mo(VI) showed a positive interference in PHF-Fe(III) and PHF-V(V) complexes, respectively.(Author)

  4. Estudo polarográfico sobre a determinação de Fe(III utilizando-se a técnica da polarografia de pulso diferencial Polarographic study about the determination of Fe(III using the technique of differencial pulse polarography

    Directory of Open Access Journals (Sweden)

    Luiz Manoel Aleixo

    2001-12-01

    Full Text Available A differential pulse polarographic study with the objective to determine iron (III in presense of copper (II in a supporting electrolyte based on citrate - EDTA was made. The best experimental conditions found were a supporting electrolyte of citrate 0.25 mol L-1, EDTA 0.050 mol L-1 and KNO3 0.50 mol L-1, pH 5.00. In this media iron (III showed a polarographic peak in -0.08 V and the copper (II in -0.34 V, both vs. Ag/AgCl (saturated KCl. Thus, a analytical method was developed and applied to determine iron (III in brass alloy, a matrix were copper is in large excess over iron. The results obtained showed no interference of copper in the iron determination. The value of 0.21% of iron in the sample alloy composition was obtained and the method was validated by atomic absortion and recovery test, and the results exhibited a good agreement with the proposed method.

  5. Ferrous Iron Oxidation under Varying pO2 Levels: The Effect of Fe(III)/Al(III) Oxide Minerals and Organic Matter.

    Science.gov (United States)

    Chen, Chunmei; Thompson, Aaron

    2018-01-16

    Abiotic Fe(II) oxidation by O 2 commonly occurs in the presence of mineral sorbents and organic matter (OM) in soils and sediments; however, this tertiary system has rarely been studied. Therefore, we examined the impacts of mineral surfaces (goethite and γ-Al 2 O 3 ) and organic matter [Suwannee River fulvic acid (SRFA)] on Fe(II) oxidation rates and the resulting Fe(III) (oxyhydr)oxides under 21 and 1% pO 2 at pH 6. We tracked Fe dynamics by adding 57 Fe(II) to 56 Fe-labeled goethite and γ-Al 2 O 3 and characterized the resulting solids using 57 Fe Mössbauer spectroscopy. We found Fe(II) oxidation was slower at low pO 2 and resulted in higher-crystallinity Fe(III) phases. Relative to oxidation of Fe(II) (aq) alone, both goethite and γ-Al 2 O 3 surfaces increased Fe(II) oxidation rates regardless of pO 2 levels, with goethite being the stronger catalyst. Goethite surfaces promoted the formation of crystalline goethite, while γ-Al 2 O 3 favored nano/small particle or disordered goethite and some lepidocrocite; oxidation of Fe(II) aq alone favored lepidocrocite. SRFA reduced oxidation rates in all treatments except the mineral-free systems at 21% pO 2 , and SRFA decreased Fe(III) phase crystallinity, facilitating low-crystalline ferrihydrite in the absence of mineral sorbents, low-crystalline lepidocrocite in the presence of γ-Al 2 O 3 , but either crystalline goethite or ferrihydrite when goethite was present. This work highlights that the oxidation rate, the types of mineral surfaces, and OM control Fe(III) precipitate composition.

  6. Dissolution of Fe(III) (hydr) oxides by metal-EDTA complexes

    Science.gov (United States)

    Ngwack, Bernd; Sigg, Laura

    1997-03-01

    The dissolution of Fe(III)(hydr)oxides (goethite and hydrous ferric oxide) by metal-EDTA complexes occurs by ligand-promoted dissolution. The process is initiated by the adsorption of metal-EDTA complexes to the surface and is followed by the dissociation of the complex at the surface and the release of Fe(III)EDTA into solution. The dissolution rate is decreased to a great extent if EDTA is complexed by metals in comparison to the uncomplexed EDTA. The rate decreases in the order EDTA CaEDTA ≫ PbEDTA > ZnEDTA > CuEDTA > Co(II)EDTA > NiEDTA. Two different rate-limiting steps determine the dissolution process: (1) detachment of Fe(III) from the oxide-structure and (2) dissociation of the metal-EDTA complexes. In the case of goethite, step 1 is slower than step 2 and the dissolution rates by various metals are similar. In the case of hydrous ferric oxide, step 2 is rate-limiting and the effect of the complexed metal is very pronounced.

  7. Reductive reactivity of iron(III) oxides in the east china sea sediments: characterization by selective extraction and kinetic dissolution.

    Science.gov (United States)

    Chen, Liang-Jin; Zhu, Mao-Xu; Yang, Gui-Peng; Huang, Xiang-Li

    2013-01-01

    Reactive Fe(III) oxides in gravity-core sediments collected from the East China Sea inner shelf were quantified by using three selective extractions (acidic hydroxylamine, acidic oxalate, bicarbonate-citrate buffered sodium dithionite). Also the reactivity of Fe(III) oxides in the sediments was characterized by kinetic dissolution using ascorbic acid as reductant at pH 3.0 and 7.5 in combination with the reactive continuum model. Three parameters derived from the kinetic method: m 0 (theoretical initial amount of ascorbate-reducible Fe(III) oxides), k' (rate constant) and γ (heterogeneity of reactivity), enable a quantitative characterization of Fe(III) oxide reactivity in a standardized way. Amorphous Fe(III) oxides quantified by acidic hydroxylamine extraction were quickly consumed in the uppermost layer during early diagenesis but were not depleted over the upper 100 cm depth. The total amounts of amorphous and poorly crystalline Fe(III) oxides are highly available for efficient buffering of dissolved sulfide. As indicated by the m 0, k' and γ, the surface sediments always have the maximum content, reactivity and heterogeneity of reactive Fe(III) oxides, while the three parameters simultaneously downcore decrease, much more quickly in the upper layer than at depth. Albeit being within a small range (within one order of magnitude) of the initial rates among sediments at different depths, incongruent dissolution could result in huge discrepancies of the later dissolution rates due to differentiating heterogeneity, which cannot be revealed by selective extraction. A strong linear correlation of the m 0 at pH 3.0 with the dithionite-extractable Fe(III) suggests that the m 0 may represent Fe(III) oxide assemblages spanning amorphous and crystalline Fe(III) oxides. Maximum microbially available Fe(III) predicted by the m 0 at pH 7.5 may include both amorphous and a fraction of other less reactive Fe(III) phases.

  8. Treatment of As(V) and As(III) by electrocoagulation using Al and Fe electrode.

    Science.gov (United States)

    Kuan, W H; Hu, C Y; Chiang, M C

    2009-01-01

    A batch electrocoagulation (EC) process with bipolar electrode and potentiodynamic polarization tests with monopolar systems were investigated as methods to explore the effects of electrode materials and initial solution pH on the As(V) and As(III) removal. The results displayed that the system with Al electrode has higher reaction rate during the initial period from 0 to 25 minutes than that of Fe electrode for alkaline condition. The pH increased with the EC time because the As(V) and As(III) removal by either co-precipitation or adsorption resulted in that the OH positions in Al-hydroxide or Fe-hydroxide were substituted by As(V) and As(III). The pH in Fe electrode system elevate higher than that in Al electrode because the As(V) removal substitutes more OH position in Fe-hydroxide than that in Al-hydroxide. EC system with Fe electrode can successfully remove the As(III) but system with Al electrode cannot because As(III) can strongly bind to the surface of Fe-hydroxide with forming inner-sphere species but weakly adsorb to the Al-hydroxide surface with forming outer-sphere species. The acidic solution can destroy the deposited hydroxide passive film then allow the metallic ions liberate into the solution, therefore, the acidic initial solution can enhance the As(V) and As(III) removal. The over potential calculation and potentiodynamic polarization tests reveal that the Fe electrode systems possess higher over potential and pitting potential than that of Al electrode system due to the fast hydrolysis of and the occurrence of Fe-hydroxide passive film.

  9. Electrochemistry of carbonaceous materials; 1. Oxidation of Sardinian coal by Fe(III) ions

    Energy Technology Data Exchange (ETDEWEB)

    Tomat, R.; Salmaso, R.; Zecchin, S. (CNR-Instituto di Polarografia ed Elettrochimica Preparativa, Padova (Italy))

    1992-04-01

    Oxidation of subbitiminous coal (Sulcis basin, Sardinia, Italy) by Fe(III) ions in aqueous H{sub 2}SO{sub 4} solution was investigated over a wide temperature range (20-80{degree}C). Experimental results are in accord with a reaction scheme involving a reversible complex between coal particles and Fe(III) ions as a first step in the oxidation process. At low coal concentration, the reaction rate follows first-order kinetics in both coal and ferric ions (overall second order), while at sufficiently high coal concentration, the reaction rate is consistent with first-order kinetics in Fe(III) concentration, appearing to be independent of coal concentration. The kinetic results obtained give preliminary information on the advantageous use of the Fe(III)/slurried coal reaction system to depolarize the anodic compartment of an electrolysis cell, for the production of H{sub 2}. 11 refs., 5 figs.

  10. Oxidation of Cr(III)-Fe(III) Mixed-phase Hydroxides by Chlorine: Implications on the Control of Hexavalent Chromium in Drinking Water.

    Science.gov (United States)

    Chebeir, Michelle; Liu, Haizhou

    2018-05-17

    The occurrence of chromium (Cr) as an inorganic contaminant in drinking water is widely reported. One source of Cr is its accumulation in iron-containing corrosion scales of drinking water distribution systems as Cr(III)-Fe(III) hydroxide, i.e., FexCr(1-x)(OH)3(s), where x represents the Fe(III) molar content and typically varies between 0.25 and 0.75. This study investigated the kinetics of inadvertent hexavalent chromium Cr(VI) formation via the oxidation of FexCr(1-x)(OH)3(s) by chlorine as a residual disinfectant in drinking water, and examined the impacts of Fe(III) content and drinking water chemical parameters including pH, bromide and bicarbonate on the rate of Cr(VI) formation. Data showed that an increase in Fe(III) molar content resulted in a significant decrease in the stoichiometric Cr(VI) yield and the rate of Cr(VI) formation, mainly due to chlorine decay induced by Fe(III) surface sites. An increase in bicarbonate enhanced the rate of Cr(VI) formation, likely due to the formation of Fe(III)-carbonato surface complexes that slowed down the scavenging reaction with chlorine. The presence of bromide significantly accelerated the oxidation of FexCr(1-x)(OH)3(s) by chlorine, resulting from the catalytic effect of bromide acting as an electron shuttle. A higher solution pH between 6 and 8.5 slowed down the oxidation of Cr(III) by chlorine. These findings suggested that the oxidative conversion of chromium-containing iron corrosion products in drinking water distribution systems can lead to the occurrence of Cr(VI) at the tap, and the abundance of iron, and a careful control of pH, bicarbonate and bromide levels can assist the control of Cr(VI) formation.

  11. Enrichment of Geobacter species in response to stimulation of Fe(III) reduction in sandy aquifer sediments

    Science.gov (United States)

    Snoeyenbos-West, O.L.; Nevin, K.P.; Anderson, R.T.; Lovely, D.R.

    2000-01-01

    Engineered stimulation of Fe(III) has been proposed as a strategy to enhance the immobilization of radioactive and toxic metals in metal-contaminated subsurface environments. Therefore, laboratory and field studies were conducted to determine which microbial populations would respond to stimulation of Fe(III) reduction in the sediments of sandy aquifers. In laboratory studies, the addition of either various organic electron donors or electron shuttle compounds stimulated Fe(III) reduction and resulted in Geobacter sequences becoming important constituents of the Bacterial 16S rDNA sequences that could be detected with PCR amplification and denaturing gradient gel electrophoresis (DGGE). Quantification of Geobacteraceae sequences with a PCR most-probable-number technique indicated that the extent to which numbers of Geobacter increased was related to the degree of stimulation of Fe(III) reduction. Geothrix species were also enriched in some instances, but were orders of magnitude less numerous than Geobacter species. Shewanella species were not detected, even when organic compounds known to be electron donors for Shewanella species were used to stimulate Fe(III) reduction in the sediments. Geobacter species were also enriched in two field experiments in which Fe(III) reduction was stimulated with the addition of benzoate or aromatic hydrocarbons. The apparent growth of Geobacter species concurrent with increased Fe(III) reduction suggests that Geobacter species were responsible for much of the Fe(III) reduction in all of the stimulation approaches evaluated in three geographically distinct aquifers. Therefore, strategies for subsurface remediation that involve enhancing the activity of indigenous Fe(III)-reducing populations in aquifers should consider the physiological properties of Geobacter species in their treatment design.

  12. Fate of Cd during microbial Fe(III) mineral reduction by a novel and Cd-tolerant Geobacter species.

    Science.gov (United States)

    Muehe, E Marie; Obst, Martin; Hitchcock, Adam; Tyliszczak, Tolek; Behrens, Sebastian; Schröder, Christian; Byrne, James M; Michel, F Marc; Krämer, Ute; Kappler, Andreas

    2013-12-17

    Fe(III) (oxyhydr)oxides affect the mobility of contaminants in the environment by providing reactive surfaces for sorption. This includes the toxic metal cadmium (Cd), which prevails in agricultural soils and is taken up by crops. Fe(III)-reducing bacteria can mobilize such contaminants by Fe(III) mineral dissolution or immobilize them by sorption to or coprecipitation with secondary Fe minerals. To date, not much is known about the fate of Fe(III) mineral-associated Cd during microbial Fe(III) reduction. Here, we describe the isolation of a new Geobacter sp. strain Cd1 from a Cd-contaminated field site, where the strain accounts for 10(4) cells g(-1) dry soil. Strain Cd1 reduces the poorly crystalline Fe(III) oxyhydroxide ferrihydrite in the presence of at least up to 112 mg Cd L(-1). During initial microbial reduction of Cd-loaded ferrihydrite, sorbed Cd was mobilized. However, during continuous microbial Fe(III) reduction, Cd was immobilized by sorption to and/or coprecipitation within newly formed secondary minerals that contained Ca, Fe, and carbonate, implying the formation of an otavite-siderite-calcite (CdCO3-FeCO3-CaCO3) mixed mineral phase. Our data shows that microbially mediated turnover of Fe minerals affects the mobility of Cd in soils, potentially altering the dynamics of Cd uptake into food or phyto-remediating plants.

  13. Computed oscillator strengths and energy levels for Fe III, Fe IV, Fe V, and Fe VI with calculated wavelengths and wavelengths derived from established data

    International Nuclear Information System (INIS)

    Fawcett, B.C.

    1989-01-01

    Calculated weighted oscillator strengths are tabulated for spectral lines of Fe III, Fe IV, Fe V, and Fe VI. The lines belong to transition arrays 3d 6 -3d 5 4p and 3d 5 4s-3d 5 4p in Fe III, 3d 5 -3d 4 4p and 3d 4 4s-3d 4 4p in Fe IV, 3d 4 -3d 3 4p and 3d 3 4s-3d 3 4p in Fe V, and 3d 3 -3d 2 4p and 3d 2 4s-3d 2 4p in Fe VI. For the calculations, Slater parameters are optimized on the basis of minimizing the discrepancies between observed and computed wavelengths. Configuration interaction was included among the 3d n , 3d n-1 4s, 3d n-2 4s 2 , 3d n-1 4d, and 3d n-1 5s even configurations and among the 3d n-1 4p, 3d n-2 4s4p, and 3d n-1 5p odd configurations, with 3p 5 3d n+1 added for Fe VI. Calculated wavelengths are compared with observational data, and the compositions of energy levels are listed. This completes a series of similar computations for these complex configurations covering Fe I to Fe VI

  14. Bioavailability of Fe(III) in Natural Soils and the Impact on Mobility of Inorganic Contaminants (Final Report)

    Energy Technology Data Exchange (ETDEWEB)

    Kosson, David S. [Vanderbilt Univ., Nashville, TN (United States). Dept. of Civil and Environmental Engineering; Cowan, Robert M. [Rutgers Univ., New Brunswick, NJ (United States). Dept. of Environmental Science; Young, Lily Y. [Rutgers Univ., New Brunswick, NJ (United States). Center for Agriculture and the Environment; Hatcherl, Eric L. [Vanderbilt Univ., Nashville, TN (United States). Dept. of Civil and Environmental Engineering; Scala, David J. [Vanderbilt Univ., Nashville, TN (United States). Dept. of Civil and Environmental Engineering

    2005-08-02

    Inorganic contaminants, such as heavy metals and radionuclides, can adhere to insoluble Fe(III) minerals resulting in decreased mobility of these contaminants through subsurface environments. Dissimilatory Fe(III)-reducing bacteria (DIRB), by reducing insoluble Fe(III) to soluble Fe(II), may enhance contaminant mobility. The Savannah River Site, South Carolina (SRS), has been subjected to both heavy metal and radionuclide contamination. The overall objective of this project is to investigate the release of inorganic contaminants such as heavy metals and radionuclides that are bound to solid phase soil Fe complexes and to elucidate the mechanisms for mobilization of these contaminants that can be associated with microbial Fe(III) reduction. This is being accomplished by (i) using uncontaminated and contaminated soils from SRS as prototype systems, (ii) evaluating the diversity of DIRBs within the samples and isolating cultures for further study, (iii) using batch microcosms to evaluate the bioavailability of Fe(III) from pure minerals and SRS soils, (iv) developing kinetic and mass transfer models that reflect the system dynamics, and (v) carrying out soil column studies to elucidate the dynamics and interactions amongst Fe(III) reduction, remineralization and contaminant mobility.

  15. Thiophene-based rhodamine as selectivef luorescence probe for Fe(III) and Al(III) in living cells.

    Science.gov (United States)

    Wang, Kun-Peng; Chen, Ju-Peng; Zhang, Si-Jie; Lei, Yang; Zhong, Hua; Chen, Shaojin; Zhou, Xin-Hong; Hu, Zhi-Qiang

    2017-09-01

    The thiophene-modified rhodamine 6G (GYJ) has been synthesized as a novel chemosensor. The sensor has sufficiently high selectivity and sensitivity for the detection of Fe 3+ and Al 3+ ions (M 3+ ) by fluorescence and ultraviolet spectroscopy with a strong ability for anti-interference performance. The binding ratio of M 3+ -GYJ complex was determined to be 2:1 according to the Job's plot. The binding constants for Fe 3+ and Al 3+ were calculated to be 3.91 × 10 8 and 5.26 × 10 8  M -2 , respectively. All these unique features made it particularly favorable for cellular imaging applications. The obvious fluorescence microscopy experiments demonstrated that the probes could contribute to the detection of Fe 3+ and Al 3+ in related cells and biological organs with satisfying resolution. Graphical abstract GYJ has high selectivity and sensitivity for the detection of Fe(III) and Al(III) with the binding ratio of 2:1.

  16. Fe (III) complex of mefloquine hydrochloride: Synthesis ...

    African Journals Online (AJOL)

    As part of the ongoing research for more effective antimalarial drug, Fe (III) complex of mefloquine hydrochloride (antimalarial drug) was synthesized using template method. Mefloquine was tentatively found to have coordinated through the hydroxyl and the two nitrogen atoms in the quinoline and piperidine in the structure, ...

  17. Treatment of groundwater containing Mn(II), Fe(II), As(III) and Sb(III) by bioaugmented quartz-sand filters.

    Science.gov (United States)

    Bai, Yaohui; Chang, Yangyang; Liang, Jinsong; Chen, Chen; Qu, Jiuhui

    2016-12-01

    High concentrations of iron (Fe(II)) and manganese (Mn(II)) often occur simultaneously in groundwater. Previously, we demonstrated that Fe(II) and Mn(II) could be oxidized to biogenic Fe-Mn oxides (BFMO) via aeration and microbial oxidation, and the formed BFMO could further oxidize and adsorb other pollutants (e.g., arsenic (As(III)) and antimony (Sb(III))). To apply this finding to groundwater remediation, we established four quartz-sand columns for treating groundwater containing Fe(II), Mn(II), As(III), and Sb(III). A Mn-oxidizing bacterium (Pseudomonas sp. QJX-1) was inoculated into two parallel bioaugmented columns. Long-term treatment (120 d) showed that bioaugmentation accelerated the formation of Fe-Mn oxides, resulting in an increase in As and Sb removal. The bioaugmented columns also exhibited higher overall treatment effect and anti-shock load capacity than that of the non-bioaugmented columns. To clarify the causal relationship between the microbial community and treatment effect, we compared the biomass of active bacteria (reverse-transcribed real-time PCR), bacterial community composition (Miseq 16S rRNA sequencing) and community function (metagenomic sequencing) between the bioaugmented and non-bioaugmented columns. Results indicated that the QJX1 strain grew steadily and attached onto the filter material surface in the bioaugmented columns. In general, the inoculated strain did not significantly alter the composition of the indigenous bacterial community, but did improve the relative abundances of xenobiotic metabolism genes and Mn oxidation gene. Thus, bioaugmentation intensified microbial degradation/utilization for the direct removal of pollutants and increased the formation of Fe-Mn oxides for the indirect removal of pollutants. Our study provides an alternative method for the treatment of groundwater containing high Fe(II), Mn(II) and As/Sb. Copyright © 2016 Elsevier Ltd. All rights reserved.

  18. Microbial Reducibility of Fe(III Phases Associated with the Genesis of Iron Ore Caves in the Iron Quadrangle, Minas Gerais, Brazil

    Directory of Open Access Journals (Sweden)

    Ceth W. Parker

    2013-11-01

    Full Text Available The iron mining regions of Brazil contain thousands of “iron ore caves” (IOCs that form within Fe(III-rich deposits. The mechanisms by which these IOCs form remain unclear, but the reductive dissolution of Fe(III (hydroxides by Fe(III reducing bacteria (FeRB could provide a microbiological mechanism for their formation. We evaluated the susceptibility of Fe(III deposits associated with these caves to reduction by the FeRB Shewanella oneidensis MR-1 to test this hypothesis. Canga, an Fe(III-rich duricrust, contained poorly crystalline Fe(III phases that were more susceptible to reduction than the Fe(III (predominantly hematite associated with banded iron formation (BIF, iron ore, and mine spoil. In all cases, the addition of a humic acid analogue enhanced Fe(III reduction, presumably by shuttling electrons from S. oneidensis to Fe(III phases. The particle size and quartz-Si content of the solids appeared to exert control on the rate and extent of Fe(III reduction by S. oneidensis, with more bioreduction of Fe(III associated with solid phases containing more quartz. Our results provide evidence that IOCs may be formed by the activities of Fe(III reducing bacteria (FeRB, and the rate of this formation is dependent on the physicochemical and mineralogical characteristics of the Fe(III phases of the surrounding rock.

  19. Mtr Extracellular Electron Transfer Pathways in Fe(III)-reducing or Fe(II)-oxidizing Bacteria: A Genomic Perspective

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Liang; Rosso, Kevin M.; Zachara, John M.; Fredrickson, Jim K.

    2012-12-01

    Originally discovered in the dissimilatory metal-reducing bacterium Shewanella oneidensis MR-1 (MR-1), the Mtr (i.e., metal-reducing) pathway exists in all characterized strains of metal-reducing Shewanella. The protein components identified to date for the Mtr pathway of MR-1 include four multi-heme c-type cytochromes (c-Cyts), CymA, MtrA, MtrC and OmcA, and a porin-like, outer membrane protein MtrB. They are strategically positioned along the width of the MR-1 cell envelope to mediate electron transfer from the quinone/quinol pool in the inner-membrane to the Fe(III)-containing minerals external to the bacterial cells. A survey of microbial genomes revealed homologues of the Mtr pathway in other dissimilatory Fe(III)-reducing bacteria, including Aeromonas hydrophila, Ferrimonas balearica and Rhodoferax ferrireducens, and in the Fe(II)-oxidizing bacteria Dechloromonas aromatica RCB, Gallionella capsiferriformans ES-2 and Sideroxydans lithotrophicus ES-1. The widespread distribution of Mtr pathways in Fe(III)-reducing or Fe(II)-oxidizing bacteria emphasizes the importance of this type of extracellular electron transfer pathway in microbial redox transformation of Fe. Their distribution in these two different functional groups of bacteria also emphasizes the bi-directional nature of electron transfer reactions carried out by the Mtr pathways. The characteristics of the Mtr pathways may be shared by other pathways used by microorganisms for exchanging electrons with their extracellular environments.

  20. Accumulation and distribution of iron, cadmium, lead and nickel in cucumber plants grown in hydroponics containing two different chelated iron supplies.

    Science.gov (United States)

    Csog, Árpád; Mihucz, Victor G; Tatár, Eniko; Fodor, Ferenc; Virág, István; Majdik, Cornelia; Záray, Gyula

    2011-07-01

    Cucumber plants grown in hydroponics containing 10 μM Cd(II), Ni(II) and Pb(II), and iron supplied as Fe(III) EDTA or Fe(III) citrate in identical concentrations, were investigated by total-reflection X-ray fluorescence spectrometry with special emphasis on the determination of iron accumulation and distribution within the different plant compartments (root, stem, cotyledon and leaves). The extent of Cd, Ni and Pb accumulation and distribution were also determined. Generally, iron and heavy-metal contaminant accumulation was higher when Fe(III) citrate was used. The accumulation of nickel and lead was higher by about 20% and 100%, respectively, if the iron supply was Fe(III) citrate. The accumulation of Cd was similar. In the case of Fe(III) citrate, the total amounts of Fe taken up were similar in the control and heavy-metal-treated plants (27-31 μmol/plant). Further, the amounts of iron transported from the root towards the shoot of the control, lead- and nickel-contaminated plants were independent of the iron(III) form. Although Fe mobility could be characterized as being low, its distribution within the shoot was not significantly affected by the heavy metals investigated. Copyright © 2011 Elsevier GmbH. All rights reserved.

  1. Effect of ferri(IIIcitrate and potassium hexacyanoferrate(III on growth of the moss Bryum argenteum Hedw. (Bryaceae in vitro

    Directory of Open Access Journals (Sweden)

    Vukojević Vanja

    2004-01-01

    Full Text Available In order to examine the manner of iron uptake from the medium, in vitro culture of moss Bryum argenteum Hedw. (Bryaceae was established. Under controlled conditions (16h light/8h dark, light intensity 47μmol m-2s-1 25±2°C, the moss was grown on basal MS medium or on MS medium enriched with various concentrations of ferri(IIIcitrate or potassium hexacyanoferrate(III. It was expected that with the organic chelate complex, Fe(III ion will be more available for the plant. Sixty days after establishing in vitro culture, the plants grown on MS medium enriched with the ferri(IIIcitrate complex were developed better than plants grown on media with the potassium hexacyanoferrate(III complex. To judge from plant production in vitro and in view of the fact that the two compounds were the only source of Fe(III, it would appear that the citrate complex makes Fe(III ions more available than potassium hexacyanoferrate(III. Further research will examine the concentrations of Fe ion uptake by plants and potential use of these tiny moss plants for the phytomining, phytoremedies and hyperaccumulating purposes.

  2. Synthesis and characterisation of the Fe(II-III) hydroxy-formate green rust

    International Nuclear Information System (INIS)

    Refait, P.; Abdelmoula, M.; Genin, J.-M. R.; Jeannin, M.

    2006-01-01

    A new methodology was envisioned in order to prepare green rust compounds build on organic anions that could intervene in microbiologically influenced corrosion processes of iron and steel. The formate ion was chosen as an example. The formation of rust was simulated by the oxidation of aqueous suspensions of Fe(OH) 2 precipitated from Fe(II) lactate and sodium hydroxide, in the presence of sodium formate to promote the formation of the corresponding green rust. The evolution of the precipitate with time was followed by transmission Moessbauer spectroscopy at 15 K. It was observed that the initial hydroxide was transformed into a new GR compound. Its spectrum is composed of three quadrupole doublets, D 1 (δ = 1.28 mm s -1 , Δ = 2.75 mm s -1 ) and D 2 (δ = 1.28 mm s -1 , Δ 2.48 mm s -1 ) that correspond to Fe(II) and D 3 (δ = 0.49 mm s -1 , Δ = 0.37 mm s -1 ) that corresponds to Fe(III). The relative area of D 3 , close to the proportion of Fe(III) in the GR, was found at 28.5 ± 1.5% (∼2/7). Raman spectroscopy confirmed that the intermediate compound was a Fe(II-III) hydroxy-formate, GR(HCOO - ).

  3. Speciative Determination of Dissolved Inorganic Fe(II), Fe(III) and Total Fe in Natural Waters by Coupling CPE with FAAS

    International Nuclear Information System (INIS)

    Gurkan, R.; Altunay, N.

    2013-01-01

    A new cloud point extraction (CPE) method for the preconcentration of trace iron speciation in natural waters prior to determination by flame atomic absorption spectrometry (FAAS) was developed in the present study. In this method, Fe(II) sensitively and selectively reacts with Calcon carboxylic acid (CCA) in presence of cetylpyridinium chloride (CPC) yielding a hydrophobic complex at pH 10.5, which is then entrapped in surfactant-rich phase. Total Fe was accurately and reliably determined after the reduction of Fe(III) to Fe(II) with sulfite. The amount of Fe(III) in samples was determined from the difference between total Fe and Fe(II). CPC was used not only as an auxiliary ligand in CPE, but also as sensitivity enhancement agent in FAAS. The nonionic surfactant, polyethylene glycol tert-octylphenyl ether (Triton X-114) was used as an extracting agent. The analytical variables affecting CPE efficiency were investigated in detail. The preconcentration/enhancement factors of 50 and 82 respectively, were obtained for the preconcentration of Fe(II) with 50 mL solution. Under the optimized conditions, the detection limit of Fe(II) in linear range of 0.2-60 μg L/sup -1/ was 0.06 μg L/sup -1/. The relative standard deviation was 2.7 percentage (20 μg L/sup -1/, N: 5), recoveries for Fe(II) were in range of 99.0-102.0 percentage for all water samples including certified reference materials (CRMs). In order to verify its accuracy, two CRMs were analyzed and the results obtained were statistically in good agreement with the certified values. (author)

  4. Study of the Thermodynamics of Chromium(III) and Chromium(VI) Binding to Fe3O4 and MnFe2O4 nanoparticles

    Science.gov (United States)

    Luther, Steven; Brogfeld, Nathan; Kim, Jisoo; Parsons, J.G.

    2013-01-01

    Removal of chromium(III) or (VI) from aqueous solution was achieved using Fe3O4, and MnFe2O4 nanomaterials. The nanomaterials were synthesized using a precipitation method and characterized using XRD. The size of the nanomaterials was determined to be 22.4 ± 0.9 nm (Fe3O4) and 15.5 ± 0.5 nm (MnFe2O4). The optimal binding pH for chromium(III) and chromium(VI) were pH 6 and pH 3. Isotherm studies were performed, under light and dark conditions, to determine the capacity of the nanomaterials. The capacities for the light studies with MnFe2O4 and Fe3O4 were determined to be 7.189 and 10.63 mg/g, respectively, for chromium(III). The capacities for the light studies with MnFe2O4 and Fe3O4 were 3.21 and 3.46 mg/g, respectively, for chromium(VI). Under dark reaction conditions the binding of chromium(III) to the MnFe2O4 and Fe3O4 nanomaterials were 5.74 and 15.9 mg/g, respectively. The binding capacity for the binding of chromium(VI) to MnFe2O4 and Fe3O4 under dark reaction conditions were 3.87 and 8.54 mg/g, respectively. The thermodynamics for the reactions showed negative ΔG values, and positive ΔH values. The ΔS values were positive for the binding of chromium(III) and for chromium(VI) binding under dark reaction conditions. The ΔS values for chromium(VI) binding under the light reaction conditions were determined to be negative. PMID:23558081

  5. THE WIDESPREAD OF Fe(III)-REDUCING BACTERIA IN NATURAL ECOSYSTEMS OF ECUADOR.

    Science.gov (United States)

    Tashyrev, O B; Govorukha, V M

    2015-01-01

    The widespread of Fe(III)-reducing microorganisms in natural ecosystems of Ecuador of La Favorita, Tungurahua volcano and Papallacta areas was experimentally proved. High efficiency of microbial precipitation of soluble iron compounds was also demonstrated. Obtained results indicate the potential ability of Fe(III)-reducing microorganisms to influence the formation of carbon and iron vector fluxes in ecosystems, as well as development of effective biotechnologies of water purification from iron compounds.

  6. The Nature of the intermediates in the reactions of Fe(III)- and Mn(III)-microperoxidase-8 with H2O2 : a rapid kinetic study

    NARCIS (Netherlands)

    Primus, J.L.; Grunenwald, S.; Hagedoorn, P.L.; Albrecht-Gary, A.M.; Mandon, D.; Veeger, C.

    2002-01-01

    Kinetic studies were performed with microperoxidase-8 (Fe(III)MP-8), the proteolytic breakdown product of horse heart cytochrome c containing an octapeptide linked to an iron protoporphyrin IX. Mn(III) was substituted for Fe(III) in Mn(III)MP-8.The mechanism of formation of the reactive metal-oxo

  7. Fe(III)-TAML activator: a potent peroxidase mimic for chemiluminescent determination of hydrogen peroxide.

    Science.gov (United States)

    Vdovenko, Marina M; Demiyanova, Alexandra S; Kopylov, Kirill E; Sakharov, Ivan Yu

    2014-07-01

    Efforts to replace native peroxidase with its low molecular weight alternatives have stimulated a search for peroxidase mimetics. Herein we describe the oxidation of luminol with hydrogen peroxide catalyzed by commercially available Fe(III)-TAML activator 1a, which was shown to be a more active catalyst than hemin. At Fe(III)-TAML activator 1a use in chemiluminescent assay for H2O2 determination the detection limit value (3σ) of 5×10(-8)M was similar to the detection limit obtained with horseradish peroxidase (1×10(-7)M) and significantly lower than that obtained in the presence of hemin (6×10(-7)M). The linear ranges (R(2)=0.98) of the assay were 6×10(-8)-1×10(-6)M and 6×10(-7)-1×10(-6)M H2O2 for Fe(III)-TAML 1a and hemin, respectively. The CV values for Fe(III)-TAML 1a-based assay measured within the working range varied from 1.0% to 3.7% (n=4), whereas in the case of hemin -5.0% to 9.7% (n=4). Moreover, the sensitivity of Fe(III)-TAML 1a-based method was 56 and 5 times higher than that of hemin- and HRP-based methods, respectively. The obtained results open good perspectives to apply Fe(III)-TAML activator 1a in CL analytical methods instead of hemin, a traditionally used peroxidase mimetic. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. Ultrasonic irradiation enhanced the ability of Fluorescein-DA-Fe(III) on sonodynamic and sonocatalytic damages of DNA molecules.

    Science.gov (United States)

    Wu, Qiong; Chen, Xia; Jia, Lizhen; Wang, Yi; Sun, Ying; Huang, Xingjun; Shen, Yuxiang; Wang, Jun

    2017-11-01

    The interaction of DNA with Bis [N,N-bis (carboxymethyl) aminomethyl] fluorescein-Ferrous(III) (Fluorescein-DA-Fe(III)) with dual functional (sonodynamic and sonocatalytic) activity was studied by UV-vis spectroscopy, fluorescence spectroscopy, FT-IR spectroscopy, circular dichroism (CD) spectroscopy and viscosity measurements. And then, the damage of DNA caused by Fluorescein-DA-Fe(III) under ultrasonic irradiation (US) was researched by agarose gel electrophoresis and cytotoxicity assay. Meanwhile, some influenced factors such as ultrasonic irradiation time and Fluorescein-DA-Fe(III) concentration on the damage degree of DNA molecules were also examined. As a control, for Bis [N,N-bis (carboxymethyl) aminomethyl] fluorescein (Fluorescein-DA), the same experiments were carried out. The results showed that both Fluorescein-DA-Fe(III) and Fluorescein-DA can interact with DNA molecules. Under ultrasonic irradiation, Fluorescein-DA shows sonodynamic activity, which can damage DNA molecules. While, in the presence of Fe(III) ion, the Fluorescein-DA-Fe(III) displays not only sonodynamic activity but also sonocatalytic activity under ultrasonic irradiation, which injures DNA more serious than Fluorescein-DA. The researches confirmed the dual function (sonodynamic activity and sonocatalytic activity) of Fluorescein-DA-Fe(III) and expanded the usage of Fluorescein-DA-Fe(III) as a sonosensitizer in sonodynamic therapy (SDT). Copyright © 2017 Elsevier B.V. All rights reserved.

  9. CoFe2O4 nanocrystalline powders prepared by citrate-gel methods: Synthesis, structure and magnetic properties

    International Nuclear Information System (INIS)

    Cannas, C.; Falqui, A.; Musinu, A.; Peddis, D.; Piccaluga, G.

    2006-01-01

    Nanocrystalline CoFe 2 O 4 powders were prepared by decomposition of metal ion citrate precursors. Four samples were synthesized from precursor solutions having different pH values in the range 2 physisorption and Transmission Electron Microscopy. Magnetic properties were explored by a SQUID magnetometer. Three out of the four samples, coming from solutions of pH 2, 4 and 7, were produced by an autocombustion reaction and are very similar as regards average size of the nanoparticles (about 20 nm), their morphology and the magnetic properties, while the fourth sample was produced by a slower thermal decomposition and is composed of smaller nanoparticles (about 10 nm)

  10. Dissociation kinetics of Fe(III)- and Al(III)-natural organic matter complexes at pH 6.0 and 8.0 and 25 °C

    Science.gov (United States)

    Jones, Adele M.; Pham, A. Ninh; Collins, Richard N.; Waite, T. David

    2009-05-01

    The rate at which iron- and aluminium-natural organic matter (NOM) complexes dissociate plays a critical role in the transport of these elements given the readiness with which they hydrolyse and precipitate. Despite this, there have only been a few reliable studies on the dissociation kinetics of these complexes suggesting half-times of some hours for the dissociation of Fe(III) and Al(III) from a strongly binding component of NOM. First-order dissociation rate constants are re-evaluated here at pH 6.0 and 8.0 and 25 °C using both cation exchange resin and competing ligand methods for Fe(III) and a cation exchange resin method only for Al(III) complexes. Both methods provide similar results at a particular pH with a two-ligand model accounting satisfactorily for the dissociation kinetics results obtained. For Fe(III), half-times on the order of 6-7 h were obtained for dissociation of the strong component and 4-5 min for dissociation of the weak component. For aluminium, the half-times were on the order of 1.5 h and 1-2 min for the strong and weak components, respectively. Overall, Fe(III) complexes with NOM are more stable than analogous complexes with Al(III), implying Fe(III) may be transported further from its source upon dilution and dispersion.

  11. Radiotracer study of the adsorption of Fe(III), Cr(III) and Cd(II) on natural and chemically modified Slovak zeolite

    International Nuclear Information System (INIS)

    Foeldesova, M.; Dillinger, P.; Lukac, P.

    1998-01-01

    In order to minimize the contamination of environment with metals in ionic form the more types of natural and chemically modified zeolites were examined to their uptake of Fe(III), Cr(III) and Cd(II) from water solutions by batch radio-exchange equilibration method. In this study was used zeolitic tuff from deposit Nizny Hrabovec (content of clinoptilolite 50-70%) with the grain size from 1.2 to 2.2 mm. The granules of zeolite were modified with the following NaOH solutions: ).5, 1, 2 and 4 mol.l -1 at 80 grad C for 4 hours. The sorption of Fe, Cr and Cd ions on all types of zeolites was studied by radio-exchange method and the sorption of Fe and Cr also flame atomic absorption method. From sorption curves the sorption coefficients were calculated. The results obtained in this work show that zeolites modified with NaOH solution are suitable for adsorption of Fe(III), Cr(III) and Cd(II) from underwater, waste water, feed water and coolant water from nuclear plants. The adsorbed zeolites can be solidified by conventional way

  12. STRUCTURE AND SOME BIOLOGICAL PROPERTIES OF Fe(III COMPLEXES WITH NITROGEN-CONTAINING LIGANDS

    Directory of Open Access Journals (Sweden)

    Ion Bulhac

    2016-06-01

    Full Text Available Four coordination compounds of iron(III with ligands based on hydrazine and sulfadiazine: FeCl3·digsemi·2H2O (I (digsemi-semicarbazide diacetic acid dihydrazide, [Fe(HLSO4] (II (НL - sulfadiazine, [Fe(H2L1(H2O2](NO33·5H2O (III (H2L1-2,6-diacetylpyridine bis(nicotinoylhydrazone and [Fe(H2L2(H2O2](NO33•1.5H2O (IV (H2L2 - 2,6-diacetylpyridine bis(isonicotinoylhydrazone were synthesized. The spectroscopic and structural characterisation as well as their biological, properties are presented.

  13. Microbial Fe (III) reduction and hydrogen production by a transposon-mutagenized strain of Pantoea agglomerans BH18

    International Nuclear Information System (INIS)

    Liu, Hongyan; Wang, Guangce

    2015-01-01

    Based on the transposon-mutagenized library of Pantoea agglomerans BH18, mutant screens were conducted to obtain the strain with the highest Fe (III) reduction and hydrogen production. Of these transposon-mutagenized mutants, the mutant strain TB230 was screened for high Fe (III)-reducing efficiency and hydrogen production. The PCR amplification and kanamycin resistance selection results indicated that the transposon insertion of the mutant strain TB230 was stable. Hydrogen production of the mutant strain TB230 was (2.21 ± 0.34) mol H 2 /mol glucose, which increased hydrogen production by over 40% compared with that of the wild type strain. The accumulation concentration of Fe (II) in the medium of the mutant strain TB230 with Fe (OH) 3 as the sole electron acceptor was (7.39 ± 0.49) mmol/l, which was approximately 3-fold greater than that of the wild type strain. The mutant strain TB230 showed high Fe (III)-reducing activity and hydrogen production by adopting glucose and pyruvate as the carbon source. In addition, the mutant strain TB230 was capable of Fe (III) reduction and hydrogen production under fresh or marine conditions. This result indicates that the mutant strain with high microbial Fe (III) reduction and hydrogen production is beneficial for the improvement of anaerobic performance. - Highlights: • The mutant strain TB230 was a transposon-mutagenized strain of Pantoea agglomerans BH18. • Strain TB230 was screened for high Fe (III)-reducing efficiency and hydrogen production. • H 2 yield and Fe (III)-reducing activity were 2.21 ± 0.34 and 7.39 ± 0.49 in marine condition. • Strain TB230 was capable of Fe (III) reduction and hydrogen production in fresh or marine condition

  14. Fe(III)-solar light induced degradation of diethyl phthalate (DEP) in aqueous solutions.

    Science.gov (United States)

    Mailhot, G; Sarakha, M; Lavedrine, B; Cáceres, J; Malato, S

    2002-11-01

    The degradation of diethyl phthalate (DEP) photoinduced by Fe(III) in aqueous solutions has been investigated under solar irradiation in the compound parabolic collector reactor at Plataforma Solar de Almeria. Hydroxyl radicals *OH, responsible of the degradation, are formed via an intramolecular photoredox process in the excited state of Fe(III) aquacomplexes. The primary step of the reaction is mainly due to the attack of *OH radicals on the aromatic ring. For prolonged irradiations DEP and its photoproducts are completely mineralized due to the regeneration of the absorbing species and the continuous formation of *OH radicals that confers a catalytic aspect to the process. Consequently, the degradation photoinduced by Fe(III) could be an efficient method of DEP removal from water.

  15. Sonochemical synthesis, structure and magnetic properties of air-stable Fe3O4/Au nanoparticles

    International Nuclear Information System (INIS)

    Wu Wei; He Quanguo; Chen Hong; Tang Jianxin; Nie Libo

    2007-01-01

    Air-stable nanoparticles of Fe 3 O 4 /Au were prepared via sonolysis of a solution mixture of hydrogen tetrachloroaureate(III) trihydrate (HAuCl 4 ) and (3-aminopropyl)triethoxysilane (APTES)-coated Fe 3 O 4 nanoparticles with further drop-addition of sodium citrate. The Fe 3 O 4 /Au nanoparticles were characterized by x-ray powder diffraction (XRD), ultraviolet-visible spectroscopy (UV-vis), scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS) and superconducting quantum interference device (SQUID) magnetometry. Nanoparticles of Fe 3 O 4 /Au obtained under appropriate conditions possess a very high saturation magnetization of about 63 emu g -1 and their average diameter is about 30 nm

  16. Removal of Sb(III and Sb(V by Ferric Chloride Coagulation: Implications of Fe Solubility

    Directory of Open Access Journals (Sweden)

    Muhammad Ali Inam

    2018-04-01

    Full Text Available Coagulation and precipitation appear to be the most efficient and economical methods for the removal of antimony from aqueous solution. In this study, antimony removal from synthetic water and Fe solubility with ferric chloride (FC coagulation has been investigated. The effects of pH, FC dosage, initial antimony loading and mixed Sb(III, Sb(V proportions on Fe solubility and antimony removal were studied. The results showed that the Sb(III removal efficiency increased with the increase of solution pH particularly due to an increase in Fe precipitation. The Sb(V removal was influenced by the solution pH due to a change in Fe solubility. However, the Fe solubility was only impaired by the Sb(III species at optimum pH 7. The removal efficiencies of both Sb species were enhanced with an increase in FC dose. The quantitative analysis of the isotherm study revealed the strong adsorption potential of Sb(III on Fe precipitates as compared to Sb(V. Furthermore, the removal behavior of antimony was inhibited in mixed proportion with high Sb(V fraction. In conclusion, this study contributes to better understanding the fate of Sb species, their mobilities, and comparative removal behavior, with implications for Fe solubility using ferric chloride in different aqueous environments.

  17. Removal of citrate and hypophosphite binary components using Fenton, photo-Fenton and electro-Fenton processes

    Institute of Scientific and Technical Information of China (English)

    Yao-Hui Huang; Hsiao-Ting Su; Li-Way Lin

    2009-01-01

    Both citrate and hypophosphite in aqueous solution were degraded by advanced oxidation processes (Fe2+/H2O2, UV/Fe2+/H2O2, and electrolysis/ Fe2+/H2O2) in this study. Comparison of these techniques in oxidation efficiency was undertaken. It was found that Fenton process could not degrade completely citrate in the presence of hypophosphite since it caused a series inhibition. Therefore, UV light (photo-Fenton) or electron current (electro-Fenton) was applied to improve the degradation efficiency of the Fenton process. Results showed that both photo-Fenton and electro-Fenton processes could overcome the inhibition of hypophosphite, especially the electro-Fenton.

  18. Effectively simultaneous naked-eye detection of Cu(II), Pb(II), Al(III) and Fe(III) using cyanidin extracted from red cabbage as chelating agent

    Science.gov (United States)

    Khaodee, Warangkhana; Aeungmaitrepirom, Wanlapa; Tuntulani, Thawatchai

    Simultaneous determination of Cu(II), Pb(II), Al(III) and Fe(III) using cyanidin as a chelating agent was investigated in terms of both quantitative and qualitative detections. Cyanidin was extracted and purified from red cabbage which is a local plant in Thailand. The selectivity of this method was examined by regulating the pH of cyanidin solution operated together with masking agents. It was found that Cu(II), Pb(II), Al(III) and Fe(III) simultaneously responded with the color change at pH 7, pH 6, pH 5 and pH 4, respectively. KF, DMG and the mixture of KF and DMG were used as masking agents for the determination of Fe(III), Al(III) and Pb(II), respectively. Results from naked-eye detection were evaluated by comparing with those of inductively coupled plasma (ICP), and there was no significant difference noticed. Cyanidin using as a multianalyte reagent could be employed for simultaneous determination of Cu(II), Pb(II), Al(III) and Fe(III) at the lowest concentration at 50, 80, 50 and 200 μM, respectively, by slightly varying pHs. Moreover, the proposed method could be potentially applied for real water samples with simplicity, rapidity, low cost and environmental safety.

  19. Kinetics of microbial Fe(III) oxyhydroxidereduction: The role of mineral properties

    NARCIS (Netherlands)

    Bonneville, Steeve

    2005-01-01

    In many soils, sediments and groundwaters, ferric iron is a major potential electron acceptor for the oxidation of organic matter. In contrast to other terminal electron acceptors (e.g. nitrate or sulfate), the concentration of Fe3+(aq), is limited by the low solubility of Fe(III) oxyhydroxides

  20. SEPARATION OF Fe (III, Cr(III, Cu(II, Ni(II, Co(II, AND Pb(II METAL IONS USING POLY(EUGENYL OXYACETIC ACID AS AN ION CARRIER BY A LIQUID MEMBRANE TRANSPORT METHOD

    Directory of Open Access Journals (Sweden)

    La Harimu

    2010-06-01

    Full Text Available Fe (III, Cr(III, Cu(II, Ni(II, Co(II, and Pb(II  metal ions had been separated using poly(eugenyl oxyacetic acid as an ion carrier by bulk liquid membrane transport method. The effect of pH, polyeugenyl oxyacetic acid ion carrier concentration, nitric acid concentration in the stripping solution, transport time, and metal concentration were optimized. The result showed that the optimum condition for transport of metal ions was at pH 4 for ion Fe(III and at pH 5 for Cr(III, Cu(II, Ni(II, Co(II, and Pb(II ions. The carrier volumes were optimum with concentration of 1 x 10-3 M at 7.5 mL for Cr(III, Cu (II,  Ni(II, Co(II ions and at 8.5 mL for Fe(III and Pb(II ions. The concentration of HNO3 in stripping phase was optimum at 2 M for Fe(III and Cu(II ions, 1 M for Cr(III, Ni(II and Co(II ions, and 0.5 M for Pb(II ion. The optimum transport times were 36 h for Fe(III and Co(II ions, and 48 h for Cr(III, Cu (II, Ni(II, and Pb(II ions. The concentration of metal ions accurately transported were 2.5 x 10-4 M for Fe(III and Cr(III ions, and 1 M for Cu (II, Ni(II, Co(II, and Pb(II ions. Compared to other metal ions the transport of Fe(III was the highest with selectivity order of Fe(III > Cr(III > Pb(II > Cu(II > Ni(II > Co(II. At optimum condition, Fe(III ion was transported through the membrane at 46.46%.   Keywords: poly(eugenyl oxyacetic acid, transport, liquid membrane, Fe (III, Cr(III, Cu(II, Ni(II, Co(II, and Pb(II ions

  1. Enhancement effects of reducing agents on the degradation of tetrachloroethene in the Fe(II)/Fe(III) catalyzed percarbonate system

    International Nuclear Information System (INIS)

    Miao, Zhouwei; Gu, Xiaogang; Lu, Shuguang; Brusseau, Mark L.; Yan, Ni; Qiu, Zhaofu; Sui, Qian

    2015-01-01

    Highlights: • PCE degradation by reducing-agent modified Fe-catalyzed percarbonate was studied. • The addition of reducing agents significantly increased PCE degradation. • Hydroxylamine hydrochloride showed the best effect on enhancing PCE degradation. • The primary PCE degradation mechanism was oxidation by hydroxyl radical. • O_2·"− participated in the degradation of PCE in reducing-agent modified system. - Abstract: In this study, the effects of reducing agents on the degradation of tetrachloroethene (PCE) were investigated in the Fe(II)/Fe(III) catalyzed sodium percarbonate (SPC) system. The addition of reducing agents, including hydroxylamine hydrochloride, sodium sulfite, ascorbic acid and sodium ascorbate, accelerated the Fe(III)/Fe(II) redox cycle, leading to a relatively steady Fe(II) concentration and higher production of free radicals. This, in turn, resulted in enhanced PCE oxidation by SPC, with almost complete PCE removal obtained for appropriate Fe and SPC concentrations. The chemical probe tests, using nitrobenzene and carbon tetrachloride, demonstrated that HO· was the predominant radical in the system and that O_2·"− played a minor role, which was further confirmed by the results of electron spin resonance measurements. PCE degradation decreased significantly with the addition of isopropanol, a HO· scavenger, supporting the hypothesis that HO· was primarily responsible for PCE degradation. It is noteworthy that Cl"− release was slightly delayed in the first 20 min, indicating that intermediate products were produced. However, these intermediates were further degraded, resulting in the complete conversion of PCE to CO_2. In conclusion, the use of reducing agents to enhance Fe(II)/Fe(III) catalyzed SPC oxidation appears to be a promising approach for the rapid degradation of organic contaminants in groundwater.

  2. Enhancement effects of reducing agents on the degradation of tetrachloroethene in the Fe(II)/Fe(III) catalyzed percarbonate system

    Energy Technology Data Exchange (ETDEWEB)

    Miao, Zhouwei [State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, East China University of Science and Technology, Shanghai 200237 (China); Soil, Water and Environmental Science Department, School of Earth and Environmental Sciences, The University of Arizona, 429 Shantz Building, Tucson, AZ 85721 (United States); Gu, Xiaogang [State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, East China University of Science and Technology, Shanghai 200237 (China); Lu, Shuguang, E-mail: lvshuguang@ecust.edu.cn [State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, East China University of Science and Technology, Shanghai 200237 (China); Brusseau, Mark L. [Soil, Water and Environmental Science Department, School of Earth and Environmental Sciences, The University of Arizona, 429 Shantz Building, Tucson, AZ 85721 (United States); Yan, Ni [Hydrology and Water Resources Department, School of Earth and Environmental Sciences, University of Arizona, 429 Shantz Building, Tucson, AZ 85721 (United States); Qiu, Zhaofu; Sui, Qian [State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, East China University of Science and Technology, Shanghai 200237 (China)

    2015-12-30

    Highlights: • PCE degradation by reducing-agent modified Fe-catalyzed percarbonate was studied. • The addition of reducing agents significantly increased PCE degradation. • Hydroxylamine hydrochloride showed the best effect on enhancing PCE degradation. • The primary PCE degradation mechanism was oxidation by hydroxyl radical. • O{sub 2}·{sup −} participated in the degradation of PCE in reducing-agent modified system. - Abstract: In this study, the effects of reducing agents on the degradation of tetrachloroethene (PCE) were investigated in the Fe(II)/Fe(III) catalyzed sodium percarbonate (SPC) system. The addition of reducing agents, including hydroxylamine hydrochloride, sodium sulfite, ascorbic acid and sodium ascorbate, accelerated the Fe(III)/Fe(II) redox cycle, leading to a relatively steady Fe(II) concentration and higher production of free radicals. This, in turn, resulted in enhanced PCE oxidation by SPC, with almost complete PCE removal obtained for appropriate Fe and SPC concentrations. The chemical probe tests, using nitrobenzene and carbon tetrachloride, demonstrated that HO· was the predominant radical in the system and that O{sub 2}·{sup −} played a minor role, which was further confirmed by the results of electron spin resonance measurements. PCE degradation decreased significantly with the addition of isopropanol, a HO· scavenger, supporting the hypothesis that HO· was primarily responsible for PCE degradation. It is noteworthy that Cl{sup −} release was slightly delayed in the first 20 min, indicating that intermediate products were produced. However, these intermediates were further degraded, resulting in the complete conversion of PCE to CO{sub 2}. In conclusion, the use of reducing agents to enhance Fe(II)/Fe(III) catalyzed SPC oxidation appears to be a promising approach for the rapid degradation of organic contaminants in groundwater.

  3. Evaluation of oral abdominal contrast agent containing ferric ammonium citrate

    International Nuclear Information System (INIS)

    Shiga, Toshiko; Kawamura, Yasutaka; Iwasaki, Toshiko

    1991-01-01

    We evaluated the effectiveness of oral MRI contrast agent containing ferric ammonium citrate. Twenty patients were arbitrarily divided into 2 groups according to the given dose of 100 and 200 mg Fe of oral MRI contrast agent. MRI was performed before and immediately after ingesting 300 ml solution of oral MRI contrast agent using a 1.5 T superconducting system (GE: Signa). Each dose of 100 and 200 mg Fe of oral MRI contrast agent produced sufficient enhancement of gastrointestinal tract, enough to make clear the pancreatic contour and porta hepatis. There was no significant change in blood and urine analysis observed after taking oral MRI contrast agent. The use of ferric ammonium citrate as an oral MRI contrast agent seems to add valuable information in performing upper abdominal MRI imaging. (author)

  4. Fe(III/TiO2-Montmorillonite Photocatalyst in Photo-Fenton-Like Degradation of Methylene Blue

    Directory of Open Access Journals (Sweden)

    Is Fatimah

    2015-01-01

    Full Text Available A photodegradation process of methylene blue (MB in aqueous solution using Fe(III/TiO2-montmorillonite photocatalyst is presented. The photocatalyst material was prepared using Indonesian natural montmorillonite in TiO2 pillarization process followed by Fe(III ion exchange. Kinetic study on MB degradation was conducted and evaluated by three kinetic models: the pseudo-first- and second-order equations and the Elovich equation. From the results, it is concluded that the degradation under the photo-Fenton-like process utilizing Fe(III/TiO2-montmorillonite photocatalyst conformed to the Elovich kinetic model.

  5. Microbial Fe(III) Oxide Reduction in Chocolate Pots Hot Springs, Yellowstone National Park

    Science.gov (United States)

    Fortney, N. W.; Roden, E. E.; Boyd, E. S.; Converse, B. J.

    2014-12-01

    Previous work on dissimilatory iron reduction (DIR) in Yellowstone National Park (YNP) has focused on high temperature, low pH environments where soluble Fe(III) is utilized as an electron acceptor for respiration. Much less attention has been paid to DIR in lower temperature, circumneutral pH environments, where solid phase Fe(III) oxides are the dominant forms of Fe(III). This study explored the potential for DIR in the warm (ca. 40-50°C), circumneutral pH Chocolate Pots hot springs (CP) in YNP. Most probable number (MPN) enumerations and enrichment culture studies confirmed the presence of endogenous microbial communities that reduced native CP Fe(III) oxides. Enrichment cultures demonstrated sustained DIR coupled to acetate and lactate oxidation through repeated transfers over ca. 450 days. Pyrosequencing of 16S rRNA genes indicated that the dominant organisms in the enrichments were closely affiliated with the well known Fe(III) reducer Geobacter metallireducens. Additional taxa included relatives of sulfate reducing bacterial genera Desulfohalobium and Thermodesulfovibrio; however, amendment of enrichments with molybdate, an inhibitor of sulfate reduction, suggested that sulfate reduction was not a primary metabolic pathway involved in DIR in the cultures. A metagenomic analysis of enrichment cultures is underway in anticipation of identifying genes involved in DIR in the less well-characterized dominant organisms. Current studies are aimed at interrogating the in situ microbial community at CP. Core samples were collected along the flow path (Fig. 1) and subdivided into 1 cm depth intervals for geochemical and microbiological analysis. The presence of significant quantities of Fe(II) in the solids indicated that DIR is active in situ. A parallel study investigated in vitro microbial DIR in sediments collected from three of the coring sites. DNA was extracted from samples from both studies for 16S rRNA gene and metagenomic sequencing in order to obtain a

  6. Microbial reductive transformation of phyllosilicate Fe(III) and U(VI) in fluvial subsurface sediments.

    Science.gov (United States)

    Lee, Ji-Hoon; Fredrickson, James K; Kukkadapu, Ravi K; Boyanov, Maxim I; Kemner, Kenneth M; Lin, Xueju; Kennedy, David W; Bjornstad, Bruce N; Konopka, Allan E; Moore, Dean A; Resch, Charles T; Phillips, Jerry L

    2012-04-03

    The microbial reduction of Fe(III) and U(VI) was investigated in shallow aquifer sediments collected from subsurface flood deposits near the Hanford Reach of the Columbia River in Washington State. Increases in 0.5 N HCl-extractable Fe(II) were observed in incubated sediments and (57)Fe Mössbauer spectroscopy revealed that Fe(III) associated with phyllosilicates and pyroxene was reduced to Fe(II). Aqueous uranium(VI) concentrations decreased in subsurface sediments incubated in sulfate-containing synthetic groundwater with the rate and extent being greater in sediment amended with organic carbon. X-ray absorption spectroscopy of bioreduced sediments indicated that 67-77% of the U signal was U(VI), probably as an adsorbed species associated with a new or modified reactive mineral phase. Phylotypes within the Deltaproteobacteria were more common in Hanford sediments incubated with U(VI) than without, and in U(VI)-free incubations, members of the Clostridiales were dominant with sulfate-reducing phylotypes more common in the sulfate-amended sediments. These results demonstrate the potential for anaerobic reduction of phyllosilicate Fe(III) and sulfate in Hanford unconfined aquifer sediments and biotransformations involving reduction and adsorption leading to decreased aqueous U concentrations.

  7. Theoretical emission line ratios for [Fe III] and [Fe VII] applicable to the optical and infrared spectra of gaseous nebulae.

    Science.gov (United States)

    Keenan, F P; Aller, L H; Ryans, R S; Hyung, S

    2001-08-14

    Recent calculations of electron impact excitation rates and Einstein A-coefficients for transitions among the 3d(6) levels of Fe III and among the 3d(2) levels of Fe VII are used to derive theoretical emission line ratios applicable to the optical and infrared spectra of gaseous nebulae. Results for [Fe III] are generated for electron temperatures T(e) = 7,000-20,000 K and densities N(e) = 10(2)-10(8) cm(-3), whereas those for [Fe VII] are provided for T(e) = 10,000-30,000 K and N(e) = 10(2)-10(8) cm(-3). The theoretical line ratios are significantly different in some instances from earlier calculations and resolve discrepancies between theory and observation found for the planetary nebulae IC 4997 and NGC 7027.

  8. Inhibition of the Fe(III)-catalyzed dopamine oxidation by ATP and its relevance to oxidative stress in Parkinson's disease.

    Science.gov (United States)

    Jiang, Dianlu; Shi, Shuyun; Zhang, Lin; Liu, Lin; Ding, Bingrong; Zhao, Bingqing; Yagnik, Gargey; Zhou, Feimeng

    2013-09-18

    Parkinson's disease (PD) is characterized by the progressive degeneration of dopaminergic cells, which implicates a role of dopamine (DA) in the etiology of PD. A possible DA degradation pathway is the Fe(III)-catalyzed oxidation of DA by oxygen, which produces neuronal toxins as side products. We investigated how ATP, an abundant and ubiquitous molecule in cellular milieu, affects the catalytic oxidation reaction of dopamine. For the first time, a unique, highly stable DA-Fe(III)-ATP ternary complex was formed and characterized in vitro. ATP as a ligand shifts the catecholate-Fe(III) ligand metal charge transfer (LMCT) band to a longer wavelength and the redox potentials of both DA and the Fe(III) center in the ternary complex. Remarkably, the additional ligation by ATP was found to significantly reverse the catalytic effect of the Fe(III) center on the DA oxidation. The reversal is attributed to the full occupation of the Fe(III) coordination sites by ATP and DA, which blocks O2 from accessing the Fe(III) center and its further reaction with DA. The biological relevance of this complex is strongly implicated by the identification of the ternary complex in the substantia nigra of rat brain and its attenuation of cytotoxicity of the Fe(III)-DA complex. Since ATP deficiency accompanies PD and neurotoxin 1-methyl-4-phenylpyridinium (MPP(+)) induced PD, deficiency of ATP and the resultant impairment toward the inhibition of the Fe(III)-catalyzed DA oxidation may contribute to the pathogenesis of PD. Our finding provides new insight into the pathways of DA oxidation and its relationship with synaptic activity.

  9. Preparation and photocatalytic performance of Fe (III)-amidoximated PAN fiber complex for oxidative degradation of azo dye under visible light irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Yongchun, E-mail: dye@tjpu.edu.cn [Division of Textile Chemistry and Ecology, School of Textile Science and Engineering, Tianjin Polytechnic University, Tianjin 300160 (China); State Key Laboratory Breeding Base of Photocatalysis, Fuzhou University, Fuzhou, 350002 (China); Han, Zhenbang [Division of Textile Chemistry and Ecology, School of Textile Science and Engineering, Tianjin Polytechnic University, Tianjin 300160 (China); Liu, Chunyan [Division of Textile Chemistry and Ecology, School of Textile Science and Engineering, Tianjin Polytechnic University, Tianjin 300160 (China); State Key Laboratory Breeding Base of Photocatalysis, Fuzhou University, Fuzhou, 350002 (China); Du, Fang [Division of Textile Chemistry and Ecology, School of Textile Science and Engineering, Tianjin Polytechnic University, Tianjin 300160 (China)

    2010-04-15

    Polyacrylonitrile (PAN) fiber was modified with hydroxylamine hydrochloride to introduce amidoxime groups onto the fiber surface. These amidoxime groups were used to react with Fe (III) ions to prepare Fe (III)-amidoximated PAN fiber complex, which was characterized using SEM, XRD, FTIR, XPS, DMA, and DRS respectively. Then the photocatalytic activity of Fe-AO-PAN was evaluated in the degradation of a typical azo dye, C. I. Reactive Red 195 in the presence of H{sub 2}O{sub 2} under visible light irradiation. Moreover, the effect of the Fe content of Fe-AO-PAN on dye degradation was also investigated. The results indicated that Fe (III) ions can crosslink between the modified PAN fiber chains by the coordination of Fe (III) ions with the amino nitrogen atoms and hydroxyl oxygen atoms of the amidoximation groups to form Fe (III)-amidoximated PAN fiber complex, and the Fe content of which is mainly determined by Fe (III) ions and amidoximation groups. Fe (III)-amidoximated PAN fiber complex is found to be activated in the visible light region. Moreover, Fe (III)-amidoximated PAN fiber complex shows the catalytic activity for dye degradation by H{sub 2}O{sub 2} at pH = 6.0 in the dark, and can be significantly enhanced by increasing light irradiation and Fe content, therefore, it can be used as a new heterogeneous Fenton photocatalyst for the effective decomposition of the dye in water. In addition, ESR spectra confirm that Fe (III)-amidoximated PAN fiber complex can generate more {center_dot}OH radicals from H{sub 2}O{sub 2} under visible light irradiation, leading to dye degradation. A possible mechanism of photocatalysis is proposed.

  10. Microbial Reduction of Fe(III) in Acidic Sediments: Isolation of Acidiphilium cryptum JF-5 Capable of Coupling the Reduction of Fe(III) to the Oxidation of Glucose

    OpenAIRE

    Küsel, Kirsten; Dorsch, Tanja; Acker, Georg; Stackebrandt, Erko

    1999-01-01

    To evaluate the microbial populations involved in the reduction of Fe(III) in an acidic, iron-rich sediment, the anaerobic flow of supplemental carbon and reductant was evaluated in sediment microcosms at the in situ temperature of 12°C. Supplemental glucose and cellobiose stimulated the formation of Fe(II); 42 and 21% of the reducing equivalents that were theoretically obtained from glucose and cellobiose, respectively, were recovered in Fe(II). Likewise, supplemental H2 was consumed by acid...

  11. Biological activity of Fe(III) aquo-complexes towards ferric chelate reductase (FCR).

    Science.gov (United States)

    Escudero, Rosa; Gómez-Gallego, Mar; Romano, Santiago; Fernández, Israel; Gutiérrez-Alonso, Ángel; Sierra, Miguel A; López-Rayo, Sandra; Nadal, Paloma; Lucena, Juan J

    2012-03-21

    In this study we have obtained experimental evidence that confirms the high activity of aquo complexes III and IV towards the enzyme FCR, responsible for the reduction of Fe(III) to Fe(II) in the process of iron acquisition by plants. The in vivo FCR assays in roots of stressed cucumber plants have shown a higher efficiency of the family of complexes III and a striking structure-activity relationship with the nature of the substituent placed in a phenyl group far away from the metal center. The results obtained in this work demonstrate that all the aquo compounds tested interact efficiently with the enzyme FCR and hence constitute a new concept of iron chelates that could be of great use in agronomy.

  12. Fe(II-III) Hydroxysalt Green Rusts; from Corrosion to Mineralogy and Abiotic to Biotic Reactions by Moessbauer Spectroscopy

    International Nuclear Information System (INIS)

    Genin, J.-M. R.

    2004-01-01

    Fe(II)-Fe(III) hydroxysalts commonly called green rusts are layered double hydroxides of formula [Fe II (1-x) Fe III x (OH) 2 ] x+ .[(x/n)A n- .(m/n)H 2 O] x- constituted of brucite-like layers containing Fe cations in the centres of OH - octahedrons and interlayers, which anions and water molecules belong to. They play a key role in corrosion and environmental sciences as well as mineralogy since they are, on the one hand, intermediate products between Fe(II) and Fe(III) states and, on the other hand, can be the major iron-bearing mineral in hydromorphic gley soils. Their crystal structure, Moessbauer spectra, methods of synthesis, abiotic as well as biotic, and some applications are presented here.

  13. Electron transfer and atom exchange between aqueous Fe(II) and structural Fe(III) in clays. Role in U and Hg(II) transformations

    Energy Technology Data Exchange (ETDEWEB)

    Scherer, Michelle [Univ. of Iowa, Iowa City, IA (United States)

    2016-08-31

    During this project, we investigated Fe electron transfer and atom exchange between aqueous Fe(II) and structural Fe(III) in clay minerals. We used selective chemical extractions, enriched Fe isotope tracer experiments, computational molecular modeling, and Mössbauer spectroscopy. Our findings indicate that structural Fe(III) in clay minerals is reduced by aqueous Fe(II) and that electron transfer occurs when Fe(II) is sorbed to either basal planes and edge OH-groups of clay mineral. Findings from highly enriched isotope experiments suggest that up to 30 % of the Fe atoms in the structure of some clay minerals exhanges with aqueous Fe(II). First principles calculations using a small polaron hopping approach suggest surprisingly fast electron mobility at room temperature in a nontronite clay mineral and are consistent with temperature dependent Mössbauer data Fast electron mobility suggests that electrons may be able to conduct through the mineral fast enough to enable exchange of Fe between the aqueous phase and clay mineral structure. over the time periods we observed. Our findings suggest that Fe in clay minerals is not as stable as previously thought.

  14. Effects of two iron sources on iron and cadmium allocation in poplar (populus alba) plants exposed to cadmium

    Energy Technology Data Exchange (ETDEWEB)

    Fodor, F.; Gaspar, L.; Cseh, E.; Sarvari, E. [Eotvos Univ., Budapest (Hungary). Dept. of Plant Physiology; Morales, F.; Gogorcena, Y.; Abadia, J. [Consejo Superior de Investigaciones Cientificas, Zaragoza (Spain). Dept. de Nutricion Vegetal; Lucena, J.J. [Madrid Univ., Madrid (Spain). Dept. de Quimica Agricola; Kropfl, K. [Eotvos Univ., Budapest (Hungary). Dept. of Technology and Environmental Chemistry

    2005-09-01

    The phytotoxicity of heavy metals is often manifested as inhibition of plant growth, nitrate assimilation and photosynthesis, as well as disturbances in plant ion and water balances. Many of these plant responses are a result of inhibition of enzyme activity caused by the binding of heavy metal ions to sulfhydryl groups in the active sites of enzymes and by substitution of essential metals. This study investigated the effects of cadmium (Cd) nitrate on the utilization and allocation of iron (Fe) in poplar plants grown in a nutrient solution with Fe(III)-EDTA or Fe(III)-citrate as the Fe source. The effects of Cd were also compared with those of Fe deprivation. Results indicated that the accumulation of Fe in roots was 10-fold higher in plants grown with Fe-citrate than with Fe-ETDA. In addition, cadmium increased leaf chlorophyll concentrations and photosynthetic rates, and these decreases were more marked in plants grown with Fe-citrate than with Fe-EDTA. In both treatments, addition of Cd caused large increases in root and shoot apoplasmic and non-apoplasmic Cd contents and increases in root Fe content. However, Cd decreased shoot Fe content, especially in plants grown with Fe-citrate. New leaves of plants grown with Fe-citrate had small cellular Fe pools, whereas these pools were large in new leaves of plants grown with Fe-EDTA. Non-apoplasmic Cd pools in new leaves were smaller in plants grown with Fe-citrate than with Fe-EDTA, which indicated that inactivation of non-apoplasmic Cd pools is facilitated more by Fe-EDTA than by Fe-citrate. In the presence of Cd, Fe-EDTA was also superior to Fe-citrate in maintaining an adequate Fe supply to poplar shoots. It was concluded that because the amount of non-apoplasmic root Fe was higher in plants grown with Fe-citrate than with Fe-EDTA, the observed differences in plant responses to Fe-EDTA and Fe-citrate may reflect distances in long-distance transport of Fe rather than its acquisition of Fe by roots. 42 refs., 6

  15. Kinetics of microbial Fe(III) oxyhydroxide reduction : The role of mineral properties

    NARCIS (Netherlands)

    Bonneville, S.C.

    2005-01-01

    In many soils, sediments and groundwaters, ferric iron is a major potential electron acceptor for the oxidation of organic matter. In contrast to other terminal electron acceptors (e.g. nitrate or sulfate), the concentration of Fe3+(aq), is limited by the low solubility of Fe(III) oxyhydroxides

  16. Synthesis of peptide templated copper nanoclusters for fluorometric determination of Fe(III) in human serum

    International Nuclear Information System (INIS)

    Tang, Ting; Ouyang, Jiang; Hu, Lanshuang; Guo, Linyan; Yang, Minghui; Chen, Xiang

    2016-01-01

    Copper nanoclusters (Cu-NCs) were prepared by reducing CuCl 2 with ascorbic acid in the presence of the short peptide template Cys-Cys-Cys-Asp-Leu. They were characterized by UV-vis absorption and fluorescence spectroscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. The Cu-NCs have a size of ∼2 nm, can be well dispersed in water and are photostable. Their fluorescence (peaking at 425 nm under 365-nm excitation) is quenched by Fe(III) ions. Based on this finding, a sensitive and selective fluorescence assay for the detection of Fe(III) was developed. Under optimized conditions and a pH value of 2.0, the assay displays a linear response in the 0.05 to 30 μM Fe(III) concentration range, with a detection limit of 20 nM based on an S/N ratio of 3. The assay was successfully applied to the determination of Fe(III) in spiked human serum where is gave recoveries that ranged from 96.2 % to 98.3 %. (author)

  17. Degradation of two fluoroquinolone antibiotics photoinduced by Fe(III)-microalgae suspension in an aqueous solution.

    Science.gov (United States)

    Ge, Liyun; Deng, Huanhuan

    2015-04-01

    The widespread presence of fluoroquinolone antibiotics (FQs) in natural ecosystems is a health hazard for humans and other living organisms. In this work, the photochemical degradation process of two antibiotics in the presence of Fe(III) and marine microalgae has been studied. Two fluoroquinolone (FQ) antibiotics, enrofloxacin (ENR) and ciprofloxacin hydrochloride (CIP), and two marine microalgae, Platymonas subcordiformis and Isochrysis galbana, were investigated under irradiation with a high-pressure mercury lamp (HPML) in a laboratory-scale experiment. The effects of the initial concentration of antibiotics on the degradation of these two FQs in Fe(III)-algae suspensions were also investigated. On the basis of the information in this study, compared to other systems, the efficiency of photo-degradation of the two FQs is better at lower FQ concentrations in the Fe(III)-algae system. Moreover, the low initial concentration of antibiotics benefits the photochemical process of antibiotics. This work demonstrated that the Fe(III)-algae system is an interesting and valuable research area and could be considered as a promising photochemical system for seawater remediation.

  18. Removal of lead from aqueous solutions by using the natural and Fe(III)-modified zeolite

    International Nuclear Information System (INIS)

    Kragović, Milan; Daković, Aleksandra; Sekulić, Živko; Trgo, Marina; Ugrina, Marin; Perić, Jelena; Gatta, G. Diego

    2012-01-01

    In the present study, the sorption of lead by the natural and Fe(III)-modified zeolite (clinoptilolite) is described. The characterization of the natural zeolite-rich rock and the Fe(III)-modified form was performed by chemical analysis, point of the zero charge (pH pzc ), X-ray powder diffraction, applying the Rietveld/RIR method for the quantitative phase analysis, and scanning electron microscopy. The effects of sorbents dose and the initial lead concentrations on its sorption by two sorbents were investigated. For both sorbents, it was determined that at lower initial concentrations of lead, ion exchange of inorganic cations in zeolites with lead, together with uptake of hydrogen dominated, while at higher initial lead concentrations beside these processes, chemisorption of lead occurred. Significantly higher sorption of lead was achieved with Fe(III)-modified zeolite. From sorption isotherms, maximum sorbed amounts of lead, under the applied experimental conditions, were 66 mg/g for the natural and 133 mg/g for Fe(III)-modified zeolite. The best fit of experimental data was achieved with the Freundlich model (R 2 ≥ 0.94).

  19. Effect of metal ion Fe(III on the performance of chlorophyll as photosensitizers on dye sensitized solar cell

    Directory of Open Access Journals (Sweden)

    Harsasi Setyawati

    Full Text Available The energy crisis is a major problem facing the world today and will need a renewable energy source that is environmentally friendly; one of these is the dye sensitized solar cell (DSSC. DSSC is photochemical electric cell that can convert solar energy into electrical energy. This research aims to study the characteristics of chlorophyll compounds with the addition of metal ions Fe(III and to determine the effect of Fe(III on the performance of chlorophyll as a photosensitizer in the DSSC. The formation of complex compounds of Fe(III-chlorophyll is shown by the phenomenon of metal ligand charge transfer (MLCT at a wavelength of 263.00 nm and absorption transition d-d at 745.00 nm. Fourier transform infrared characterization of the binding of Fe-O complex compounds appears at 486.06 cm−1. The complex compound of Fe(III-chlorophyll has a magnetic moment value of 9.62 Bohr Magneton (BM. The existence of ion Fe(III in chlorophyll can improve the performance of chlorophyll as a dye sensitizer with a maximum current of 4.00 mA/cm2, maximum voltage of 0.18 volts and efficiency values of 1.35%. Keywords: Fe(III-chlorophyll, Dye sensitized solar cell, Metal ligand charge transfer, Photosensitizer

  20. Identification of Multiple Soluble Fe(III Reductases in Gram-Positive Thermophilic Bacterium Thermoanaerobacter indiensis BSB-33

    Directory of Open Access Journals (Sweden)

    Subrata Pal

    2014-01-01

    Full Text Available Thermoanaerobacter indiensis BSB-33 has been earlier shown to reduce Fe(III and Cr(VI anaerobically at 60°C optimally. Further, the Gram-positive thermophilic bacterium contains Cr(VI reduction activity in both the membrane and cytoplasm. The soluble fraction prepared from T. indiensis cells grown at 60°C was found to contain the majority of Fe(III reduction activity of the microorganism and produced four distinct bands in nondenaturing Fe(III reductase activity gel. Proteins from each of these bands were partially purified by chromatography and identified by mass spectrometry (MS with the help of T. indiensis proteome sequences. Two paralogous dihydrolipoamide dehydrogenases (LPDs, thioredoxin reductase (Trx, NADP(H-nitrite reductase (Ntr, and thioredoxin disulfide reductase (Tdr were determined to be responsible for Fe(III reductase activity. Amino acid sequence and three-dimensional (3D structural similarity analyses of the T. indiensis Fe(III reductases were carried out with Cr(VI reducing proteins from other bacteria. The two LPDs and Tdr showed very significant sequence and structural identity, respectively, with Cr(VI reducing dihydrolipoamide dehydrogenase from Thermus scotoductus and thioredoxin disulfide reductase from Desulfovibrio desulfuricans. It appears that in addition to their iron reducing activity T. indiensis LPDs and Tdr are possibly involved in Cr(VI reduction as well.

  1. Advanced Experimental Analysis of Controls on Microbial Fe(III) Oxide Reduction - Final Report - 09/16/1996 - 03/16/2001; FINAL

    International Nuclear Information System (INIS)

    Roden, Eric E.

    2001-01-01

    Considering the broad influence that microbial Fe(III) oxide reduction can have on subsurface metal/organic contaminant biogeochemistry, understanding the mechanisms that control this process is critical for predicting the behavior and fate of these contaminants in anaerobic subsurface environments. Knowledge of the factors that influence the rates of growth and activity of Fe(III) oxide-reducing bacteria is critical for predicting (i.e., modeling) the long-term influence of these organisms on the fate of contaminants in the subsurface, and for effectively utilizing Fe(III) oxide reduction and associated geochemical affects for the purpose of subsurface metal/organic contamination bioremediation. This research project will refine existing models for microbiological and geochemical controls on Fe(III) oxide reduction, using laboratory reactor systems that mimic, to varying degrees, the physical and chemical conditions of the subsurface. Novel experimental methods for studying the kinetics of microbial Fe(III) oxide reduction and measuring growth rates of Fe(III) oxide-reducing bacteria will be developed. These new methodologies will be directly applicable to studies on subsurface contaminant transformations directly coupled to or influenced by microbial Fe(III) oxide reduction

  2. Revisiting the iron pools in cucumber roots: identification and localization.

    Science.gov (United States)

    Kovács, Krisztina; Pechoušek, Jiří; Machala, Libor; Zbořil, Radek; Klencsár, Zoltán; Solti, Ádám; Tóth, Brigitta; Müller, Brigitta; Pham, Hong Diep; Kristóf, Zoltán; Fodor, Ferenc

    2016-07-01

    Fe deficiency responses in Strategy I causes a shift from the formation of partially removable hydrous ferric oxide on the root surface to the accumulation of Fe-citrate in the xylem. Iron may accumulate in various chemical forms during its uptake and assimilation in roots. The permanent and transient Fe microenvironments formed during these processes in cucumber which takes up Fe in a reduction based process (Strategy I) have been investigated. The identification of Fe microenvironments was carried out with (57)Fe Mössbauer spectroscopy and immunoblotting, whereas reductive washing and high-resolution microscopy was applied for the localization. In plants supplied with (57)Fe(III)-citrate, a transient presence of Fe-carboxylates in removable forms and the accumulation of partly removable, amorphous hydrous ferric oxide/hydroxyde have been identified in the apoplast and on the root surface, respectively. The latter may at least partly be the consequence of bacterial activity at the root surface. Ferritin accumulation did not occur at optimal Fe supply. Under Fe deficiency, highly soluble ferrous hexaaqua complex is transiently formed along with the accumulation of Fe-carboxylates, likely Fe-citrate. As (57)Fe-citrate is non-removable from the root samples of Fe deficient plants, the major site of accumulation is suggested to be the root xylem. Reductive washing results in another ferrous microenvironment remaining in the root apoplast, the Fe(II)-bipyridyl complex, which accounts for ~30 % of the total Fe content of the root samples treated for 10 min and rinsed with CaSO4 solution. When (57)Fe(III)-EDTA or (57)Fe(III)-EDDHA was applied as Fe-source higher soluble ferrous Fe accumulation was accompanied by a lower total Fe content, confirming that chelates are more efficient in maintaining soluble Fe in the medium while less stable natural complexes as Fe-citrate may perform better in Fe accumulation.

  3. FeS-coated sand for removal of arsenic(III) under anaerobic conditions in permeable reactive barriers

    Science.gov (United States)

    Han, Y.-S.; Gallegos, T.J.; Demond, A.H.; Hayes, K.F.

    2011-01-01

    Iron sulfide (as mackinawite, FeS) has shown considerable promise as a material for the removal of As(III) under anoxic conditions. However, as a nanoparticulate material, synthetic FeS is not suitable for use in conventional permeable reactive barriers (PRBs). This study developed a methodology for coating a natural silica sand to produce a material of an appropriate diameter for a PRB. Aging time, pH, rinse time, and volume ratios were varied, with a maximum coating of 4.0 mg FeS/g sand achieved using a pH 5.5 solution at a 1:4 volume ratio (sand: 2 g/L FeS suspension), three days of aging and no rinsing. Comparing the mass deposited on the sand, which had a natural iron-oxide coating, with and without chemical washing showed that the iron-oxide coating was essential to the formation of a stable FeS coating. Scanning electron microscopy images of the FeS-coated sand showed a patchwise FeS surface coating. X-ray photoelectron spectroscopy showed a partial oxidation of the Fe(II) to Fe(III) during the coating process, and some oxidation of S to polysulfides. Removal of As(III) by FeS-coated sand was 30% of that by nanoparticulate FeS at pH 5 and 7. At pH 9, the relative removal was 400%, perhaps due to the natural oxide coating of the sand or a secondary mineral phase from mackinawite oxidation. Although many studies have investigated the coating of sands with iron oxides, little prior work reports coating with iron sulfides. The results suggest that a suitable PRB material for the removal of As(III) under anoxic conditions can be produced through the deposition of a coating of FeS onto natural silica sand with an iron-oxide coating. ?? 2010 Elsevier Ltd.

  4. Synchrotron radiation photoelectron spectroscopy study of dextran-coated Fe3O4 magnetic nanoparticles

    International Nuclear Information System (INIS)

    Li Shaoxia; Meng Qiang; Wang Bing; Feng Weiyue; Wang Zhuo; Kui Rexi; Qian Haijie; Wang Jia'o

    2009-01-01

    Dextran-coated Fe 3 O 4 nanoparticles were prepared by untrasonification of Fe 3 O 4 nanoparticles with dextran at 85 degree C in sodium citrate medium. The surface chemical component, structure and bond of uncoated and dextran-coated nanoparticles were measured by synchrotron radiation XPS(X-ray photoelectron spectroscopy). Qualitative and quantitative analysis of C1s and O1s of Fe 3 O 4 and dextran-Fe 3 O 4 showed that the Fe 3 O 4 nanoparticles were successively coated by sodium citrate via Fe-O-C bond, and dextrans, which can be linked with their carboxylate moiety via hydrogen bond. Sodium citrate could enhance the disperse stability of reaction system and hydrophilicity of dextran-Fe 3 O 4 . (authors)

  5. Fe(III)-loaded collagen fiber as a heterogeneous catalyst for the photo-assisted decomposition of Malachite Green

    International Nuclear Information System (INIS)

    Liu Xiaohu; Tang Rui; He Qiang; Liao Xuepin; Shi Bi

    2010-01-01

    A heterogeneous catalyst for Fenton reaction was prepared by immobilizing Fe(III) onto collagen fiber and its catalytic activity for the photo-assisted decomposition of Malachite Green (MG) was investigated. The results indicated that this Fe(III)-immobilized collagen fiber (Fe-CF) can effectively catalyse the decoloration and decomposition/mineralization of MG in aqueous solution. Catalysed by Fe-CF, MG solution was completely decolorized in 30 min, while 55.0% of TOC was removed from the dye solution within 120 min in the presence of H 2 O 2 and UVA irradiation (365 nm, 10 W). Fe-CF was recycled for seven times with certain activity loss (32.6% in decoloration, 18.5% in TOC removal), and its catalytic activity can be easily recovered by re-immobilization of Fe(III). Therefore, Fe-CF could act as an efficient and cost-effective catalyst for the photo-assisted decomposition of MG, and shows potential applications in practice.

  6. Gene expression correlates with process rates quantified for sulfate- and Fe(III-reducing bacteria in U(VI-contaminated sediments

    Directory of Open Access Journals (Sweden)

    Denise M Akob

    2012-08-01

    Full Text Available Though iron- and sulfate-reducing bacteria are well known for mediating uranium(VI reduction in contaminated subsurface environments, quantifying the in situ activity of the microbial groups responsible remains a challenge. The objective of this study was to demonstrate the use of quantitative molecular tools that target mRNA transcripts of key genes related to Fe(III and sulfate reduction pathways in order to monitor these processes during in situ U(VI remediation in the subsurface. Expression of the Geobacteraceae-specific citrate synthase gene (gltA and the dissimilatory (bisulfite reductase gene (dsrA, were correlated with the activity of iron- or sulfate-reducing microorganisms, respectively, under stimulated bioremediation conditions in microcosms of sediments sampled from the U.S. Department of Energy’s Oak Ridge Integrated Field Research Challenge (OR-IFRC site at Oak Ridge, Tennessee. In addition, Geobacteraceae-specific gltA and dsrA transcript levels were determined in parallel with the predominant electron acceptors present in moderately and highly contaminated subsurface sediments from the OR-IFRC. Phylogenetic analysis of the cDNA generated from dsrA mRNA, sulfate-reducing bacteria-specific 16S rRNA, and gltA mRNA identified activity of specific microbial groups. Active sulfate reducers were members of the Desulfovibrio, Desulfobacterium, and Desulfotomaculum genera. Members of the subsurface Geobacter clade, closely related to uranium-reducing Geobacter uraniireducens and Geobacter daltonii, were the metabolically-active iron-reducers in biostimulated microcosms and in situ core samples. Direct correlation of transcripts and process rates demonstrated evidence of competition between the functional guilds in subsurface sediments. We further showed that active populations of Fe(III-reducing bacteria and sulfate-reducing bacteria are present in OR-IFRC sediments and are good potential targets for in situ bioremediation.

  7. Flow Velocity Effects on Fe(III Clogging during Managed Aquifer Recharge Using Urban Storm Water

    Directory of Open Access Journals (Sweden)

    Xinqiang Du

    2018-03-01

    Full Text Available Storm water harvesting and storage has been employed for nearly a hundred years, and using storm water to recharge aquifers is one of the most important ways to relieve water scarcity in arid and semi-arid regions. However, it cannot be widely adopted because of clogging problems. The risk of chemical clogging is mostly associated with iron oxyhydroxide precipitation; anhydrous ferric oxide (HFO clogging remains a problem in many wellfields. This paper investigates Fe(III clogging levels at three flow velocities (Darcy velocities, 0.46, 1.62 and 4.55 m/d. The results indicate that clogging increases with flow velocity, and is mostly affected by the first 0–3 cm of the column. The highest water velocity caused full clogging in 35 h, whereas the lowest took 53 h to reach an stable 60% reduction in hydraulic conductivity. For the high flow velocity, over 90% of the HFO was deposited in the 0–1 cm section. In contrast, the lowest flow velocity deposited only 75% in this section. Fe(III deposition was used as an approximation for Fe(OH3. High flow velocity may promote Fe(OH3 flocculent precipitate, thus increasing Fe(III deposition. The main mechanism for a porous matrix interception of Fe(III colloidal particles was surface filtration. Thus, the effects of deposition, clogging phenomena, and physicochemical mechanisms, are more significant at higher velocities.

  8. Biogenic Fe(III) minerals lower the efficiency of iron-mineral based commercial filter systems for arsenic removal

    DEFF Research Database (Denmark)

    Kleinert, Susanne; Muehe, Eva M.; Posth, Nicole

    2011-01-01

    Millions of people worldwide are affected by As (arsenic) contaminated groundwater. Fe(III) (oxy)hydroxides sorb As efficiently and are therefore used in water purification filters. Commercial filters containing abiogenic Fe(III) (oxy)hydroxides (GEH) showed varying As removal, and it was unclear...

  9. Bacteria attenuation by iron electrocoagulation governed by interactions between bacterial phosphate groups and Fe(III) precipitates

    NARCIS (Netherlands)

    Delaire, Caroline; van Genuchten, Case M.; Amrose, Susan E.; Gadgil, Ashok J.

    2016-01-01

    Iron electrocoagulation (Fe-EC) is a low-cost process in which Fe(II) generated from an Fe(0) anode reacts with dissolved O2 to form (1) Fe(III) precipitates with an affinity for bacterial cell walls and (2) bactericidal reactive oxidants. Previous work suggests that Fe-EC is a promising treatment

  10. The Reduction of Cr(VI) to Cr(III) by Natural Fe-Bearing Minerals: A Synchrotron XAS Study

    Science.gov (United States)

    Xu, H.; Guo, X.; Ding, M.; Migdissov, A. A.; Boukhalfa, H.; Sun, C.; Roback, R. C.; Reimus, P. W.; Katzman, D.

    2017-12-01

    Cr(VI) in the form of CrO42- is a pollutant species in groundwater and soils that can pose health and environmental problems. Cr(VI) associated with use as a corrosion inhibitor at a power plant from 1956-1972 is present in a deep groundwater aquifer at Los Alamos National Laboratory. A potential remediation strategy for the Cr contamination is reduction of Cr(VI) to Cr(III) via the acceptance of electrons from naturally occurring or induced Fe(II) occurring in Fe-bearing minerals. In this work, using synchrotron-based X-ray techniques, we investigated the Cr reduction behavior by Fe-bearing minerals from outcrop and core samples representative of the contaminated portion of the aquifer. Samples were exposed to solutions with a range of known Cr (VI) concentrations. XANES and EXAFS spectra showed that all the Cr(VI) had been reduced to Cr(III), and micro XRF mapping revealed close correlation of Cr and Fe distribution, implying that Fe(II) in minerals reduced Cr(VI) in the solution. Similar behavior was observed from in-situ XANES measurements on Cr reduction and adsorption by mineral separates from the rock samples in Cr(VI)-bearing solutions. In addition, to obtain reference parameters for interpreting the data of natural samples, we collected Cr and Fe EXAFS spectra of Cr(III)-Fe(III) hydroxide solid solutions, which show progressive changes in the local structure around Cr and Fe over the whole series.

  11. Removal of Rhodamine B under visible irradiation in the presence of Fe⁰, H₂O₂, citrate and aeration at circumneutral pH.

    Science.gov (United States)

    Hong, Jun; Lu, Sijia; Zhang, Caixiang; Qi, Shihua; Wang, Yanxin

    2011-09-01

    A new Vis-Fe(0)-H(2)O(2)-citrate-O(2) system comprising zero-valent iron, hydrogen peroxide, citrate anion and aeration at circumneutral pH under visible irradiation was studied. 21 μmol L(-1) of Rhodamine B (RhB) was chosen as the substrate to be tested. Experiments were conducted under conditions of 2.9 mmol L(-1) of H(2)O(2), 12.6g of Fe(0) and 1.0 mmol L(-1) of citrate at pH 7.5. Results showed that, in 1h reaction, 54% of RhB was removed with corresponding 26% of COD reduced. Meanwhile, the amount of released dissolved irons from Fe(0) surface was found to be at a very low level as removal in 3h reaction. Control and factor influencing experiments showed that the prohibitive extents of individual factor importance on RhB removal followed a decreasing order of Fe(0)>H(2)O(2)>citrate>Vis>O(2). This study showed an excellent system that could remove refractory organic compounds from water in laboratory researches, and also provided a good idea to reduce secondary contamination by dissolved irons in future investigations. Copyright © 2011 Elsevier Ltd. All rights reserved.

  12. Production of hydroxyl radicals from abiotic oxidation of pyrite by oxygen under circumneutral conditions in the presence of low-molecular-weight organic acids

    Science.gov (United States)

    Zhang, Peng; Yuan, Songhu

    2017-12-01

    Besides acidic environments, pyrite oxidation also occurs in circumneutral environments, such as well-buffered marine and estuarine sediments and salt marshes where low-molecular-weight organic acids (LMWOAs) (e.g., citrate and oxalate) prevail. However, the production of hydroxyl radicals (radOH) from pyrite oxidation by oxygen (O2) in these circumneutral environments is poorly understood. In this study, radOH production was measured during the abiotic oxidation of pyrite by O2 under circumneutral conditions. A pyrite suspension (50 g/L pyrite) that was buffered at pH 6-8 was exposed to air for oxygenation in the dark. Benzoate (20 mM) was added into the suspension to trap radOH. At pH 7, the cumulative radOH reached 7.5 μM within 420 min in the absence of LMWOAs, whereas it increased to 14.8, 12 and 11.2 μM in the presence of 1 mM ethylenediaminotetraacetate, citrate and oxalate, respectively. When the citrate concentration, which serves as a LMWOAs model, was increased from 0.5 to 5 mM, the cumulative radOH increased from 10.3 to 27.3 μM within 420 min at pH 7. With the decrease in pH from 8 to 6, the cumulative radOH increased from 2.1 to 23.3 μM in the absence of LMWOAs, but it increased from 8.8 to 134.9 μM in the presence of 3 mM citrate. The presence of LMWOAs enhanced the radOH production from pyrite oxidation under circumneutral conditions. In the absence of LMOWAs, radOH is produced mostly from the oxidation of adsorbed Fe(II) by O2. In the presence of citrate, radOH production is attributed mainly to the oxidation of Fe(II)-citrate- by O2 and secondarily to the oxidation of H2O on surface-sulfur defects. The acceleration of pyrite oxidation by Fe(III)-citrate increases radOH production. Fe(II)-citrate- is generated mainly from the complexation of adsorbed Fe(II) by citrate and the reduction of Fe(III)-citrate, and the generation is suppressed by the oxidation of adsorbed Fe(II). Fe(III)-citrate is generated predominantly from Fe(II)-citrate

  13. Mechanisms for Electron Transfer Through Pili to Fe(III) Oxide in Geobacter

    Energy Technology Data Exchange (ETDEWEB)

    Lovley, Derek R. [Univ. of Massachusetts, Amherst, MA (United States)

    2015-03-09

    The purpose of these studies was to aid the Department of Energy in its goal of understanding how microorganisms involved in the bioremediation of metals and radionuclides sustain their activity in the subsurface. This information is required in order to incorporate biological processes into decision making for environmental remediation and long-term stewardship of contaminated sites. The proposed research was designed to elucidate the mechanisms for electron transfer to Fe(III) oxides in Geobacter species because Geobacter species are abundant dissimilatory metal-reducing microorganisms in a diversity of sites in which uranium is undergoing natural attenuation via the reduction of soluble U(VI) to insoluble U(IV) or when this process is artificially stimulated with the addition of organic electron donors. This study investigated the novel, but highly controversial, concept that the final conduit for electron transfer to Fe(III) oxides are electrically conductive pili. The specific objectives were to: 1) further evaluate the conductivity along the pili of Geobacter sulfurreducens and related organisms; 2) determine the mechanisms for pili conductivity; and 3) investigate the role of pili in Fe(III) oxide reduction. The studies demonstrated that the pili of G. sulfurreducens are conductive along their length. Surprisingly, the pili possess a metallic-like conductivity similar to that observed in synthetic organic conducting polymers such as polyaniline. Detailed physical analysis of the pili, as well as studies in which the structure of the pili was genetically modified, demonstrated that the metallic-like conductivity of the pili could be attributed to overlapping pi-pi orbitals of aromatic amino acids. Other potential mechanisms for conductivity, such as electron hopping between cytochromes associated with the pili were definitively ruled out. Pili were also found to be essential for Fe(III) oxide reduction in G. metallireducens. Ecological studies demonstrated

  14. Characterization of metal-bound water in bioactive Fe(III)-cyclophane complexes

    Science.gov (United States)

    Salazar-Medina, A. J.; Gámez-Corrales, R.; Ramírez, J. Z.; González-Aguilar, G. A.; Velázquez-Contreras, E. F.

    2018-02-01

    Binuclear Fe(III) complexes, Fe2PO and Fe2PC, have functions of antioxidants as well as superoxide dismutase and peroxidase mimickers. The role of water molecules in the non-cytotoxic properties of these complexes have been studied by thermogravimetric and IR/Raman-spectroscopic methods. The thermogravimetric analysis of Fe2PO shows the presence of nine water molecules (Fe2PO·9H2O), three of which are directly coordinated to the metallic ion; the remaining six molecules occupy the secondary coordination sphere. For Fe2PC, eight water molecules were detected (Fe2PC·8H2O), and only one of them directly coordinates to the metallic ion. IR/Raman spectrum analyses corroborate the presence of water molecules in both metallic complexes and the mode of coordination to the ligand, on the basis of bands characteristic of hydration water at ∼3300 cm-1 and bands of adsorbed water between 430 and 490 cm-1. A pentacoordinate geometry is proposed for Fe2PO and a hexacoordinated geometry for Fe2PC. Those results are consistent with theoretical calculations performed through a semiempirical PM7 method. The presence of coordinated water molecules is closely related to the reactivity of Fe2PO and Fe2PC in solution.

  15. Influence of dihydroxybenzenes on paracetamol and ciprofloxacin degradation and iron(III) reduction in Fenton processes.

    Science.gov (United States)

    Costa E Silva, Beatriz; de Lima Perini, João Angelo; Nogueira, Raquel F Pupo

    2017-03-01

    The degradation of paracetamol (PCT) and ciprofloxacin (CIP) was compared in relation to the generation of dihydroxylated products, Fe(III) reduction and reaction rate in the presence of dihydroxybenzene (DHB) compounds, or under irradiation with free iron (Fe 3+ ) or citrate complex (Fecit) in Fenton or photo-Fenton process. The formation of hydroquinone (HQ) was observed only during PCT degradation in the dark, which increased drastically the rate of PCT degradation, since HQ formed was able to reduce Fe 3+ and contributed to PCT degradation efficiency. When HQ was initially added, PCT and CIP degradation rate in the dark was much higher in comparison to the absence of HQ, due to the higher and faster formation of Fe 2+ at the beginning of reaction. In the absence of HQ, no CIP degradation was observed; however, when HQ was added after 30 min, the degradation rate increased drastically. Ten PCT hydroxylated intermediates were identified in the absence of HQ, which could contribute for Fe(III) reduction and consequently to the degradation in a similar way as HQ. During CIP degradation, only one product of hydroxyl radical attack on benzene ring and substitution of the fluorine atom was identified when HQ was added to the reaction medium.

  16. Cr(III), Fe(III) and Co(III) complexes of tetradentate (ONNO) Schiff base ligands: Synthesis, characterization, properties and biological activity

    Science.gov (United States)

    Keskioğlu, Eren; Gündüzalp, Ayla Balaban; Çete, Servet; Hamurcu, Fatma; Erk, Birgül

    2008-08-01

    A series of metal complexes were synthesized from equimolar amounts of Schiff bases: 1,4-bis[3-(2-hydroxy-1-naphthaldimine)propyl]piperazine (bappnaf) and 1,8-bis[3-(2-hydroxy-1-naphthaldimine)- p-menthane (damnaf) with metal chlorides. All of synthesized compounds were characterized by elemental analyses, spectral (UV-vis, IR, 1H- 13C NMR, LC-MS) and thermal (TGA-DTA) methods, magnetic and conductance measurements. Schiff base complexes supposed in tetragonal geometry have the general formula [M(bappnaf or damnaf)]Cl· nH 2O, where M = Cr(III), Co(III) and n = 2, 3. But also Fe(III) complexes have octahedral geometry by the coordination of two water molecules and the formula is [Fe(bappnaf or damnaf)(H 2O) 2]Cl. The changes in the selected vibration bands in FT-IR indicate that Schiff bases behave as (ONNO) tetradentate ligands and coordinate to metal ions from two phenolic oxygen atoms and two azomethine nitrogen atoms. Conductance measurements suggest 1:1 electrolytic nature of the metal complexes. The synthesized compounds except bappnaf ligand have the antimicrobial activity against the bacteria: Escherichia coli (ATCC 11230), Yersinia enterocolitica (ATCC 1501), Bacillus magaterium (RSKK 5117), Bacillus subtilis (RSKK 244), Bacillus cereus (RSKK 863) and the fungi: Candida albicans (ATCC 10239). These results have been considerably interest in piperazine derivatives due to their significant applications in antimicrobial studies.

  17. Cofortification of ferric pyrophosphate and citric acid/trisodium citrate into extruded rice grains doubles iron bioavailability through in situ generation of soluble ferric pyrophosphate citrate complexes.

    Science.gov (United States)

    Hackl, Laura; Cercamondi, Colin I; Zeder, Christophe; Wild, Daniela; Adelmann, Horst; Zimmermann, Michael B; Moretti, Diego

    2016-05-01

    Iron fortification of rice is a promising strategy for improving iron nutrition. However, it is technically challenging because rice is consumed as intact grains, and ferric pyrophosphate (FePP), which is usually used for rice fortification, has low bioavailability. We investigated whether the addition of a citric acid/trisodium citrate (CA/TSC) mixture before extrusion increases iron absorption in humans from FePP-fortified extruded rice grains. We conducted an iron absorption study in iron-sufficient young women (n = 20), in which each participant consumed 4 different meals (4 mg Fe/meal): 1) extruded FePP-fortified rice (No CA/TSC); 2) extruded FePP-fortified rice with CA/TSC added before extrusion (CA/TSC extruded); 3) extruded FePP-fortified rice with CA/TSC solution added after cooking and before consumption (CA/TSC solution); and 4) nonextruded rice fortified with a FeSO4 solution added after cooking and before consumption (reference). Iron absorption was calculated from erythrocyte incorporation of stable iron isotopes 14 d after administration. In in vitro experiments, we assessed the soluble and dialyzable iron from rice meals in which CA/TSC was added at different preparation stages and from meals with different iron:CA:TSC ratios. Fractional iron absorption was significantly higher from CA/TSC-extruded meals (3.2%) than from No CA/TSC (1.7%) and CA/TSC solution (1.7%; all P solubility and dialyzability were higher in CA/TSC-extruded rice than in rice with No CA/TSC and CA/TSC solution, and solubility increased with higher amounts of added CA and TSC in extruded rice. Iron bioavailability nearly doubled when CA/TSC was extruded with FePP into fortified rice, resulting in iron bioavailability comparable to that of FeSO4 We attribute this effect to an in situ generation of soluble FePP citrate moieties during extrusion and/or cooking because of the close physical proximity of FePP and CA/TSC in the extruded rice matrix. This trial was registered at

  18. Green rusts synthesis by coprecipitation of Fe II-Fe III ions and mass-balance diagram

    Science.gov (United States)

    Ruby, Christian; Aïssa, Rabha; Géhin, Antoine; Cortot, Jérôme; Abdelmoula, Mustapha; Génin, Jean-Marie

    2006-06-01

    A basic solution is progressively added to various mixed Fe II-Fe III solutions. The nature and the relative quantities of the compounds that form can be visualised in a mass-balance diagram. The formation of hydroxysulphate green rust {GR( SO42-)} is preceded by the precipitation of a sulphated ferric basic salt that transforms in a badly ordered ferric oxyhydroxide. Then octahedrally coordinated Fe II species and SO42- anions are adsorbed on the FeOOH surface and GR( SO42-) is formed at the solid/solution interface. By using the same method of preparation, other types of green rust were synthesised, e.g. hydroxycarbonate green rust {GR( CO32-)}. Like other layered double hydroxides, green rusts obey the general chemical formula [ṡ[ṡmHO]x+ with x⩽1/3. Al-substituted hydroxysulphate green rust consists of small hexagonal crystals with a lateral size ˜50 nm, which is significantly smaller than the size of the GR( SO42-) crystals (˜500 nm). To cite this article: C. Ruby et al., C. R. Geoscience 338 (2006).

  19. Enhanced biotic and abiotic transformation of Cr(vi) by quinone-reducing bacteria/dissolved organic matter/Fe(iii) in anaerobic environment.

    Science.gov (United States)

    Huang, Bin; Gu, Lipeng; He, Huan; Xu, Zhixiang; Pan, Xuejun

    2016-09-14

    This study investigated the simultaneous transformation of Cr(vi) via a closely coupled biotic and abiotic pathway in an anaerobic system of quinone-reducing bacteria/dissolved organic matters (DOM)/Fe(iii). Batch studies were conducted with quinone-reducing bacteria to assess the influences of sodium formate (NaFc), electron shuttling compounds (DOM) and the Fe(iii) on Cr(vi) reduction rates as these chemical species are likely to be present in the environment during in situ bioremediation. Results indicated that the concentration of sodium formate and anthraquinone-2-sodium sulfonate (AQS) had apparently an effect on Cr(vi) reduction. The fastest decrease in rate for incubation supplemented with 5 mM sodium formate and 0.8 mM AQS showed that Fe(iii)/DOM significantly promoted the reduction of Cr(vi). Presumably due to the presence of more easily utilizable sodium formate, DOM and Fe(iii) have indirect Cr(vi) reduction capability. The coexisting cycles of Fe(ii)/Fe(iii) and DOM(ox)/DOM(red) exhibited a higher redox function than the individual cycle, and their abiotic coupling action can significantly enhance Cr(vi) reduction by quinone-reducing bacteria.

  20. Colorimetric method for enzymatic screening assay of ATP using Fe(III)-xylenol orange complex formation.

    Science.gov (United States)

    Ishida, Akihiko; Yamada, Yasuko; Kamidate, Tamio

    2008-11-01

    In hygiene management, recently there has been a significant need for screening methods for microbial contamination by visual observation or with commonly used colorimetric apparatus. The amount of adenosine triphosphate (ATP) can serve as the index of a microorganism. This paper describes the development of a colorimetric method for the assay of ATP, using enzymatic cycling and Fe(III)-xylenol orange (XO) complex formation. The color characteristics of the Fe(III)-XO complexes, which show a distinct color change from yellow to purple, assist the visual observation in screening work. In this method, a trace amount of ATP was converted to pyruvate, which was further amplified exponentially with coupled enzymatic reactions. Eventually, pyruvate was converted to the Fe(III)-XO complexes through pyruvate oxidase reaction and Fe(II) oxidation. As the assay result, yellow or purple color was observed: A yellow color indicates that the ATP concentration is lower than the criterion of the test, and a purple color indicates that the ATP concentration is higher than the criterion. The method was applied to the assay of ATP extracted from Escherichia coli cells added to cow milk.

  1. Thermodynamic model for solution behavior and solid-liquid equilibrium in Na-Al(III)-Fe(III)-Cr(III)-Cl-H2O system at 25°C

    Science.gov (United States)

    André, Laurent; Christov, Christomir; Lassin, Arnault; Azaroual, Mohamed

    2018-03-01

    The knowledge of the thermodynamic behavior of multicomponent aqueous electrolyte systems is of main interest in geo-, and environmental-sciences. The main objective of this study is the development of a high accuracy thermodynamic model for solution behavior, and highly soluble M(III)Cl3(s) (M= Al, Fe, Cr) minerals solubility in Na-Al(III)-Cr(III)-Fe(III)-Cl-H2O system at 25°C. Comprehensive thermodynamic models that accurately predict aluminium, chromium and iron aqueous chemistry and M(III) mineral solubilities as a function of pH, solution composition and concentration are critical for understanding many important geochemical and environmental processes involving these metals (e.g., mineral dissolution/alteration, rock formation, changes in rock permeability and fluid flow, soil formation, mass transport, toxic M(III) remediation). Such a model would also have many industrial applications (e.g., aluminium, chromium and iron production, and their corrosion, solve scaling problems in geothermal energy and oil production). Comparisons of solubility and activity calculations with the experimental data in binary and ternary systems indicate that model predictions are within the uncertainty of the data. Limitations of the model due to data insufficiencies are discussed. The solubility modeling approach, implemented to the Pitzer specific interaction equations is employed. The resulting parameterization was developed for the geochemical Pitzer formalism based PHREEQC database.

  2. Spectrophotometric determination of dopamine hydrochloride in pharmaceutical, banana, urine and serum samples by potassium ferricyanide-Fe(III).

    Science.gov (United States)

    Guo, Li; Zhang, Yan; Li, Quanmin

    2009-12-01

    In the present work, we developed a simple, sensitive and inexpensive method to determine dopamine hydrochloride using potassium ferricyanide-Fe(III) by spectrophotometry. The results show that Fe(III) is deoxidized to Fe(II) by dopamine hydrochloride at pH 4.0, and then Fe(II) reacts with potassium ferricyanide to form a soluble prussian blue (KFe(III)[Fe(II)(CN)6]). The absorbance of this product was monitored over time using a spectrophotometer at an absorption maximum of 735 nm, and the amount of dopamine hydrochloride could be calculated based on the absorbance. A good linear relationship of the concentration of dopamine hydrochloride versus absorbance was observed, and a linear regression equation of A = 0.022 + 0.16921C (microg mL(-1)) was obtained. Moreover, the apparent molar absorption coefficient for the indirect determination of dopamine hydrochloride was 3.2 x 10(4) L mol(-1) cm(-1). This described method has been used to determine dopamine hydrochloride in pharmaceutical, banana, urine and serum samples with satisfactory results.

  3. Iron overload of human colon adenocarcinoma cells studied by synchrotron-based X-ray techniques

    NARCIS (Netherlands)

    Mihucz, Victor G.; Meirer, Florian; Polgári, Zsófia; Réti, Andrea; Pepponi, Giancarlo; Ingerle, Dieter; Szoboszlai, Norbert; Streli, Christina

    2016-01-01

    Fast- and slow-proliferating human adenocarcinoma colorectal cells, HT-29 and HCA-7, respectively, overloaded with transferrin (Tf), Fe(III) citrate, Fe(III) chloride and Fe(II) sulfate were studied by synchrotron radiation total-reflection X-ray spectrometry (TXRF), TXRF-X-ray absorption near edge

  4. Affinity for a malignant tumor and organs of sup(99m)Tc-citrate complex

    Energy Technology Data Exchange (ETDEWEB)

    Ando, A; Sanada, S; Hiraki, T [Kanazawa Univ. (Japan). School of Paramedicine; Hisada, K; Nakazawa, N

    1976-12-01

    In order to investigate the tumor affinity of sup(99m)Tc-citrate complex, it was synthesized in three different ways. By (1) reducing sup(99m)TcO/sub 4//sup -/ with FeCl/sub 3//sup -/ ascorbic acid in 0.15 M sodium citrate, (2) reducing sup(99m)TcO/sub 4//sup -/ with SnCl/sub 2/ solution in 0.15 M sodium citrate, and (3) reducing sup(99m)TcO/sub 4//sup -/ with NaBH/sub 4/ in 0.45 sodium citrate. It was presumed from thinlayer chromatography that the sup(99m)Tc-citrate complexes synthesized in three ways were chemically different. These sup(99m)Tc-citrate complexes were injected intravenously into the rats subcutaneously transplanted with Yoshida sarcoma. These rats were sacrificed at one hour and three hours after injection. The radioactivity of the tumor, blood, muscle, liver, kidney, spleen and urine was measured by well-type scintillation counter. The retention values in these organs and the excretion rates in the urine were calculated. sup(99m)Tc-citrate complex synthesized by reducing sup(99m)TcO/sub 4//sup -/ with SnCl/sub 2/ solution had very strong affinity for the malignant tumor but the other two sup(99m)Tc-citrate complexes had no affinity to the malignant tumor. Excretion rates (% dose) of sup(99m)Tc-citrate complexes in one hour were from 65% to 75%.

  5. Arsenic removal from alkaline leaching solution using Fe (III) precipitation.

    Science.gov (United States)

    Wang, Yongliang; Lv, Cuicui; Xiao, Li; Fu, Guoyan; Liu, Ya; Ye, Shufeng; Chen, Yunfa

    2018-02-02

    The alkaline leaching solution from arsenic-containing gold concentrate contains a large amount of arsenate ions, which should be removed because it is harmful to the production process and to the environment. In this study, conventional Fe (III) precipitation was used to remove arsenic from the leaching solution. The precipitation reaction was carried out at the normal temperature, and the effects of pH value and Fe/As ratio on the arsenic removal were investigated. The results show that the removal rate of arsenic is distinctive at different pH values, and the effect is best within the pH range of 5.25-5.96. The removal rate can be further increased by increasing the ratio of Fe/As. When the pH = 5.25-5.96 and Fe/As > 1.8, the arsenic in the solution can be reduced to below 5 mg/L. However, the crystallinity of ferric arsenate is poor, and the particle size is small, most of which is about 1 μm. The leaching toxicity test shows the leaching toxicity of precipitates gradually decreased by the increase of Fe/As. The precipitates can be stored safely as the ratio of Fe/As exceeded 2.5.

  6. Coordination polymers of Fe(iii) and Al(iii) ions with TCA ligand: distinctive fluorescence, CO2 uptake, redox-activity and oxygen evolution reaction.

    Science.gov (United States)

    Dhara, Barun; Sappati, Subrahmanyam; Singh, Santosh K; Kurungot, Sreekumar; Ghosh, Prasenjit; Ballav, Nirmalya

    2016-04-28

    Fe and Al belong to different groups in the periodic table, one from the p-block and the other from the d-block. In spite of their different groups, they have the similarity of exhibiting a stable 3+ oxidation state. Here we have prepared Fe(iii) and Al(iii) based coordination polymers in the form of metal-organic gels with the 4,4',4''-tricarboxyltriphenylamine (TCA) ligand, namely Fe-TCA and Al-TCA, and evaluated some important physicochemical properties. Specifically, the electrical conductivity, redox-activity, porosity, and electrocatalytic activity (oxygen evolution reaction) of the Fe-TCA system were noted to be remarkably higher than those of the Al-TCA system. As for the photophysical properties, almost complete quenching of the fluorescence originating from TCA was observed in case of the Fe-TCA system, whereas for the Al-TCA system a significant retention of fluorescence with red-shifted emission was observed. Quantum mechanical calculations based on density functional theory (DFT) were performed to unravel the origin of such discriminative behaviour of these coordination polymer systems.

  7. FecB, a periplasmic ferric-citrate transporter from E. coli, can bind different forms of ferric-citrate as well as a wide variety of metal-free and metal-loaded tricarboxylic acids.

    Science.gov (United States)

    Banerjee, Sambuddha; Paul, Subrata; Nguyen, Leonard T; Chu, Byron C H; Vogel, Hans J

    2016-01-01

    The Escherichia coli Fec system, consisting of an outer membrane receptor (FecA), a periplasmic substrate binding protein (FecB) and an inner membrane permease-ATPase type transporter (FecC/D), plays an important role in the uptake and transport of Fe(3+)-citrate. Although several FecB sequences from various organisms have been reported, there are no biophysical or structural data available for this protein to date. In this work, using isothermal titration calorimetry (ITC), we report for the first time the ability of FecB to bind different species of Fe(3+)-citrate as well as other citrate complexes with trivalent (Ga(3+), Al(3+), Sc(3+) and In(3+)) and a representative divalent metal ion (Mg(2+)) with low μM affinity. Interestingly, ITC experiments with various iron-free di- and tricarboxylic acids show that FecB can bind tricarboxylates with μM affinity but not biologically relevant dicarboxylates. The ability of FecB to bind with metal-free citrate is also observed in (1)H,(15)N HSQC-NMR titration experiments reported here at two different pH values. Further, differential scanning calorimetry (DSC) experiments indicate that the ligand-bound form of FecB has greater thermal stability than ligand-free FecB under all pH and ligand conditions tested, which is consistent with the idea of domain closure subsequent to ligand binding for this type of periplasmic binding proteins.

  8. Modification of Natural Zeolite with Fe(III) and Its Application as Adsorbent Chloride and Carbonate ions

    Science.gov (United States)

    Suhartana; Sukmasari, Emmanuella; Azmiyawati, Choiril

    2018-04-01

    The aim of the research is to natural zeolite with Fe(III) using anion exchange process to improve the anion exchange capacity. Natural zeolite was activated using HNO3 1 N and then mixed with FeCl3 solution and refluxed followed by oven and calcination at a temperature of 550°C. The influence of Fe(III) to zeolite was characterized by FTIR while presence of Fe in zeolite characterized by AAS. Zeolite and Zeolite-Fe adsorption capacity of chloride and carbonate anions were determined through adsorption test by variation of pH and contact time. In advanced, and then to determining the Fe adsorbed concentration at Zeolite using UV-Vis spectrophotometer. FTIR analysis result showed that the addition of Fe does not affect the zeolite’s structure but change the intensity of the zeolite spectra. The Fe concentration in Zeolite-Fe of 714 mg L-1, indicate that Fe was present in the zeolite. Both Zeolite and Zeolite-Fe adsorbtion results showed that optimum pH of Chloride anion is 2, with adsorption capacity 2,33 x 10-3 gg-1 and optimum contact time is 8 minutes. While Zeolite and Zeolite-Fe adsorbtion results showed that optimum pH of Carbonate anion is 5, with adsorption capacity 5,31 x 10-3 gg-1 and optimum contact time is 8 minutes.

  9. Enhanced abiotic and biotic contributions to dechlorination of pentachlorophenol during Fe(III) reduction by an iron-reducing bacterium Clostridium beijerinckii Z

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yan [College of Environmental and Natural Resource Sciences, Zhejiang Provincial Key Laboratory of Subtropical Soil and Plant Nutrition, Zhejiang University, Hangzhou 310058 (China); He, Yan, E-mail: yhe2006@zju.edu.cn [College of Environmental and Natural Resource Sciences, Zhejiang Provincial Key Laboratory of Subtropical Soil and Plant Nutrition, Zhejiang University, Hangzhou 310058 (China); Feng, Xiaoli [College of Environmental and Natural Resource Sciences, Zhejiang Provincial Key Laboratory of Subtropical Soil and Plant Nutrition, Zhejiang University, Hangzhou 310058 (China); Liang, Luyi [Experiment Teaching Center for Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Xu, Jianming, E-mail: jmxu@zju.edu.cn [College of Environmental and Natural Resource Sciences, Zhejiang Provincial Key Laboratory of Subtropical Soil and Plant Nutrition, Zhejiang University, Hangzhou 310058 (China); Brookes, Philip C.; Wu, Jianjun [College of Environmental and Natural Resource Sciences, Zhejiang Provincial Key Laboratory of Subtropical Soil and Plant Nutrition, Zhejiang University, Hangzhou 310058 (China)

    2014-03-01

    A novel Fe(III) reducing bacterium, Clostridium beijerinckii Z, was isolated from glucose amended paddy slurries, and shown to dechlorinate pentachlorophenol (PCP). Fifty percent of added PCP was removed by C. beijerinckii Z alone, which increased to 83% in the presence of both C. beijerinckii Z and ferrihydrite after 11 days of incubation. Without C. beijerinckii Z, the surface-bound Fe(II) also abiotically dechlorinated more than 40% of the added PCP. This indicated that the biotic dechlorination by C. beijerinckii Z is a dominant process causing PCP transformation through anaerobic dechlorination, and that the dechlorination rates can be accelerated by simultaneous reduction of Fe(III). A biochemical electron transfer coupling process between sorbed Fe(II) produced by C. beijerinckii Z and reductive dehalogenation is a possible mechanism. This finding increases our knowledge of the role of Fe(III) reducing genera of Clostridium in dechlorinating halogenated organic pollutants, such as PCP, in anaerobic paddy soils. - Highlights: • A novel Fe(III) reducing bacterium Clostridium beijerinckii Z was isolated and could dechlorinate pentachlorophenol. • Anaerobic transformation of PCP by C. beijerinckii Z could be accelerated by simultaneous reduction of Fe(III). • Biochemical electron transfer coupling between Fe redox cycling and reductive dechlorination was the mechanism involved. • The finding increases our knowledge of Clostridium sp. regarding their multiple functions for dechlorinating pollutants.

  10. Enhanced abiotic and biotic contributions to dechlorination of pentachlorophenol during Fe(III) reduction by an iron-reducing bacterium Clostridium beijerinckii Z

    International Nuclear Information System (INIS)

    Xu, Yan; He, Yan; Feng, Xiaoli; Liang, Luyi; Xu, Jianming; Brookes, Philip C.; Wu, Jianjun

    2014-01-01

    A novel Fe(III) reducing bacterium, Clostridium beijerinckii Z, was isolated from glucose amended paddy slurries, and shown to dechlorinate pentachlorophenol (PCP). Fifty percent of added PCP was removed by C. beijerinckii Z alone, which increased to 83% in the presence of both C. beijerinckii Z and ferrihydrite after 11 days of incubation. Without C. beijerinckii Z, the surface-bound Fe(II) also abiotically dechlorinated more than 40% of the added PCP. This indicated that the biotic dechlorination by C. beijerinckii Z is a dominant process causing PCP transformation through anaerobic dechlorination, and that the dechlorination rates can be accelerated by simultaneous reduction of Fe(III). A biochemical electron transfer coupling process between sorbed Fe(II) produced by C. beijerinckii Z and reductive dehalogenation is a possible mechanism. This finding increases our knowledge of the role of Fe(III) reducing genera of Clostridium in dechlorinating halogenated organic pollutants, such as PCP, in anaerobic paddy soils. - Highlights: • A novel Fe(III) reducing bacterium Clostridium beijerinckii Z was isolated and could dechlorinate pentachlorophenol. • Anaerobic transformation of PCP by C. beijerinckii Z could be accelerated by simultaneous reduction of Fe(III). • Biochemical electron transfer coupling between Fe redox cycling and reductive dechlorination was the mechanism involved. • The finding increases our knowledge of Clostridium sp. regarding their multiple functions for dechlorinating pollutants

  11. Mechanistic investigation of Fe(III) oxide reduction by low molecular weight organic sulfur species

    Science.gov (United States)

    Eitel, Eryn M.; Taillefert, Martial

    2017-10-01

    Low molecular weight organic sulfur species, often referred to as thiols, are known to be ubiquitous in aquatic environments and represent important chemical reductants of Fe(III) oxides. Thiols are excellent electron shuttles used during dissimilatory iron reduction, and in this capacity could indirectly affect the redox state of sediments, release adsorbed contaminants via reductive dissolution, and influence the carbon cycle through alteration of bacterial respiration processes. Interestingly, the reduction of Fe(III) oxides by thiols has not been previously investigated in environmentally relevant conditions, likely due to analytical limitations associated with the detection of thiols and their oxidized products. In this study, a novel electrochemical method was developed to simultaneously determine thiol/disulfide pair concentrations in situ during the reduction of ferrihydrite in batch reactors. First order rate laws with respect to initial thiol concentration were confirmed for Fe(III) oxyhydroxide reduction by four common thiols: cysteine, homocysteine, cysteamine, and glutathione. Zero order was determined for both Fe(III) oxyhydroxide and proton concentration at circumneutral pH. A kinetic model detailing the molecular mechanism of the reaction was optimized with proposed intermediate surface structures. Although metal oxide overall reduction rate constants were inversely proportional to the complexity of the thiol structure, the extent of metal reduction increased with structure complexity, indicating that surface complexes play a significant role in the ability of these thiols to reduce iron. Taken together, these results demonstrate the importance of considering the molecular reaction mechanism at the iron oxide surface when investigating the potential for thiols to act as electron shuttles during dissimilatory iron reduction in natural environments.

  12. Petrophilic, Fe(III Reducing Exoelectrogen Citrobacter sp. KVM11, Isolated From Hydrocarbon Fed Microbial Electrochemical Remediation Systems

    Directory of Open Access Journals (Sweden)

    Krishnaveni Venkidusamy

    2018-03-01

    Full Text Available Exoelectrogenic biofilms capable of extracellular electron transfer are important in advanced technologies such as those used in microbial electrochemical remediation systems (MERS Few bacterial strains have been, nevertheless, obtained from MERS exoelectrogenic biofilms and characterized for bioremediation potential. Here we report the identification of one such bacterial strain, Citrobacter sp. KVM11, a petrophilic, iron reducing bacterial strain isolated from hydrocarbon fed MERS, producing anodic currents in microbial electrochemical systems. Fe(III reduction of 90.01 ± 0.43% was observed during 5 weeks of incubation with Fe(III supplemented liquid cultures. Biodegradation screening assays showed that the hydrocarbon degradation had been carried out by metabolically active cells accompanied by growth. The characteristic feature of diazo dye decolorization was used as a simple criterion for evaluating the electrochemical activity in the candidate microbe. The electrochemical activities of the strain KVM11 were characterized in a single chamber fuel cell and three electrode electrochemical cells. The inoculation of strain KVM11 amended with acetate and citrate as the sole carbon and energy sources has resulted in an increase in anodic currents (maximum current density of 212 ± 3 and 359 ± mA/m2 with respective coulombic efficiencies of 19.5 and 34.9% in a single chamber fuel cells. Cyclic voltammetry studies showed that anaerobically grown cells of strain KVM11 are electrochemically active whereas aerobically grown cells lacked the electrochemical activity. Electrobioremediation potential of the strain KVM11 was investigated in hydrocarbonoclastic and dye detoxification conditions using MERS. About 89.60% of 400 mg l-1 azo dye was removed during the first 24 h of operation and it reached below detection limits by the end of the batch operation (60 h. Current generation and biodegradation capabilities of strain KVM11 were examined using an

  13. Petrophilic, Fe(III) Reducing Exoelectrogen Citrobacter sp. KVM11, Isolated From Hydrocarbon Fed Microbial Electrochemical Remediation Systems

    Science.gov (United States)

    Venkidusamy, Krishnaveni; Hari, Ananda Rao; Megharaj, Mallavarapu

    2018-01-01

    Exoelectrogenic biofilms capable of extracellular electron transfer are important in advanced technologies such as those used in microbial electrochemical remediation systems (MERS) Few bacterial strains have been, nevertheless, obtained from MERS exoelectrogenic biofilms and characterized for bioremediation potential. Here we report the identification of one such bacterial strain, Citrobacter sp. KVM11, a petrophilic, iron reducing bacterial strain isolated from hydrocarbon fed MERS, producing anodic currents in microbial electrochemical systems. Fe(III) reduction of 90.01 ± 0.43% was observed during 5 weeks of incubation with Fe(III) supplemented liquid cultures. Biodegradation screening assays showed that the hydrocarbon degradation had been carried out by metabolically active cells accompanied by growth. The characteristic feature of diazo dye decolorization was used as a simple criterion for evaluating the electrochemical activity in the candidate microbe. The electrochemical activities of the strain KVM11 were characterized in a single chamber fuel cell and three electrode electrochemical cells. The inoculation of strain KVM11 amended with acetate and citrate as the sole carbon and energy sources has resulted in an increase in anodic currents (maximum current density) of 212 ± 3 and 359 ± mA/m2 with respective coulombic efficiencies of 19.5 and 34.9% in a single chamber fuel cells. Cyclic voltammetry studies showed that anaerobically grown cells of strain KVM11 are electrochemically active whereas aerobically grown cells lacked the electrochemical activity. Electrobioremediation potential of the strain KVM11 was investigated in hydrocarbonoclastic and dye detoxification conditions using MERS. About 89.60% of 400 mg l-1 azo dye was removed during the first 24 h of operation and it reached below detection limits by the end of the batch operation (60 h). Current generation and biodegradation capabilities of strain KVM11 were examined using an initial

  14. Thermodynamic model for solution behavior and solid-liquid equilibrium in Na-Al(III-Fe(III-Cr(III-Cl-H2O system at 25°C

    Directory of Open Access Journals (Sweden)

    André Laurent

    2018-03-01

    Full Text Available The knowledge of the thermodynamic behavior of multicomponent aqueous electrolyte systems is of main interest in geo-, and environmental-sciences. The main objective of this study is the development of a high accuracy thermodynamic model for solution behavior, and highly soluble M(IIICl3(s (M= Al, Fe, Cr minerals solubility in Na-Al(III-Cr(III-Fe(III-Cl-H2O system at 25°C. Comprehensive thermodynamic models that accurately predict aluminium, chromium and iron aqueous chemistry and M(III mineral solubilities as a function of pH, solution composition and concentration are critical for understanding many important geochemical and environmental processes involving these metals (e.g., mineral dissolution/alteration, rock formation, changes in rock permeability and fluid flow, soil formation, mass transport, toxic M(III remediation. Such a model would also have many industrial applications (e.g., aluminium, chromium and iron production, and their corrosion, solve scaling problems in geothermal energy and oil production. Comparisons of solubility and activity calculations with the experimental data in binary and ternary systems indicate that model predictions are within the uncertainty of the data. Limitations of the model due to data insufficiencies are discussed. The solubility modeling approach, implemented to the Pitzer specific interaction equations is employed. The resulting parameterization was developed for the geochemical Pitzer formalism based PHREEQC database.

  15. Effects of nano calcium carbonate and nano calcium citrate on toxicity in ICR mice and on bone mineral density in an ovariectomized mice model

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Sherry; Chen, Jin Ching; Hsu, Chin Wei; Chang, Walter H, E-mail: whchang@cycu.edu.t [Center for Nano Bioengineering, Chung Yuan Christian University, Chung Li 32023, Taiwan (China); Department of Biomedical Engineering, Chung Yuan Christian University, Chung Li 32023, Taiwan (China)

    2009-09-16

    Taking calcium supplements can reduce the risk of developing osteoporosis, but they are not readily absorbed in the gastrointestinal tract. Nanotechnology is expected to resolve this problem. In the present study, we examined whether the bioavailability of calcium carbonate and calcium citrate can be improved by reducing the particle size. The morphology of nano calcium carbonate and nano calcium citrate was characterized by dynamic laser-light scattering (DLS), field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). The measurements obtained from DLS, FE-SEM and TEM were comparable. Acute and sub-chronic toxicity tests were performed to establish the safety of these products after oral administration. The no-observed-adverse-effect levels of nano calcium carbonate and nano calcium citrate were 1.3 and 2.3 g kg{sup -1} body weight, respectively. The results of our in vivo studies indicate that administering nano calcium carbonate and nano calcium citrate can enhance the serum calcium concentration and maintain the whole-body bone mineral density in ovariectomized mice. These data suggest that nano calcium carbonate and nano calcium citrate are more bioavailable than micro calcium carbonate and micro calcium citrate, respectively.

  16. PVC-membrane potentiometric sensors based on a recently synthesized Schiff base for Fe(III ion

    Directory of Open Access Journals (Sweden)

    S. Yousef Ebrahimipur

    2012-12-01

    Full Text Available A potentiometric iron sensor based on the use 3-(2-diethylamino-ethylimino-1,3-dihydro-indol-2-one (DEDIO as an ionophore in poly(vinyl chloride (PVC matrix, is reported. The plasticized membrane sensor exhibits a Nernstian response for Fe(III ions over a wide concentration range (2.0 × 10-6 - 5.0 × 10-2 M with a super Nernstian slope of 26(plus or minus 1 mV per decade. It has a fast response time of less than 12 s and can be used for ten weeks without any considerable divergences in its potentials the electrode can be used in the pH range 4.5-8.0. The proposed sensor shows fairly good discriminating ability towards Fe(III ion in comparison with a large number of alkali, alkaline earth, transition and heavy metal ions. The sensor was used as indicator electrode in potentiometric titration of Fe(III ions vs. EDTA.DOI: http://dx.doi.org/10.4314/bcse.v26i1.7

  17. Reduction of Fe(III) oxides by phylogenetically and physiologically diverse thermophilic methanogens.

    Science.gov (United States)

    Yamada, Chihaya; Kato, Souichiro; Kimura, Satoshi; Ishii, Masaharu; Igarashi, Yasuo

    2014-09-01

    Three thermophilic methanogens (Methanothermobacter thermautotrophicus, Methanosaeta thermophila, and Methanosarcina thermophila) were investigated for their ability to reduce poorly crystalline Fe(III) oxides (ferrihydrite) and the inhibitory effects of ferrihydrite on their methanogenesis. This study demonstrated that Fe(II) generation from ferrihydrite occurs in the cultures of the three thermophilic methanogens only when H2 was supplied as the source of reducing equivalents, even in the cultures of Mst. thermophila that do not grow on and produce CH4 from H2/CO2. While supplementation of ferrihydrite resulted in complete inhibition or suppression of methanogenesis by the thermophilic methanogens, ferrihydrite reduction by the methanogens at least partially alleviates the inhibitory effects. Microscopic and crystallographic analyses on the ferrihydrite-reducing Msr. thermophila cultures exhibited generation of magnetite on its cell surfaces through partial reduction of ferrihydrite. These findings suggest that at least certain thermophilic methanogens have the ability to extracellularly transfer electrons to insoluble Fe(III) compounds, affecting their methanogenic activities, which would in turn have significant impacts on materials and energy cycles in thermophilic anoxic environments. © 2014 Federation of European Microbiological Societies. Published by John Wiley & Sons Ltd. All rights reserved.

  18. Geobacter daltonii sp. nov., an Fe(III)- and uranium(VI)-reducing bacterium isolated from a shallow subsurface exposed to mixed heavy metal and hydrocarbon contamination.

    Science.gov (United States)

    Prakash, Om; Gihring, Thomas M; Dalton, Dava D; Chin, Kuk-Jeong; Green, Stefan J; Akob, Denise M; Wanger, Greg; Kostka, Joel E

    2010-03-01

    An Fe(III)- and uranium(VI)-reducing bacterium, designated strain FRC-32(T), was isolated from a contaminated subsurface of the USA Department of Energy Oak Ridge Field Research Center (ORFRC) in Oak Ridge, Tennessee, where the sediments are exposed to mixed waste contamination of radionuclides and hydrocarbons. Analyses of both 16S rRNA gene and the Geobacteraceae-specific citrate synthase (gltA) mRNA gene sequences retrieved from ORFRC sediments indicated that this strain was abundant and active in ORFRC subsurface sediments undergoing uranium(VI) bioremediation. The organism belonged to the subsurface clade of the genus Geobacter and shared 92-98 % 16S rRNA gene and 75-81 % rpoB gene sequence similarities with other recognized species of the genus. In comparison to its closest relative, Geobacter uraniireducens Rf4(T), according to 16S rRNA gene sequence similarity, strain FRC-32(T) showed a DNA-DNA relatedness value of 21 %. Cells of strain FRC-32(T) were Gram-negative, non-spore-forming, curved rods, 1.0-1.5 microm long and 0.3-0.5 microm in diameter; the cells formed pink colonies in a semisolid cultivation medium, a characteristic feature of the genus Geobacter. The isolate was an obligate anaerobe, had temperature and pH optima for growth at 30 degrees C and pH 6.7-7.3, respectively, and could tolerate up to 0.7 % NaCl although growth was better in the absence of NaCl. Similar to other members of the Geobacter group, strain FRC-32(T) conserved energy for growth from the respiration of Fe(III)-oxyhydroxide coupled with the oxidation of acetate. Strain FRC-32(T) was metabolically versatile and, unlike its closest relative, G. uraniireducens, was capable of utilizing formate, butyrate and butanol as electron donors and soluble ferric iron (as ferric citrate) and elemental sulfur as electron acceptors. Growth on aromatic compounds including benzoate and toluene was predicted from preliminary genomic analyses and was confirmed through successive transfer with

  19. Impact of Fe(III) as an effective electron-shuttle mediator for enhanced Cr(VI) reduction in microbial fuel cells: Reduction of diffusional resistances and cathode overpotentials

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Qiang [Key Laboratory of Industrial Ecology and Environmental Engineering, Ministry of Education (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China); Huang, Liping, E-mail: lipinghuang@dlut.edu.cn [Key Laboratory of Industrial Ecology and Environmental Engineering, Ministry of Education (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China); Pan, Yuzhen [College of Chemistry, Dalian University of Technology, Dalian 116024 (China); Quan, Xie [Key Laboratory of Industrial Ecology and Environmental Engineering, Ministry of Education (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024 (China); Li Puma, Gianluca, E-mail: g.lipuma@lboro.ac.uk [Environmental Nanocatalysis & Photoreaction Engineering, Department of Chemical Engineering, Loughborough University, Loughborough LE11 3TU (United Kingdom)

    2017-01-05

    Highlights: • Fe(III) shuttles electrons for enhanced reduction of Cr(VI) in MFCs. • The coulombic efficiency increases by 1.6 fold in the presence of Fe(III). • The reduction of Cr(VI) occurs via an indirect Fe(III) mediation mechanism. • Fe(III) decreases the diffusional resistances and the cathode overpotentials. - Abstract: The role of Fe(III) was investigated as an electron-shuttle mediator to enhance the reduction rate of the toxic heavy metal hexavalent chromium (Cr(VI)) in wastewaters, using microbial fuel cells (MFCs). The direct reduction of chromate (CrO{sub 4}{sup −}) and dichromate (Cr{sub 2}O{sub 7}{sup 2−}) anions in MFCs was hampered by the electrical repulsion between the negatively charged cathode and Cr(VI) functional groups. In contrast, in the presence of Fe(III), the conversion of Cr(VI) and the cathodic coulombic efficiency in the MFCs were 65.6% and 81.7%, respectively, 1.6 times and 1.4 folds as those recorded in the absence of Fe(III). Multiple analytical approaches, including linear sweep voltammetry, Tafel plot, cyclic voltammetry, electrochemical impedance spectroscopy and kinetic calculations demonstrated that the complete reduction of Cr(VI) occurred through an indirect mechanism mediated by Fe(III). The direct reduction of Cr(VI) with cathode electrons in the presence of Fe(III) was insignificant. Fe(III) played a critical role in decreasing both the diffusional resistance of Cr(VI) species and the overpotential for Cr(VI) reduction. This study demonstrated that the reduction of Cr(VI) in MFCs was effective in the presence of Fe(III), providing an alternative and environmentally benign approach for efficient remediation of Cr(VI) contaminated sites with simultaneous production of renewable energy.

  20. Impact of Fe(III) as an effective electron-shuttle mediator for enhanced Cr(VI) reduction in microbial fuel cells: Reduction of diffusional resistances and cathode overpotentials

    International Nuclear Information System (INIS)

    Wang, Qiang; Huang, Liping; Pan, Yuzhen; Quan, Xie; Li Puma, Gianluca

    2017-01-01

    Highlights: • Fe(III) shuttles electrons for enhanced reduction of Cr(VI) in MFCs. • The coulombic efficiency increases by 1.6 fold in the presence of Fe(III). • The reduction of Cr(VI) occurs via an indirect Fe(III) mediation mechanism. • Fe(III) decreases the diffusional resistances and the cathode overpotentials. - Abstract: The role of Fe(III) was investigated as an electron-shuttle mediator to enhance the reduction rate of the toxic heavy metal hexavalent chromium (Cr(VI)) in wastewaters, using microbial fuel cells (MFCs). The direct reduction of chromate (CrO_4"−) and dichromate (Cr_2O_7"2"−) anions in MFCs was hampered by the electrical repulsion between the negatively charged cathode and Cr(VI) functional groups. In contrast, in the presence of Fe(III), the conversion of Cr(VI) and the cathodic coulombic efficiency in the MFCs were 65.6% and 81.7%, respectively, 1.6 times and 1.4 folds as those recorded in the absence of Fe(III). Multiple analytical approaches, including linear sweep voltammetry, Tafel plot, cyclic voltammetry, electrochemical impedance spectroscopy and kinetic calculations demonstrated that the complete reduction of Cr(VI) occurred through an indirect mechanism mediated by Fe(III). The direct reduction of Cr(VI) with cathode electrons in the presence of Fe(III) was insignificant. Fe(III) played a critical role in decreasing both the diffusional resistance of Cr(VI) species and the overpotential for Cr(VI) reduction. This study demonstrated that the reduction of Cr(VI) in MFCs was effective in the presence of Fe(III), providing an alternative and environmentally benign approach for efficient remediation of Cr(VI) contaminated sites with simultaneous production of renewable energy.

  1. Redox topotactic reactions in Fe{sup II - III} (oxy)hydroxycarbonate new minerals related to fougerite in gleysols: 'trebeurdenite and moessbauerite'

    Energy Technology Data Exchange (ETDEWEB)

    Genin, Jean-Marie R., E-mail: jean-marie.genin@esstin.uhp-nancy.fr [Institut Jean Barriol FR2843 CNRS-Universite de Lorraine, ESSTIN (France); Guerin, O. [Ecole Pratique des Hautes Etudes, Laboratoire de Geomorphologie (France); Herbillon, A. J. [Universite Catholique de Louvain, Unite des Sciences du Sol (Belgium); Kuzmann, E. [Eoetvoes Lorand Univ., Chemistry Department (Hungary); Mills, S. J. [Geosciences Museum Victoria (Australia); Morin, G.; Ona-Nguema, G. [Univ. P. and M. Curie, Institut Mineralogie and Phys. Milieux Condenses (France); Ruby, C. [Institut Jean Barriol FR2843 CNRS-Universite de Lorraine, ESSTIN (France); Upadhyay, C. [IT-Banaras Hindu Univ., School of Materials Science and Technology (India)

    2012-03-15

    Fougerite mineral responsible for the bluish-green shade of gleysols in aquifers was identified as Fe{sup II - III} oxyhydroxycarbonate, [Fe{sub 6}({sub 1-x)}{sup II} Fe{sub 6x}{sup III} O{sub 12}H{sub 2(7 - 3x)}]{sup 2 + } {center_dot} [CO{sub 3}{sup 2-} {center_dot} 3H{sub 2}O]{sup 2 - } where the average ferric molar fraction x = [Fe{sup III}/Fe{sub total}] was restricted to the [1/3-2/3] range, up till now. In this paper, Moessbauer spectra of gleys extracted from the schorre of maritime marshes have values of x in the [2/3-1] range. Magnetic properties of homologous chemical compounds studied by Moessbauer spectroscopy are explained with long range order of Fe{sup III} ions within Fe cation layers for x = 1/3, 2/3 and 1. Observed values are mixtures of topotactic domains that are in fact minerals with names proposed to IMA: fougerite for x = 1/3, trebeurdenite for x = 2/3 and moessbauerite for x = 1.

  2. A Structural Molar Volume Model for Oxide Melts Part III: Fe Oxide-Containing Melts

    Science.gov (United States)

    Thibodeau, Eric; Gheribi, Aimen E.; Jung, In-Ho

    2016-04-01

    As part III of this series, the model is extended to iron oxide-containing melts. All available experimental data in the FeO-Fe2O3-Na2O-K2O-MgO-CaO-MnO-Al2O3-SiO2 system were critically evaluated based on the experimental condition. The variations of FeO and Fe2O3 in the melts were taken into account by using FactSage to calculate the Fe2+/Fe3+ distribution. The molar volume model with unary and binary model parameters can be used to predict the molar volume of the molten oxide of the Li2O-Na2O-K2O-MgO-CaO-MnO-PbO-FeO-Fe2O3-Al2O3-SiO2 system in the entire range of compositions, temperatures, and oxygen partial pressures from Fe saturation to 1 atm pressure.

  3. Reductive and oxidative degradation of iopamidol, iodinated X-ray contrast media, by Fe(III)-oxalate under UV and visible light treatment.

    Science.gov (United States)

    Zhao, Cen; Arroyo-Mora, Luis E; DeCaprio, Anthony P; Sharma, Virender K; Dionysiou, Dionysios D; O'Shea, Kevin E

    2014-12-15

    Iopamidol, widely employed as iodinated X-ray contrast media (ICM), is readily degraded in a Fe(III)-oxalate photochemical system under UV (350 nm) and visible light (450 nm) irradiation. The degradation is nicely modeled by pseudo first order kinetics. The rates of hydroxyl radical (OH) production for Fe(III)-oxalate/H2O2/UV (350 nm) and Fe(III)-oxalate/H2O2/visible (450 nm) systems were 1.19 ± 0.12 and 0.30 ± 0.01 μM/min, respectively. The steady-state concentration of hydroxyl radical (OH) for the Fe(III)-oxalate/H2O2/UV (350 nm) conditions was 10.88 ± 1.13 × 10(-14) M and 2.7 ± 0.1 × 10(-14) M for the Fe(III)-oxalate/H2O2/visible (450 nm). The rate of superoxide anion radical (O2(-)) production under Fe(III)-oxalate/H2O2/UV (350 nm) was 0.19 ± 0.02 μM/min with a steady-state concentration of 5.43 ± 0.473 × 10(-10) M. Detailed product studies using liquid chromatography coupled to Q-TOF/MS demonstrate both reduction (multiple dehalogenations) and oxidation (aromatic ring and side chains) contribute to the degradation pathways. The reduction processes appear to be initiated by the carbon dioxide anion radical (CO2(-)) while oxidation processes are consistent with OH initiated reaction pathways. Unlike most advanced oxidation processes the Fe(III)-oxalate/H2O2/photochemical system can initiate to both reductive and oxidative degradation processes. The observed reductive dehalogenation is an attractive remediation strategy for halogenated organic compounds as the process can dramatically reduce the formation of the problematic disinfection by-products often associated with oxidative treatment processes. Copyright © 2014 Elsevier Ltd. All rights reserved.

  4. Reduction of Fe(III), Cr(VI), U(VI), and Tc(VII) by Deinococcus radiodurans R1

    International Nuclear Information System (INIS)

    Fredrickson, J.K.; Kostandarithes, H.M.; Li, S.W.; Plymake, A.E.; Daly, M.J.

    2000-01-01

    Deinococcus radiodurans is an exceptionally radiation-resistant microorganism capable of surviving acute exposures to ionizing radiation doses of 15,000 Gy and previously described as having a strictly aerobic respiratory metabolism. Under strict anaerobic conditions, D. radiodurans R1 reduced Fe(III)-nitrilotriacetic acid coupled to the oxidation of lactate to CO 2 and acetate but was unable to link this process to growth. D. radiodurans reduced the humic acid analog anthraquinone-2,6-disulfonate (AQDS) to its dihydroquinone form, AH 2 DS, which subsequently transferred electrons to the Fe(III) oxides hydrous ferric oxide and goethite via a previously described electron shuttle mechanism. D. radiodurans reduced the solid-phase Fe(III) oxides in the presence of either 0.1 mM AQDS or leonardite humic acids (2 mg ml -1 ) but not in their absence. D. radiodurans also reduced U(VI) and Tc(VII) in the presence of AQDS. In contrast, Cr(VI) was directly reduced in anaerobic cultures with lactate although the rate of reduction was higher in the presence of AQDS. The results are the first evidence that D. radiodurans can reduce Fe(III) coupled to the oxidation of lactate or other organic compounds. Also, D. radiodurans, in combination with humic acids or synthetic electron shuttle agents, can reduce U and Tc and thus has potential applications for remediation of metal- and radionuclide-contaminated sites where ionizing radiation or other DNA-damaging agents may restrict the activity of more sensitive organisms

  5. Synthesis of Ce(III)-doped Fe3O4 magnetic particles for efficient removal of antimony from aqueous solution

    International Nuclear Information System (INIS)

    Qi, Zenglu; Joshi, Tista Prasai; Liu, Ruiping; Liu, Huijuan; Qu, Jiuhui

    2017-01-01

    Highlights: • Doping of Ce into Fe 3 O 4 was achieved based on a facile solvothermal method. • After doping, the removal capacity was increased by 5 times for “Sb(V)” and 2 times for “Sb(III)”. • Decreasing pH improved adsorption of Sb(V) but decreased adsorption of Sb(III). • Antimony sorption mechanisms on Ce-doped Fe 3 O 4 were illustrated. - Abstract: Aqueous antimony (Sb) pollution from human activity is of great concern in drinking water due to its adverse health effect. Magnetic Fe 3 O 4 particles, with high separation ability from solution, have been considered as a low-cost Sb adsorbent for contaminants. However, the limited adsorption capacity has restricted its practical application. In this study, a solvothermal approach was developed for doping Ce(III) into Fe 3 O 4 , thereby increasing the adsorption efficacy for both Sb(III) and Sb(V). In contrast to un-doped Fe 3 O 4 , the adsorption capacity towards Sb(III) and Sb(V) in Ce-doped materials increased from 111.4 to 224.2 mg/g and from 37.2 to 188.1 mg/g at neutral pH, respectively. Based on the combined results of XPS, XRD, and FTIR, it confirmed that Ce atom successfully doped into the Fe 3 O 4 structure, resulting in the decreased particle size, increased the surface area, and isoelectric point. Furthermore, the vibrating sample magnetometer (VSM) results showed that the Ce doping process had some side effects on the primitive magnetic property, but remaining the high separation potential during water treatment. According to the high removal efficiency and magnetic property, the Ce-doped Fe 3 O 4 of great simplicity should be a promising adsorbent for aqueous Sb removal.

  6. Impact of Microcystis aeruginosa Exudate on the Formation and Reactivity of Iron Oxide Particles Following Fe(II) and Fe(III) Addition.

    Science.gov (United States)

    Garg, Shikha; Wang, Kai; Waite, T David

    2017-05-16

    Impact of the organic exudate secreted by a toxic strain of Microcystis aeruginosa on the formation, aggregation, and reactivity of iron oxides that are formed on addition of Fe(II) and Fe(III) salts to a solution of the exudate is investigated in this study. The exudate has a stabilizing effect on the particles formed with decreased aggregation rate and increased critical coagulant concentration required for diffusion-limited aggregation to occur. These results suggest that the presence of algal exudates from Microcystis aeruginosa may significantly influence particle aggregation both in natural water bodies where Fe(II) oxidation results in oxide formation and in water treatment where Fe(III) salts are commonly added to aid particle growth and contaminant capture. The exudate also affects the reactivity of iron oxide particles formed with exudate coated particles undergoing faster dissolution than bare iron oxide particles. This has implications to iron availability, especially where algae procure iron via dissolution of iron oxide particles as a result of either reaction with reducing moieties, light-mediated ligand to metal charge transfer and/or reaction with siderophores. The increased reactivity of exudate coated particles is attributed, for the most part, to the smaller size of these particles, higher surface area and increased accessibility of surface sites.

  7. Understanding of the mode of action of Fe(III)-EDDHA as iron chlorosis corrector based on its photochemical and redox behavior.

    Science.gov (United States)

    Gómez-Gallego, Mar; Pellico, Daniel; Ramírez-López, Pedro; Mancheño, María J; Romano, Santiago; de la Torre, María C; Sierra, Miguel A

    2005-10-07

    The very low reduction potential of the chelate Fe(III)-EDDHA (EDDHA = ethylenediamine N,N'-bis(2-hydroxy)phenylacetic acid) makes it unreactive in photochemically or chemically induced electron transfer processes. The lack of reactivity of this complex toward light invalidates photodegradation as an alternative mechanism for environmental elimination. However, in spite of its low reduction potential, the biological reduction of Fe(III)-EDDHA is very effective. Based on electrochemical measurements, it is proposed that Fe(III)-EDDHA itself is not the substrate of the enzyme ferric chelate reductase. Likely, at the more acidic pH in the vicinity of the roots, the ferric chelate in a closed form (FeL-) could generate a vacant coordination site that leads to an open hexacoordinate species (FeHL) where the reduction of the metal by the enzyme takes place.

  8. Fe (III - Galactomannan Solid and Aqueous Complexes: Potentiometric, EPR Spectroscopy and Thermal Data

    Directory of Open Access Journals (Sweden)

    Mercê Ana L. R.

    2001-01-01

    Full Text Available Galactomannans can be employed in food industries to modify the final rheological properties of the products. Since they are not absorbed by the living organisms they can also be used in dietary foods. The equilibria involving the interactions of Fe(III and galactomannans and arabinogalactan of several leguminous plants were characterized by potentiometric titrations and EPR spectroscopy. The log of the equilibrium constants for the formation of ML species, where M is the metal ion and L is the monomeric unit of the biopolymers, were 15.4, 14.1 and 18.5, for the galactomannans of C. fastuosa, L. leucocephala and S. macranthera, respectively. Log K values for protonated species (MHL were 3.1, 3.3, and were not detected for the galactomannan of S. macranthera. The log K values for the formation of ML2 were 14.1, 13.3 and 15.2, respectively. Early formation of insoluble products in the equilibrium with arabinogalactan and Fe(III prevented acquisition of reliable data. The solid complexes assays showed a great dipolar interaction between two Fe(III ions in the inner structure of the biopolymer which increased as the degree of substitution of the galactomannan decreased, and also showed the resulting thermal stability. The complexes impart a new possibility of providing essential metal ions in dietary foods since decomplexation of the complexes can occur at different pH values existing in the human body.

  9. Fe(III)-functionalized carbon dots—Highly efficient photoluminescence redox catalyst for hydrogenations of olefins and decomposition of hydrogen peroxide

    KAUST Repository

    Bourlinos, Athanasios B.

    2017-03-21

    We present the first bottom-up approach to synthesize Fe(III)-functionalized carbon dots (CDs) from molecular precursors without the need of conventional thermal or microwave treatment and additional reagents. Specifically, sonication of xylene in the presence of anhydrous FeCl3 results in oxidative coupling of the aromatic substrate towards Fe(III)-functionalized CDs. The as-prepared CDs are spherical in shape with a size of 3–8 nm, highly dispersible in organic solvents and display wavelength-dependent photoluminescence (PL). The iron ions attached to the surface endow the CDs with superior catalytic activity for olefin hydrogenation with excellent conversion and selectivity (up to 100%). The Fe(III)-CDs are more effective in the hydrogenation of a series of electron donating or withdrawing olefin substrates compared to conventional homogeneous or heterogeneous Fe(III)-based catalysts. The as-prepared heterogeneous nanocatalyst can be used repeatedly without any loss of catalytic activity. Importantly, the stability of the new catalysts can be easily monitored by PL intensity or quantum yield measurements, which certainly opens the doors for real time monitoring in a range of applications. Additionally, to the best of our knowledge, for the first time, the oxidative property of Fe-CDs was also explored in decomposition of hydrogen peroxide in water with the first order rate constant of 0.7 × 10−2 min−1, proving the versatile catalytic properties of such hybrid systems.

  10. Fe(III)-functionalized carbon dots—Highly efficient photoluminescence redox catalyst for hydrogenations of olefins and decomposition of hydrogen peroxide

    KAUST Repository

    Bourlinos, Athanasios B.; Rathi, Anuj K.; Gawande, Manoj B.; Hola, Katerina; Goswami, Anandarup; Kalytchuk, Sergii; Karakassides, Michael A.; Kouloumpis, Antonios; Gournis, Dimitrios; Deligiannakis, Yannis; Giannelis, Emmanuel P.; Zboril, Radek

    2017-01-01

    We present the first bottom-up approach to synthesize Fe(III)-functionalized carbon dots (CDs) from molecular precursors without the need of conventional thermal or microwave treatment and additional reagents. Specifically, sonication of xylene in the presence of anhydrous FeCl3 results in oxidative coupling of the aromatic substrate towards Fe(III)-functionalized CDs. The as-prepared CDs are spherical in shape with a size of 3–8 nm, highly dispersible in organic solvents and display wavelength-dependent photoluminescence (PL). The iron ions attached to the surface endow the CDs with superior catalytic activity for olefin hydrogenation with excellent conversion and selectivity (up to 100%). The Fe(III)-CDs are more effective in the hydrogenation of a series of electron donating or withdrawing olefin substrates compared to conventional homogeneous or heterogeneous Fe(III)-based catalysts. The as-prepared heterogeneous nanocatalyst can be used repeatedly without any loss of catalytic activity. Importantly, the stability of the new catalysts can be easily monitored by PL intensity or quantum yield measurements, which certainly opens the doors for real time monitoring in a range of applications. Additionally, to the best of our knowledge, for the first time, the oxidative property of Fe-CDs was also explored in decomposition of hydrogen peroxide in water with the first order rate constant of 0.7 × 10−2 min−1, proving the versatile catalytic properties of such hybrid systems.

  11. Chemical sporulation and germination: cytoprotective nanocoating of individual mammalian cells with a degradable tannic acid-FeIII complex

    Science.gov (United States)

    Lee, Juno; Cho, Hyeoncheol; Choi, Jinsu; Kim, Doyeon; Hong, Daewha; Park, Ji Hun; Yang, Sung Ho; Choi, Insung S.

    2015-11-01

    Individual mammalian cells were coated with cytoprotective and degradable films by cytocompatible processes maintaining the cell viability. Three types of mammalian cells (HeLa, NIH 3T3, and Jurkat cells) were coated with a metal-organic complex of tannic acid (TA) and ferric ion, and the TA-FeIII nanocoat effectively protected the coated mammalian cells against UV-C irradiation and a toxic compound. More importantly, the cell proliferation was controlled by programmed formation and degradation of the TA-FeIII nanocoat, mimicking the sporulation and germination processes found in nature.Individual mammalian cells were coated with cytoprotective and degradable films by cytocompatible processes maintaining the cell viability. Three types of mammalian cells (HeLa, NIH 3T3, and Jurkat cells) were coated with a metal-organic complex of tannic acid (TA) and ferric ion, and the TA-FeIII nanocoat effectively protected the coated mammalian cells against UV-C irradiation and a toxic compound. More importantly, the cell proliferation was controlled by programmed formation and degradation of the TA-FeIII nanocoat, mimicking the sporulation and germination processes found in nature. Electronic supplementary information (ESI) available: Experimental details, LSCM images, and SEM and TEM images. See DOI: 10.1039/c5nr05573c

  12. Development of a biomarker for Geobacter activity and strain composition: Proteogenomic analysis of the citrate synthase protein during bioremediation of U(VI)

    Energy Technology Data Exchange (ETDEWEB)

    Wilkins, M.J.; Callister, S.J.; Miletto, M.; Williams, K.H.; Nicora, C.D.; Lovley, D.R.; Long, P.E.; Lipton, M.S.

    2010-02-15

    Monitoring the activity of target microorganisms during stimulated bioremediation is a key problem for the development of effective remediation strategies. At the US Department of Energy's Integrated Field Research Challenge (IFRC) site in Rifle, CO, the stimulation of Geobacter growth and activity via subsurface acetate addition leads to precipitation of U(VI) from groundwater as U(IV). Citrate synthase (gltA) is a key enzyme in Geobacter central metabolism that controls flux into the TCA cycle. Here, we utilize shotgun proteomic methods to demonstrate that the measurement of gltA peptides can be used to track Geobacter activity and strain evolution during in situ biostimulation. Abundances of conserved gltA peptides tracked Fe(III) reduction and changes in U(VI) concentrations during biostimulation, whereas changing patterns of unique peptide abundances between samples suggested sample-specific strain shifts within the Geobacter population. Abundances of unique peptides indicated potential differences at the strain level between Fe(III)-reducing populations stimulated during in situ biostimulation experiments conducted a year apart at the Rifle IFRC. These results offer a novel technique for the rapid screening of large numbers of proteomic samples for Geobacter species and will aid monitoring of subsurface bioremediation efforts that rely on metal reduction for desired outcomes.

  13. Turn-on fluorogenic and chromogenic detection of Fe(III) and its application in living cell imaging

    International Nuclear Information System (INIS)

    Sivaraman, Gandhi; Sathiyaraja, Vijayaraj; Chellappa, Duraisamy

    2014-01-01

    Two rhodamine-based sensors RDI-1, RDI-2 was designed and synthesized by incorporation of the rhodamine 6G fluorophore and 2-formyl imidazole as the recognizing unit via the imine linkages. RDI-1, RDI-2 exhibits very high selectivity and an excellent sensitivity towards Fe(III) ions in aqueous buffer solution on compared with other probes. The color change from colorless to pink and turn-on fluorescence after binding with iron (III) was observed. Based on jobs plot and ESI-MS studies, the 1:1 binding mode was proposed. Live cell imaging experiments with each probe showed that these probes widely applicable to detect Fe 3+ in living cells. -- Highlights: • Two rhodamine based probes was synthesized and used to recognize iron (III). • The chemosensors can be applied to detect iron(III) ions by color and turn-on fluorescent changes. • The very low detection limit was reported. • The applicability of these probes for live cell fluorescence imaging was studied

  14. Turn-on fluorogenic and chromogenic detection of Fe(III) and its application in living cell imaging

    Energy Technology Data Exchange (ETDEWEB)

    Sivaraman, Gandhi; Sathiyaraja, Vijayaraj; Chellappa, Duraisamy, E-mail: dcmku123@gmail.com

    2014-01-15

    Two rhodamine-based sensors RDI-1, RDI-2 was designed and synthesized by incorporation of the rhodamine 6G fluorophore and 2-formyl imidazole as the recognizing unit via the imine linkages. RDI-1, RDI-2 exhibits very high selectivity and an excellent sensitivity towards Fe(III) ions in aqueous buffer solution on compared with other probes. The color change from colorless to pink and turn-on fluorescence after binding with iron (III) was observed. Based on jobs plot and ESI-MS studies, the 1:1 binding mode was proposed. Live cell imaging experiments with each probe showed that these probes widely applicable to detect Fe{sup 3+} in living cells. -- Highlights: • Two rhodamine based probes was synthesized and used to recognize iron (III). • The chemosensors can be applied to detect iron(III) ions by color and turn-on fluorescent changes. • The very low detection limit was reported. • The applicability of these probes for live cell fluorescence imaging was studied.

  15. Photochemistry of Fe(Iii)-Carboxylates in Polysaccharide-Based Materials with Tunable Mechanical Properties

    Science.gov (United States)

    Giammanco, Giuseppe E.

    We present the formulation and study of light-responsive materials based on carboxylate-containing polysaccharides. The functional groups in these natural polymers allow for strong interactions with transition metal ions such as Fe(III). The known photochemistry of hydroxycarboxylic acids in natural waters inspired us in exploring the visible light induced photochemistry of the carboxylates in these polysaccharides when coordinated to Fe(III) ions. Described in this dissertation are the design and characterization of the Fe(III)-polysaccharide materials, specifically the mechanistic aspects of the photochemistry and the effects that these reactions have on the structure of the polymer materials. We present a study of the quantitative photochemistry of different polysaccharide systems, where the presence of uronic acids was important for the photoreaction to take place. Alginate (Alg), pectate (Pec), hyaluronic acid (Hya), xanthan gum (Xan), and a polysaccharide extracted from the Noni fruit (NoniPs), were among the natural uronic acid-containing polysaccharide (UCPS) systems we analyzed. Potato starch, lacking of uronate groups, did not present any photochemistry in the presence of Fe(III); however, we were able to induce a photochemical response in this polysaccharide upon chemical manipulation of its functional groups. Important structure-function relationships were drawn from this study. The uronate moiety present in these polysaccharides is then envisioned as a tool to induce response to light in a variety of materials. Following this approach, we report the formulation of materials for controlled drug release, able to encapsulate and release different drug models only upon illumination with visible light. Furthermore, hybrid hydrogels were prepared from UPCS and non-responsive polymers. Different properties of these materials could be tuned by controlling the irradiation time, intensity and location. These hybrid gels were evaluated as scaffolds for tissue

  16. Simultaneous Oxidation and Sequestration of As(III) from Water by Using Redox Polymer-Based Fe(III) Oxide Nanocomposite.

    Science.gov (United States)

    Zhang, Xiaolin; Wu, Mengfei; Dong, Hao; Li, Hongchao; Pan, Bingcai

    2017-06-06

    Water decontamination from As(III) is an urgent but still challenging task. Herein, we fabricated a bifunctional nanocomposite HFO@PS-Cl for highly efficient removal of As(III), with active chlorine covalently binding spherical polystyrene host for in situ oxidation of As(III) to As(V), and Fe(III) hydroxide (HFO) nanoparticles (NPs) embedded inside for specific As(V) removal. HFO@PS-Cl could work effectively in a wide pH range (5-9), and other substances like sulfate, chloride, bicarbonate, silicate, and humic acid exert insignificant effect on As(III) removal. As(III) sequestration is realized via two pathways, that is, oxidation to As(V) by the active chlorine followed by specific As(V) adsorption onto HFO NPs, and As(III) adsorption onto HFO NPs followed by oxidation to As(V). The exhausted HFO@PS-Cl could be refreshed for cyclic runs with insignificant capacity loss by the combined regeneration strategy, that is, alkaline solution to rinse the adsorbed As(V) and NaClO solution to renew the host oxidation capability. In addition, fixed-bed experiments demonstrated that the HFO@PS-Cl column could generate >1760 bed volume (BV) effluent from a synthetic As(III)-containing groundwater to meet the drinking water standard (nanocomposites, HFO@PS-N and HFO@D201 could only generate 450 and 600 BV effluents under otherwise identical conditions.

  17. Sorption Mechanisms of Cesium on Cu II2Fe II(CN) 6and Cu II3[Fe III(CN) 6] 2Hexacyanoferrates and Their Relation to the Crystalline Structure

    Science.gov (United States)

    Ayrault, S.; Jimenez, B.; Garnier, E.; Fedoroff, M.; Jones, D. J.; Loos-Neskovic, C.

    1998-12-01

    CuII2FeII(CN)6·xH2O and CuII3[FeIII(CN)6]2·xH2O can be prepared with reproducible chemical compositions and structures after careful washing. They have cubicFmoverline3mstructures with iron vacancies. In CuII2FeII(CN)6, copper occupies two different sites: Cu1 in position 4blinked to Fe through the CN groups, and Cu2 not linked to the CN groups and partially occupying the interstitial 24epositions. The second type of site is not present in CuII3[FeIII(CN)6]2. Sorption kinetics and isotherms were determined for cesium on both hexacyanoferrates by batch experiments. On CuII3[FeIII(CN)6]2, the maximum uptake is only 0.073 Cs/Fe (at./at.). On CuII2FeII(CN)6, the uptake reaches 1.5 Cs/Fe. The sorption kinetics include at least two steps: at1/2variation until approximately 72 h and then a slow evolution studied up to 6 months. The sorption mechanism is complex. The main process seems to be diffusion of ion pairs, followed by a reorganization of the solid, resulting in one or more new solid phases. The presence of the Cu2 site seems to play a favorable role in the sorption. Owing to its good midterm stability and the first rapid step of exchange, CuII2FeII(CN)6·xH2O seems to be one of the most promising compounds for the recovery of cesium from nuclear liquid wastes.

  18. Construction of a cellulase hyper-expression system in Trichoderma reesei by promoter and enzyme engineering

    NARCIS (Netherlands)

    Zou, G.; Shi, S.; Jiang, Y.; van den Brink, J.; de Vries, R.P.; Chen, L.; Zhang, J.; Ma, L.; Wang, C.; Zhou, Z.

    2012-01-01

    Background A bacterial strain previously isolated from pyrite mine drainage and named BAS-10 was tentatively identified as Klebsiella oxytoca. Unlikely other enterobacteria, BAS-10 is able to grow on Fe(III)-citrate as sole carbon and energy source, yielding acetic acid and CO2 coupled with Fe(III)

  19. A Simple Small Size and Low Cost Sensor Based on Surface Plasmon Resonance for Selective Detection of Fe(III

    Directory of Open Access Journals (Sweden)

    Nunzio Cennamo

    2014-03-01

    Full Text Available A simple, small size, and low cost sensor based on a Deferoxamine Self Assembled Monolayer (DFO-SAM and Surface Plasmon Resonance (SPR transduction, in connection with a Plastic Optical Fiber (POF, has been developed for the selective detection of Fe(III. DFO-SAM sensors based on appropriate electrochemical techniques can be frequently found in the scientific literature. In this work, we present the first example of a DFO-SAM sensor based on SPR in an optical fiber. The SPR sensing platform was realized by removing the cladding of a plastic optical fiber along half the circumference, spin coating a buffer of Microposit S1813 photoresist on the exposed core, and finally sputtering a thin gold film. The hydroxamate siderophore deferoxamine (DFO, having high binding affinity for Fe(III, is then used in its immobilized form, as self-assembled monolayer on the gold layer surface of the POF sensor. The results showed that the DFO-SAM-POF-sensor was able to sense the formation of the Fe(III/DFO complex in the range of concentrations between 1 μm and 50 μm with a linearity range from 0 to 30 μm of Fe(III. The selectivity of the sensor was also proved by interference tests.

  20. A simple small size and low cost sensor based on surface plasmon resonance for selective detection of Fe(III).

    Science.gov (United States)

    Cennamo, Nunzio; Alberti, Giancarla; Pesavento, Maria; D'Agostino, Girolamo; Quattrini, Federico; Biesuz, Raffaela; Zeni, Luigi

    2014-03-07

    A simple, small size, and low cost sensor based on a Deferoxamine Self Assembled Monolayer (DFO-SAM) and Surface Plasmon Resonance (SPR) transduction, in connection with a Plastic Optical Fiber (POF), has been developed for the selective detection of Fe(III). DFO-SAM sensors based on appropriate electrochemical techniques can be frequently found in the scientific literature. In this work, we present the first example of a DFO-SAM sensor based on SPR in an optical fiber. The SPR sensing platform was realized by removing the cladding of a plastic optical fiber along half the circumference, spin coating a buffer of Microposit S1813 photoresist on the exposed core, and finally sputtering a thin gold film. The hydroxamate siderophore deferoxamine (DFO), having high binding affinity for Fe(III), is then used in its immobilized form, as self-assembled monolayer on the gold layer surface of the POF sensor. The results showed that the DFO-SAM-POF-sensor was able to sense the formation of the Fe(III)/DFO complex in the range of concentrations between 1 μm and 50 μm with a linearity range from 0 to 30 μm of Fe(III). The selectivity of the sensor was also proved by interference tests.

  1. Colorimetric sensing of oxalate based on its inhibitory effect on the reaction of Fe (III) with curcumin nanoparticles

    Science.gov (United States)

    Pourreza, Nahid; Lotfizadeh, Neda; Golmohammadi, Hamed

    2018-03-01

    In this research, a new colorimetric method for the determination of oxalate using curcumin nanoparticles (CURNs) in the presence Fe (III) is introduced. The method is based on the inhibitory effect of oxalate ion on the reaction of (CURNs) with Fe (III) in acidic media. This reaction was monitored by measuring the increase in absorbance of CURNs-Fe3 + complex in the presence of oxalate ion at 427 nm. The effect of different parameters such as the pH of the sample solution, concentration of Fe (III), concentration of CURNs and the reaction time was examined and optimized. Under optimum experimental conditions, the absorption intensity was linear with the concentration of oxalate in the range of 0.15 to 1.70 μg mL- 1. The limit of detection (LOD) was 0.077 μg mL- 1 and the relative standard deviations (RSD) for 8 replicate measurements of 0.40 and 1.05 μg mL- 1 of oxalate were 4.20% and 2.74%, respectively. The developed method was successfully employed to the determination of oxalate in water, food and urine samples with satisfactory results.

  2. Syntheses, crystal structures, and magnetic properties of four new cyano-bridged bimetallic complexes based on the mer-[Fe(III)(qcq)(CN)3]- building block.

    Science.gov (United States)

    Shen, Xiaoping; Zhou, Hongbo; Yan, Jiahao; Li, Yanfeng; Zhou, Hu

    2014-01-06

    Four new cyano-bridged bimetallic complexes, [{Mn(III)(salen)}2{Fe(III)(qcq)(CN)3}2]n·3nCH3CN·nH2O (1) [salen = N,N'-ethylenebis(salicylideneiminato) dianion; qcq(-) = 8-(2-quinoline-2-carboxamido)quinoline anion], [{Mn(III)(salpn)}2{Fe(III)(qcq)(CN)3}2]n·4nH2O (2) [salpn = N,N'-1,2-propylenebis(salicylideneiminato)dianion], [{Mn(II)(bipy)(CH3OH)}{Fe(III)(qcq)(CN)3}2]2·2H2O·2CH3OH (3) (bipy = 2,2'-bipyridine), and [{Mn(II)(phen)2}{Fe(III)(qcq)(CN)3}2]·CH3CN·2H2O (4) (phen = 1,10-phenanthroline) have been synthesized and characterized both structurally and magnetically. The structures of 1 and 2 are both unique 1-D linear branch chains with additional structural units of {Mn(III)(salen/salpn)}{Fe(III)(qcq)(CN)3} dangling on the sides. In contrast, 3 and 4 are cyano-bridged bimetallic hexanuclear and trinuclear clusters, respectively. The intermolecular short contacts such as π-π interactions and hydrogen bonds extend 1-4 into high dimensional supermolecular networks. Magnetic investigation reveals the dominant intramolecular antiferromagnetic interactions in 1, 3, and 4, while ferromagnetic and antiferromagnetic interactions coexist in 2. Alternating current measurement at low temperature indicates the existence of slow magnetic relaxation in 1 and 2, which should be due to the single ion anisotropy of Mn(III).

  3. Asymmetric Diels-Alder Reaction of α,β-Unsaturated Oxazolidin-2-one Derivatives Catalyzed by a Chiral Fe(III)-Bipyridine Diol Complex.

    Science.gov (United States)

    Li, Mao; Carreras, Virginie; Jalba, Angela; Ollevier, Thierry

    2018-02-16

    An asymmetric Fe III -bipyridine diol catalyzed Diels-Alder reaction of α,β-unsaturated oxazolidin-2-ones has been developed. Among various Fe II /Fe III salts, Fe(ClO 4 ) 3 ·6H 2 O was selected as the Lewis acid of choice. The use of a low catalyst loading (2 mol % of Fe(ClO 4 ) 3 ·6H 2 O and 2.4 mol % of Bolm's ligand) afforded high yields (up to 99%) and high enantiomeric excesses (up to 98%) of endo-cycloadducts for the Diels-Alder reaction between cyclopentadiene and substituted acryloyloxazolidin-2-ones. Other noncyclic dienes led to decreased enantioselectivities. A proposed model supports the observed stereoinduction.

  4. Iron and Arsenic Speciation During As(III) Oxidation by Manganese Oxides in the Presence of Fe(II): Molecular-Level Characterization Using XAFS, Mössbauer, and TEM Analysis

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Yun [Environmental Soil Chemistry Research Group, Delaware Environmental Institute, University of Delaware, Newark, Delaware 19716, United States; Kukkadapu, Ravi K. [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Livi, Kenneth J. T. [The High-Resolution Analytical Electron Microbeam Facility, Department of Earth and Planetary Sciences, The Johns Hopkins University, Baltimore, Maryland 21218, United States; Xu, Wenqian [Department of Chemistry, Brookhaven National Lab, Upton, New York 11796, United States; Li, Wei [Environmental Soil Chemistry Research Group, Delaware Environmental Institute, University of Delaware, Newark, Delaware 19716, United States; Key Laboratory of Surficial Geochemistry, Ministry of Education, School of Earth Sciences and Engineering, Nanjing University, Nanjing 210046, People’s Republic of China; Sparks, Donald L. [Environmental Soil Chemistry Research Group, Delaware Environmental Institute, University of Delaware, Newark, Delaware 19716, United States

    2018-01-17

    The redox state and speciation of metalloid arsenic (As) determine its toxicity and mobility. Knowledge of biogeochemical processes influencing the As redox state is therefore important to understand and predict its environmental behavior. Many previous studies examined As(III) oxidation by various Mn-oxides, but little is known the environmental influences (e.g. co-existing ions) on such process. In this study, we investigated the mechanisms of As(III) oxidation by a poorly crystalline hexagonal birnessite (δ-MnO2) in the presence of Fe(II) using X-ray absorption spectroscopy (XAS), Mössbauer spectroscopy and transmission electron microscopy (TEM) coupled with energy-dispersive X-ray spectroscopy (EDS). As K-edge X-ray absorption near edge spectroscopy (XANES) analysis revealed that, at low Fe(II) concentration (100 μM), As(V) was the predominant As species on the solid phase, while at higher Fe(II) concentration (200-1000 μM), both As(III) and As(V) were sorbed on the solid phase. As K-edge extended X-ray absorption fine structure spectroscopy (EXAFS) analysis showed an increasing As-Mn/Fe distance over time, indicating As prefers to bind with the newly formed Fe(III)-(hydr)oxides. As adsorbed on Fe(III)-(hydr)oxides as a bidentate binuclear corner-sharing complex. Both Mössbauer and TEM-EDS investigations demonstrated that the oxidized Fe(III) products formed during Fe(II) oxidation by δ-MnO2 were predominantly ferrihydrite, goethite, and ferric arsenate like compounds. However, Fe EXAFS analysis also suggested the formation of a small amount of lepidocrocite. The Mn K-edge XANES data indicated that As(III) and Fe(II) oxidation occurs as a two electron transfer with δ-MnO2 and the observed Mn(III) is due to conproportionation of surface sorbed Mn(II) with Mn(IV) in δ-MnO2 structure. This study reveals that the mechanisms of As(III) oxidation by δ-MnO2 in the presence of Fe(II) are very complex, involving many simultaneous reactions, and the formation of

  5. Effect of low-molecular-weight organic acids on photo-degradation of phenanthrene catalyzed by Fe(III)-smectite under visible light.

    Science.gov (United States)

    Jia, Hanzhong; Chen, Hongxia; Nulaji, Gulimire; Li, Xiyou; Wang, Chuanyi

    2015-11-01

    The photolysis of polycyclic aromatic hydrocarbons (PAHs) is potentially an important process for its transformation and fate on contaminated soil surfaces. In this study, phenanthrene is employed as a model to explore PAH photodegradation with the assistance of Fe(III)-smectite under visible-light while focusing on roles played by five low-molecular-weight organic acids (LMWOAs), i.e., malic acid, oxalic acid, citric acid, ethylenediaminetetraacetic acid (EDTA), and nitrilotriacetic acid. Our results show that oxalic acid is most effective in promoting the photodegradation of phenanthrene, while only a slight increase in the rate of phenanthrene photodegradation is observed in the presence of malic acid. Electron paramagnetic resonance experiments confirm the formation of CO2(-) radicals in the presence of malic and oxalic acid, which provides strong evidence for generating OH and subsequent photoreaction pathways. The presence of EDTA or nitrilotriacetic acid significantly inhibits both Fe(II) formation and phenanthrene photodegradation because these organic anions tend to chelate with Fe(III), leading to decreases in the electron-accepting potential of Fe(III)-smectite and a weakened interaction between phenanthrene and Fe(III)-smectite. These observations provide valuable insights into the transformation and fate of PAHs in the natural soil environment and demonstrate the potential for using some LMWOAs as additives for the remediation of contaminated soil. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Formation of the Fe(II)-Fe(III) hydroxysulphate green rust during marine corrosion of steel

    International Nuclear Information System (INIS)

    Refait, Ph.; Memet, J.-B.; Bon, C.; Sabot, R.; Genin, J.-M.R.

    2003-01-01

    Rust layers formed on steel sheet piles immersed 1 m above the mud line for 25 years were analysed by Raman spectroscopy, scanning electron microscopy and elemental X-ray mappings (Fe, S, O). They consist of three main strata, the inner one mainly composed of magnetite, the intermediate one of iron(III) oxyhydroxides and the outer one of hydroxysulphate green rust GR(SO 4 2- ). Simulations of GRs formation in solutions having large [Cl - ]/[SO 4 2- ] ratios revealed that the hydroxysulphate GR(SO 4 2- ) was obtained instead of the hydroxychloride GR(Cl - ), as demonstrated by X-ray diffraction and transmission Moessbauer spectroscopy analyses. Measurements of the [S], [Fe] and [Cl] concentrations allowed us to establish that GR(SO 4 2- ) formed along with a drastic impoverishment of the solution in sulphate ions; the [Cl - ]/[SO 4 2- ] ratio increased from 12 to 240. The GR, acting like a 'sulphate pump', may favour the colonisation of the rust layers by sulphate reducing bacteria

  7. Synthesis of Ce(III)-doped Fe{sub 3}O{sub 4} magnetic particles for efficient removal of antimony from aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Qi, Zenglu; Joshi, Tista Prasai [Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Liu, Ruiping, E-mail: liuruiping@rcees.ac.cn [Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Liu, Huijuan [University of Chinese Academy of Sciences, Beijing 100049 (China); State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085 (China); Qu, Jiuhui [Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); University of Chinese Academy of Sciences, Beijing 100049 (China)

    2017-05-05

    Highlights: • Doping of Ce into Fe{sub 3}O{sub 4} was achieved based on a facile solvothermal method. • After doping, the removal capacity was increased by 5 times for “Sb(V)” and 2 times for “Sb(III)”. • Decreasing pH improved adsorption of Sb(V) but decreased adsorption of Sb(III). • Antimony sorption mechanisms on Ce-doped Fe{sub 3}O{sub 4} were illustrated. - Abstract: Aqueous antimony (Sb) pollution from human activity is of great concern in drinking water due to its adverse health effect. Magnetic Fe{sub 3}O{sub 4} particles, with high separation ability from solution, have been considered as a low-cost Sb adsorbent for contaminants. However, the limited adsorption capacity has restricted its practical application. In this study, a solvothermal approach was developed for doping Ce(III) into Fe{sub 3}O{sub 4}, thereby increasing the adsorption efficacy for both Sb(III) and Sb(V). In contrast to un-doped Fe{sub 3}O{sub 4}, the adsorption capacity towards Sb(III) and Sb(V) in Ce-doped materials increased from 111.4 to 224.2 mg/g and from 37.2 to 188.1 mg/g at neutral pH, respectively. Based on the combined results of XPS, XRD, and FTIR, it confirmed that Ce atom successfully doped into the Fe{sub 3}O{sub 4} structure, resulting in the decreased particle size, increased the surface area, and isoelectric point. Furthermore, the vibrating sample magnetometer (VSM) results showed that the Ce doping process had some side effects on the primitive magnetic property, but remaining the high separation potential during water treatment. According to the high removal efficiency and magnetic property, the Ce-doped Fe{sub 3}O{sub 4} of great simplicity should be a promising adsorbent for aqueous Sb removal.

  8. Pentachlorophenol radical cations generated on Fe(III)-montmorillonite initiate octachlorodibenzo-p-dioxin formation in clays: DFT and FTIR studies

    Science.gov (United States)

    Gu, Cheng; Liu, Cun; Johnston, Cliff T.; Teppen, Brian J.; Li, Hui; Boyd, Stephen A.

    2011-01-01

    Octachlorodibenzodioxin (OCDD) forms spontaneously from pentachlorophenol (PCP) on the surfaces of Fe(III)-saturated smectite clay (1). Here, we used in situ FTIR methods and quantum mechanical calculations to determine the mechanism by which this reaction is initiated. As the clay was dehydrated, vibrational spectra showed new peaks that grew and then reversibly disappeared as the clay rehydrated. First principle DFT calculations of hydrated Fe-PCP clusters reproduced these transient FTIR peaks when inner-sphere complexation and concomitant electron transfer produced Fe(II) and PCP radical cations. Thus, our experimental (FTIR) and theoretical (quantum mechanical) results mutually support the hypothesis that OCDD formation on Fe-smectite surfaces is initiated by the reversible formation of metastable PCP radical cations via single electron transfer from PCP to Fe(III). The negatively charged clay surface apparently selects for this reaction mechanism by stabilizing PCP radical cations. PMID:21254769

  9. Redox topotactic reactions in Fe II - III (oxy)hydroxycarbonate new minerals related to fougèrite in gleysols: "trébeurdenite and mössbauerite"

    Science.gov (United States)

    Génin, Jean-Marie R.; Guérin, O.; Herbillon, A. J.; Kuzmann, E.; Mills, S. J.; Morin, G.; Ona-Nguema, G.; Ruby, C.; Upadhyay, C.

    2012-03-01

    Fougèrite mineral responsible for the bluish-green shade of gleysols in aquifers was identified as FeII - III oxyhydroxycarbonate, [Fe^II_{6(1-x) }Fe^III_{6x}O12H2(7 - 3 x)]2 + · [CO3^{2-} · 3H2O]2 - where the average ferric molar fraction x = [FeIII/Fetotal] was restricted to the [1/3-2/3] range, up till now. In this paper, Mössbauer spectra of gleys extracted from the schorre of maritime marshes have values of x in the [2/3-1] range. Magnetic properties of homologous chemical compounds studied by Mössbauer spectroscopy are explained with long range order of FeIII ions within Fe cation layers for x = 1/3, 2/3 and 1. Observed values are mixtures of topotactic domains that are in fact minerals with names proposed to IMA: fougèrite for x = 1/3, trébeurdenite for x = 2/3 and mössbauerite for x = 1.

  10. Microbial Diversity and Characteristics in Anaerobic Environments in KURT Groundwater

    International Nuclear Information System (INIS)

    Roh, Yul; Oh, Jong Min; Rhee, Sung Keun; Yong, Jong Joong

    2008-03-01

    The Underground Research Tunnel (URT) located in Korea Atomic Energy Research Institute (KAERI), Daejeon, South Korea was recently constructed as an experimental site to study radionuclide transport, biogeochemistry, radionuclide-mineral interactions for the geological disposal of high level nuclear waste. Groundwater sampled from URT was used to examine microbial diversity and to enrich metal reducing bacteria for studying microbe-metal interactions. Genomic analysis indicated that the groundwater contained diverse microorganisms such as metal reducers, metal oxidizers, anaerobic denitrifying bacteria, and bacteria for reductive dechlorination. Metal-reducing bacteria enriched from the groundwater was used to study metal reduction and biomineralization. The metal-reducing bacteria enriched with acetate or lactate as the electron donors showed the bacteria reduced Fe(III)-citrate, Fe(III) oxyhydroxide, Mn(IV) oxide, and Cr(VI) as the electron acceptors. Preliminary study indicated that the enriched bacteria were able to use glucose, lactate, acetate, and hydrogen as electron donors while reducing Fe(III)-citrate or Fe(III) oxyhydroxide as the electron acceptor. The bacteria exhibited diverse mineral precipitation capabilities including the formation of magnetite, siderite, and rhodochrosite. The results indicated that Fe(III)- and metal-reducing communities are present in URT at the KAERI

  11. Microbial Diversity in KURT Groundwater and Biomineralization Characteristics

    International Nuclear Information System (INIS)

    Roh, Yul; Rhee, Sung Keun; Oh, Jong Min; Park, Byung Jun

    2009-03-01

    The Underground Research Tunnel (URT) located in Korea Atomic Energy Research Institute (KAERI), Daejeon, South Korea was recently constructed as an experimental site to study radionuclide transport, biogeochemistry, radionuclide-mineral interactions for the geological disposal of high level nuclear waste. Groundwater sampled from URT was used to examine microbial diversity and to enrich metal reducing bacteria for studying microbe-metal interactions. Genomic analysis indicated that the groundwater contained diverse microorganisms such as metal reducers, metal oxidizers, anaerobic denitrifying bacteria, and bacteria for reductive dechlorination. Metal-reducing bacteria enriched from the groundwater was used to study metal reduction and biomineralization. The metal-reducing bacteria enriched with acetate or lactate as the electron donors showed the bacteria reduced Fe(III)-citrate, Fe(III) oxyhydroxides, Mn(IV) oxide, and Cr(VI) as the electron acceptors. Preliminary study indicated that the enriched bacteria were able to use glucose, lactate, acetate, and hydrogen as electron donors while reducing Fe(III)-citrate or Fe(III) oxyhydroxide as the electron acceptor. The bacteria exhibited diverse mineral precipitation capabilities including the formation of magnetite, siderite, and rhodochrosite. The results indicated that Fe(III)- and metal-reducing communities are present in URT at the KAERI

  12. Citrate and renal calculi: an update

    Science.gov (United States)

    Pak, C. Y.

    1994-01-01

    Citrate is an inhibitor of the crystallization of stone-forming calcium salts. Hypocitraturia, frequently encountered in patients with nephrolithiasis, is therefore an important risk factor for stone formation. Potassium citrate provides physiological and physicochemical correction and inhibits new stone formation, not only in hypocitraturic calcium nephrolithiasis but also in uric acid nephrolithiasis. Inhibition of stone recurrence has now been validated by a randomized trial. Ongoing research has disclosed additional causes of hypocitraturia (sodium excess, low intestinal alkali absorption, but not primary citrate malabsorption). Moreover, new insights on potassium citrate action have been shown, notably that some of absorbed citrate escapes oxidation and contributes to the citraturic response, that ingestion with a meal does not sacrifice physiological or physicochemical action, that orange juice mimics but does not completely duplicate its actions, that potassium citrate may have a beneficial bone-sparing effect, that it may reduce stone fragments following ESWL, and that danger of aluminum toxicity is not great in subjects with functioning kidneys. Finally, the research on potassium citrate has led to two promising products, calcium citrate as an optimum calcium supplement and potassium-magnesium citrate which may be superior to potassium citrate in the management of stone disease.

  13. The potential impact of microbial Fe(III) reduction on subsurface U(VI) mobility at a low level radioactive waste storage site

    International Nuclear Information System (INIS)

    Wilkins, M.J.; Livens, F.R.; Vaughan, D.J.; Lloyd, J.R.; Beadle, I.; Small, J.S.

    2005-01-01

    Full text of publication follows: Fe(III) oxy-hydroxides have the potential to be utilised as terminal electron acceptors by indigenous microbial communities in the British Nuclear Fuels (BNFL) low level radioactive waste storage site at Drigg (Cumbria, UK) and these organisms may have a critical control on the biogeochemical cycling of several environmentally important radionuclides. In terms of radiological impact at Drigg, uranium is the most significant contributor to radiological impact and it is strongly influenced by biogeochemical processes. In terms of mass (moles) it is also the most abundant radionuclide in the Drigg inventory. Thus, the potential biotic and abiotic effects of Fe(III) reduction on U(VI) mobility in the Drigg subsurface are of interest. Culture-dependent and molecular techniques showed that the sediments in and around the Drigg site contained a diversity of Fe(III)-reducing bacteria. A series of microcosm experiments were utilised to create environmentally relevant experimental conditions. Microcosms set up using Drigg sediment and synthetic ground water were spiked with 100 μM U(VI) and acetate as an electron donor. U(VI) concentrations in groundwater were measured using a chemical assay while total U levels were determined using ICP-MS. Fe(II) levels were determined using the ferrozine method. Sediment surface areas were measured using BET analysis. The low surface area of the sediments resulted in only a small proportion of the 100 μM U(VI) spike sorbing onto mineral surfaces. The addition of ferri-hydrite to some microcosms resulted in an immediate lowering of soluble U(VI) concentrations, suggesting that the formation of soluble U(VI) complexes were not responsible for the minimal adsorption. The presence of biogenic Fe(II) in the microcosms did not affect the soluble U(VI) concentration. Similarly, soluble U(VI) levels remained unchanged when sediments were spiked with U(VI) post-microbial Fe(III) reduction. However, a lowering in

  14. Citrat og nyresten

    DEFF Research Database (Denmark)

    Osther, P J

    1993-01-01

    Citrate is an important naturally occurring inhibitor of calcium stone formation in urine. Urinary citrate excretion was examined in 43 consecutive patients with recurrent idiopathic calcium nephrolithiasis and in 50 normal controls by a specific enzymatic technique. Hypocitraturia (<1.6 mmol/24h...

  15. Sphaerotilus natans encrusted with nanoball-shaped Fe(III) oxide minerals formed by nitrate-reducing mixotrophic Fe(II) oxidation.

    Science.gov (United States)

    Park, Sunhwa; Kim, Dong-Hun; Lee, Ji-Hoon; Hur, Hor-Gil

    2014-10-01

    Ferrous iron has been known to function as an electron source for iron-oxidizing microorganisms in both anoxic and oxic environments. A diversity of bacteria has been known to oxidize both soluble and solid-phase Fe(II) forms coupled to the reduction of nitrate. Here, we show for the first time Fe(II) oxidation by Sphaerotilus natans strain DSM 6575(T) under mixotrophic condition. Sphaerotilus natans has been known to form a sheath structure enclosing long chains of rod-shaped cells, resulting in a thick biofilm formation under oxic conditions. Here, we also demonstrate that strain DSM 6575(T) grows mixotrophically with pyruvate, Fe(II) as electron donors and nitrate as an electron acceptor and single cells of strain DSM 6575(T) are dominant under anoxic conditions. Furthermore, strain DSM 6575(T) forms nanoball-shaped amorphous Fe(III) oxide minerals encrusting on the cell surfaces through the mixotrophic iron oxidation reaction under anoxic conditions. We propose that cell encrustation results from the indirect Fe(II) oxidation by biogenic nitrite during nitrate reduction and that causes the bacterial morphological change to individual rod-shaped single cells from filamentous sheath structures. This study extends the group of existing microorganisms capable of mixotrophic Fe(II) oxidation by a new strain, S. natans strain DSM 6575(T) , and could contribute to biogeochemical cycles of Fe and N in the environment. © 2014 The Authors. FEMS Microbiology Ecology published by John Wiley & Sons Ltd on behalf of Federation of European Microbiological Societies.

  16. Development of biodegradable polymer based tamoxifen citrate loaded nanoparticles and effect of some manufacturing process parameters on them: a physicochemical and in-vitro evaluation

    Directory of Open Access Journals (Sweden)

    Basudev Sahana

    2010-08-01

    Full Text Available Basudev Sahana, Kousik Santra, Sumit Basu, Biswajit MukherjeeDepartment of Pharmaceutical Technology, Jadavpur University, Kolkata, IndiaAbstract: The aim of the present study was to develop nanoparticles of tamoxifen citrate, a non-steroidal antiestrogenic drug used for the treatment of breast cancer. Biodegradable poly (D, L- lactide-co-glycolide-85:15 (PLGA was used to develop nanoparticles of tamoxifen citrate by multiple emulsification (w/o/w and solvent evaporation technique. Drug-polymer ratio, polyvinyl alcohol concentrations, and homogenizing speeds were varied at different stages of preparation to optimize the desired size and release profile of drug. The characterization of particle morphology and shape was performed by field emission scanning electron microscope (FE-SEM and particle size distribution patterns were studied by direct light scattering method using zeta sizer. In vitro drug release study showed that release profile of tamoxifen from biodegradable nanoparticles varied due to the change in speed of centrifugation for separation. Drug loading efficiency varied from 18.60% to 71.98%. The FE-SEM study showed that biodegradable nanoparticles were smooth and spherical in shape. The stability studies of tamoxifen citrate in the experimental nanoparticles showed the structural integrity of tamoxifen citrate in PLGA nanoparticles up to 60°C in the tested temperatures. Nanoparticles containing tamoxifen citrate could be useful for the controlled delivery of the drug for a prolonged period.Keywords: biodegradable, nanoparticles, PLGA, stability, tamoxifen citrate

  17. Electrochemical Sensing toward Trace As(III Based on Mesoporous MnFe2O4/Au Hybrid Nanospheres Modified Glass Carbon Electrode

    Directory of Open Access Journals (Sweden)

    Shaofeng Zhou

    2016-06-01

    Full Text Available Au nanoparticles decorated mesoporous MnFe2O4 nanocrystal clusters (MnFe2O4/Au hybrid nanospheres were used for the electrochemical sensing of As(III by square wave anodic stripping voltammetry (SWASV. Modified on a cheap glass carbon electrode, these MnFe2O4/Au hybrid nanospheres show favorable sensitivity (0.315 μA/ppb and limit of detection (LOD (3.37 ppb toward As(III under the optimized conditions in 0.1 M NaAc-HAc (pH 5.0 by depositing for 150 s at the deposition potential of −0.9 V. No obvious interference from Cd(II and Hg(II was recognized during the detection of As(III. Additionally, the developed electrode displayed good reproducibility, stability, and repeatability, and offered potential practical applicability for electrochemical detection of As(III in real water samples. The present work provides a potential method for the design of new and cheap sensors in the application of electrochemical determination toward trace As(III and other toxic metal ions.

  18. Photooxidation of different organic dyes (RB, MO, TB, and BG) using Fe(III)-doped TiO2 nanophotocatalyst prepared by novel chemical method

    International Nuclear Information System (INIS)

    Ghorai, Tanmay K.; Biswas, Soumya K.; Pramanik, Panchanan

    2008-01-01

    The nano-structured Fe(III)-doped TiO 2 photocatalysts with anatase phase have been developed for the oxidation of non-biodegradable different organic dyes like methyl orange (MO), rhodamine B (RB), thymol blue (TB) and bromocresol green (BG) using UV-Hg-lamp. The different compositions of Fe x Ti 1-x O 2 (x = 0.005, 0.01, 0.05, and 0.1) nanocatalysts synthesized by chemical method (CM), have been characterized by X-ray diffraction (XRD), UV-vis diffuse reflectance spectra, specific surface area (BET), transmission electronic microscopy (TEM) analysis, XPS, ESR and zeta potential. From XRD analysis, the results indicate that all the compositions of Fe(III) doped in TiO 2 catalysts gives only anatase phase not rutile phase. For complete degradation of all the solutions of the dyes (MO, RB, TB, and BG), the composition with x = 0.005 is more photoactive compared all other compositions of Fe x Ti 1-x O 2 , and degussa P25. The decolorization rate of different dyes decreases as Fe(III) concentration in TiO 2 increases. The energy band gap of Fe(III)-doped TiO 2 is found to be 2.38 eV. The oxidation state of iron has been found to be 3+ from XPS and ESR show that Fe 3+ is in low spin state

  19. On the ortho-positronium quenching reactions promoted by Fe(II), Fe(III), Co(III), Ni(II), Zn(II) and Cd(II) cyanocomplexes

    Science.gov (United States)

    Fantola Lazzarini, Anna L.; Lazzarini, Ennio

    The o-Ps quenching reactions promoted in aqueous solutions by the following six cyanocomplexes: [Fe(CN) 6] 4-; [Co(CN) 6] 3-; [Zn(CN) 4] 2-; [Cd(CN) 6] 2-; [Fe(CN) 6] 3-; [Ni(CN) 4] 2- were investigated. The first four reactions probably consist in o-Ps addition across the CN bond, their rate constants at room temperature, Tr, being ⩽(0.04±0.02) × 10 9 M -1 s -1, i.e. almost at the limit of experimental errors. The rate constant of the fifth reaction, in o-Ps oxydation, at Tr is (20.3±0.4) × 10 9 M -1 s -1. The [Ni(CN) 4] 2-k value at Tr, is (0.27±0.01) × 10 9 M -1 s -1, i.e. 100 times less than the rate constants of o-Ps oxydation, but 10 times larger than those of the o-Ps addition across the CN bond. The [Ni(CN) 4] 2- reaction probably results in formation of the following positronido complex: [Ni(CN) 4Ps] 2-. However, it is worth noting that the existence of such a complex is only indirectly deduced. In fact it arises from comparison of the [Ni(CN) 4] 2- rate constant with those of the Fe(II), Zn(II), Cd(II), and Co(III) cyanocomplexes, which, like the Ni(II) cyanocomplex, do not promote o-Ps oxydation or spin exchange reactions.

  20. Potential Remobilization of Toxic Anions during Reduction of Arsenated and Chromated Schwertmannite by the Dissimilatory Fe(III)-Reducing Bacterium Acidiphilium cryptum JF-5

    International Nuclear Information System (INIS)

    Regenspurg, Simona; Goessner, Anita; Peiffer, Stefan; Kuesel, Kirsten

    2002-01-01

    Schwertmannite, an iron(III)-oxyhydroxysulfate formed in acidic mining-impacted stream or lake waters often contaminated with toxic elements like arsenate or chromate, is able to incorporate high amounts of these oxyanions. Detoxification of the water might be achieved if precipitated arsenated or chromated schwertmannite is fixed in the sediment. However, under reduced conditions, reductive dissolution of iron oxides mediated by the activity of Fe(III)-reducing bacteria might mobilize arsenate and chromate again. In this study, the reduction of synthesized arsenated or chromated schwertmannite by the acidophilic Fe(III)-reducer Acidiphilium cryptum JF-5, isolated from an acidic mining-impacted sediment, was investigated. In TSB medium at pH 2.7 with glucose as electron donor, A. cryptum JF-5 reduced about 10% of the total Fe(III) present in pure synthetic schwertmannite but only 5% of Fe(III) present in arsenated schwertmannite. In contrast to sulfate that was released during the reductive dissolution of pure schwertmannite, arsenate was not released during the reduction of arsenated schwertmannite probably due to the high surface complexation constant of arsenate and Fe(III). In medium containing chromated schwertmannite, no Fe(II) was formed, and no glucose was consumed indicating that chromate might have been toxic to cells of A. cryptum JF-5. Both As(V) or Cr(VI) could not be utilized as electron acceptor by A. cryptum JF-5. A comparison between autoclaved (121 o C for 20 min) and non-autoclaved schwertmannite samples demonstrated that nearly 100%of the bound sulfate was released during heating, and FTIR spectra indicated a transformation of schwertmannite to goethite. This structural change was not observed with autoclaved arsenated or chromated schwertmannite. These results suggest that the mobility of arsenate and chromate is not enhanced by the activity of acidophilic Fe(III)-reducing bacteria in mining-impacted sediments. In contrast, the presence of

  1. Zeolite-Y entrapped Ru(III and Fe(III complexes as heterogeneous catalysts for catalytic oxidation of cyclohexane reaction

    Directory of Open Access Journals (Sweden)

    Chetan K. Modi

    2017-02-01

    Full Text Available Catalysis is probably one of the greatest contributions of chemistry to both economic growth and environmental protection. Herein we report the catalytic behavior of zeolite-Y entrapped Ru(III and Fe(III complexes with general formulae [M(VTCH2·2H2O]+-Y and [M(VFCH2·2H2O]+-Y [where, VTCH = vanillin thiophene-2-carboxylic hydrazone and VFCH = vanillin furoic-2-carboxylic hydrazone] over the oxidation of cyclohexane forming cyclohexanone and cyclohexanol. The samples were corroborated by various physico-chemical techniques. These zeolite-Y based complexes are stable and recyclable under current reaction conditions. Amongst them, [Ru(VTCH2⋅2H2O]+-Y showed higher catalytic activity (41.1% with cyclohexanone (84.6% selectivity.

  2. Fe(III) and Fe(II) ions different effects on Enterococcus hirae cell growth and membrane-associated ATPase activity

    Energy Technology Data Exchange (ETDEWEB)

    Vardanyan, Zaruhi [Department of Biophysics of the Biology Faculty, Yerevan State University, 1 A. Manoukian Str., 0025 Yerevan (Armenia); Trchounian, Armen, E-mail: trchounian@ysu.am [Department of Biophysics of the Biology Faculty, Yerevan State University, 1 A. Manoukian Str., 0025 Yerevan (Armenia)

    2012-01-06

    Highlights: Black-Right-Pointing-Pointer Fe{sup 3+} stimulates but Fe{sup 2+} suppresses Enterococcus hirae wild-type and atpD mutant growth. Black-Right-Pointing-Pointer Fe ions change oxidation-reduction potential drop during cell growth. Black-Right-Pointing-Pointer Fe{sup 3+} and Fe{sup 2+} have opposite effects on a membrane-associated ATPase activity. Black-Right-Pointing-Pointer These effects are either in the presence of F{sub 0}F{sub 1} inhibitor or non-functional F{sub 0}F{sub 1}. Black-Right-Pointing-Pointer Fe ions decrease protons and coupled potassium ions fluxes across the membrane. -- Abstract: Enterococcus hirae is able to grow under anaerobic conditions during glucose fermentation (pH 8.0) which is accompanied by acidification of the medium and drop in its oxidation-reduction potential (E{sub h}) from positive values to negative ones (down to {approx}-200 mV). In this study, iron (III) ions (Fe{sup 3+}) have been shown to affect bacterial growth in a concentration-dependent manner (within the range of 0.05-2 mM) by decreasing lag phase duration and increasing specific growth rate. While iron(II) ions (Fe{sup 2+}) had opposite effects which were reflected by suppressing bacterial growth. These ions also affected the changes in E{sub h} values during bacterial growth. It was revealed that ATPase activity with and without N,N Prime -dicyclohexylcarbodiimide (DCCD), an inhibitor of the F{sub 0}F{sub 1}-ATPase, increased in the presence of even low Fe{sup 3+} concentration (0.05 mM) but decreased in the presence of Fe{sup 2+}. It was established that Fe{sup 3+} and Fe{sup 2+} both significantly inhibited the proton-potassium exchange of bacteria, but stronger effects were in the case of Fe{sup 2+} with DCCD. Such results were observed with both wild-type ATCC9790 and atpD mutant (with defective F{sub 0}F{sub 1}) MS116 strains but they were different with Fe{sup 3+} and Fe{sup 2+}. It is suggested that the effects of Fe{sup 3+} might be due to

  3. Genome-scale comparison and constraint-based metabolic reconstruction of the facultative anaerobic Fe(III-reducer Rhodoferax ferrireducens

    Directory of Open Access Journals (Sweden)

    Daugherty Sean

    2009-09-01

    Full Text Available Abstract Background Rhodoferax ferrireducens is a metabolically versatile, Fe(III-reducing, subsurface microorganism that is likely to play an important role in the carbon and metal cycles in the subsurface. It also has the unique ability to convert sugars to electricity, oxidizing the sugars to carbon dioxide with quantitative electron transfer to graphite electrodes in microbial fuel cells. In order to expand our limited knowledge about R. ferrireducens, the complete genome sequence of this organism was further annotated and then the physiology of R. ferrireducens was investigated with a constraint-based, genome-scale in silico metabolic model and laboratory studies. Results The iterative modeling and experimental approach unveiled exciting, previously unknown physiological features, including an expanded range of substrates that support growth, such as cellobiose and citrate, and provided additional insights into important features such as the stoichiometry of the electron transport chain and the ability to grow via fumarate dismutation. Further analysis explained why R. ferrireducens is unable to grow via photosynthesis or fermentation of sugars like other members of this genus and uncovered novel genes for benzoate metabolism. The genome also revealed that R. ferrireducens is well-adapted for growth in the subsurface because it appears to be capable of dealing with a number of environmental insults, including heavy metals, aromatic compounds, nutrient limitation and oxidative stress. Conclusion This study demonstrates that combining genome-scale modeling with the annotation of a new genome sequence can guide experimental studies and accelerate the understanding of the physiology of under-studied yet environmentally relevant microorganisms.

  4. Photochemical Degradation of Dimethyl Phthalate by Fe(III)/tartrate/H{sub 2}O{sub 2} System

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Xianghua; Ding, Shimin; Xie, Faping [Yangtze Normal Univ., Fuling (China)

    2012-11-15

    Photochemical degradation of dimethyl phthalate (DMP) in Fe(III)/tartrate/H{sub 2}O{sub 2} system was investigated utilizing fluorescent lamps as the primary light source. Effects of initial pH, light source, and initial concentration of each reactant on DMP photodegradation was examined. The results show that the system was able to effectively photodegrade DMP utilizing visible light. Fluorescent lamp, halide lamp, UV lamp and sunlight could all be used as the light sources. The optimal pH ranged among 3.0-4.0 for the system. Increases of the initial concentrations of Fe(III) and H{sub 2}O{sub 2} accelerated the photodegradation of DMP, whereas excessively high initial tartrate concentration resulted in the decrease of photodegradation efficiency and rate of DMP.

  5. Cr(III,Mn(II,Fe(III,Co(II,Ni(II,Cu(II and Zn(II Complexes with Diisobutyldithiocarbamato Ligand

    Directory of Open Access Journals (Sweden)

    Mohammad Tarique

    2011-01-01

    Full Text Available The synthesis of sulphur and nitrogen containing dithiocarbamato ligand derived from diisobutylamine as well as its coordination compounds with 3d series transition metals is presented. These synthesized compounds were characterized on the basis of elemental analysis, conductometric measurements and IR spectral studies. The analytical data showed the stoichiometry 1:2 and 1:3 for the compounds of the types ML2 {M=Mn(II, Co(II, Ni(II, Cu(II and Zn(II} and M'L3{M'=Cr(III and Fe(III} respectively. The conductometric measurements proved the non-electrolytic behaviour of all the compounds. The bidentate nature of dithiocarbamato moiety was confirmed on the basis of IR spectral data.

  6. Blood to brain iron uptake in one Rhesus monkey using [Fe-52]-citrate and positron emission tomography (PET): influence of haloperidol

    Energy Technology Data Exchange (ETDEWEB)

    Leenders, K L [Paul Scherrer Inst., Villigen (Switzerland); [Neurology Dept., Univ. Hospital, Zuerich (Switzerland); Antonini, A; Schwarzbach, R; Smith-Jones, P; Reist, H [Paul Scherrer Inst., Villigen (Switzerland); Youdim, M [Pharmacology Dept., Technion, Haifa (Israel); Henn, V [Neurology Dept., Univ. Hospital, Zuerich (Switzerland)

    1994-12-31

    Iron is highly concentrated in the basal ganglia of the brain. The involvement of cerebral iron and its handling systems in neurodegenerative brain diseases like Parkinson`s disease and tardive dyskinesia is currently under close investigation. There is evidence from animal studies that neuroleptics can increase iron uptake into brain. This effect appeared to be due to alteration of blood-brain barrier transport by the neuroleptics, particularly chlorpromazine and haloperidol, but not clozapine. We have investigated one Rhesus monkey using positron emission tomography (PET) and [Fe-52]-citrate before and during haloperidol administration. After drug withdrawal during a period of 1.5 year the investigation procedure was repeated. The results show that in the investigated monkey haloperidol induces a reversible marked increase of iron transport across the blood brain barrier concomitant with a large increase in elimination rate of the tracer from the blood. (author).

  7. Blood to brain iron uptake in one Rhesus monkey using [Fe-52]-citrate and positron emission tomography (PET): influence of haloperidol

    International Nuclear Information System (INIS)

    Leenders, K.L.; Antonini, A.; Schwarzbach, R.; Smith-Jones, P.; Reist, H.; Youdim, M.; Henn, V.

    1994-01-01

    Iron is highly concentrated in the basal ganglia of the brain. The involvement of cerebral iron and its handling systems in neurodegenerative brain diseases like Parkinson's disease and tardive dyskinesia is currently under close investigation. There is evidence from animal studies that neuroleptics can increase iron uptake into brain. This effect appeared to be due to alteration of blood-brain barrier transport by the neuroleptics, particularly chlorpromazine and haloperidol, but not clozapine. We have investigated one Rhesus monkey using positron emission tomography (PET) and [Fe-52]-citrate before and during haloperidol administration. After drug withdrawal during a period of 1.5 year the investigation procedure was repeated. The results show that in the investigated monkey haloperidol induces a reversible marked increase of iron transport across the blood brain barrier concomitant with a large increase in elimination rate of the tracer from the blood. (author)

  8. Influence of La doping and synthesis method on the properties of CoFe{sub 2}O{sub 4} nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Mansour, S.F. [Physics Department, Faculty of Science, Zagazig University, Zagazig (Egypt); Hemeda, O.M. [Physics Department, Faculty of Science, Tanta University, Tanta (Egypt); El-Dek, S.I., E-mail: didi5550000@gmail.com [Materials Science and Nanotechnology Department, Faculty of Post Graduate Studies for Advanced Sciences (PSAS), Beni-Suef University, Beni-Suef (Egypt); Salem, B.I. [Physics Department, Faculty of Science, Tanta University, Tanta (Egypt)

    2016-12-15

    Nanocrystals of La doped CoFe{sub 2}O{sub 4} were synthesized using three different techniques: flash autocombustion, citrate–nitrate and the standard ceramic technique. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to characterize the obtained nanocrystals. All samples were crystallized in a spinel structure with cubic symmetry. The decrease in the lattice constant was endorsed to the large difference in ionic radii of both La{sup +3} (1.216 Å) and Fe (0.65 Å) in 6-f coordination. The citrate method displayed superior M{sub s} values amongst all techniques. The coercivity was found to exhibit largest values for the citrate method and then the flash while smallest values are associated with ceramic technique. - Highlights: • CoLa{sub x}Fe{sub 2−x}O{sub 4} nanocrystals crystallized in spinel cubic structure using 3 techniques. • The decrease in the lattice constant is due to the difference in ionic radius of La{sup +3} and Fe{sup 3+}. • The citrate method exhibit largest values of M{sub s} amongst all techniques. • Coercivity exhibits largest values for citrate and then flash, smallest for ceramic technique.

  9. Polarized Neutron Diffraction to Probe Local Magnetic Anisotropy of a Low-Spin Fe(III) Complex.

    Science.gov (United States)

    Ridier, Karl; Mondal, Abhishake; Boilleau, Corentin; Cador, Olivier; Gillon, Béatrice; Chaboussant, Grégory; Le Guennic, Boris; Costuas, Karine; Lescouëzec, Rodrigue

    2016-03-14

    We have determined by polarized neutron diffraction (PND) the low-temperature molecular magnetic susceptibility tensor of the anisotropic low-spin complex PPh4 [Fe(III) (Tp)(CN)3]⋅H2O. We found the existence of a pronounced molecular easy magnetization axis, almost parallel to the C3 pseudo-axis of the molecule, which also corresponds to a trigonal elongation direction of the octahedral coordination sphere of the Fe(III) ion. The PND results are coherent with electron paramagnetic resonance (EPR) spectroscopy, magnetometry, and ab initio investigations. Through this particular example, we demonstrate the capabilities of PND to provide a unique, direct, and straightforward picture of the magnetic anisotropy and susceptibility tensors, offering a clear-cut way to establish magneto-structural correlations in paramagnetic molecular complexes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Effect of surfactant amount on the morphology and magnetic properties of monodisperse ZnFe{sub 2}O{sub 4} nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Haitao, E-mail: zht95711lunwen@163.com; Liu, Ruiping; Zhang, Qiang; Wang, Qiao

    2016-03-15

    Graphical abstract: Polyol process to monodisperse ZnFe{sub 2}O{sub 4} nanoparticles. - Highlights: • An one-step, facile and inexpensive synthetic route to monodisperse ZnFe{sub 2}O{sub 4} nanoparticles is described. • The sodium citrate stabilized ZnFe{sub 2}O{sub 4} nanoparticles with a diameter in the 5–8 nm size range can be easily dispersed in water. • The synthesis is very robust in terms of variations of experimental parameters. • ZnFe{sub 2}O{sub 4} nanoparticles present ferrimagnetic behavior at room temperature with a small hysteresis. - Abstract: The spinel ZnFe{sub 2}O{sub 4} ferrites with sodium citrate as a surfactant were fabricated by polyol process. The effect of surfactant amount on the structure, morphology and magnetic properties of ZnFe{sub 2}O{sub 4} ferrites were investigated by X-ray diffraction(XRD), transmission electron microscope (TEM), thermogravimetric and differential scanning calorimetry (TG–DSC) and vibrating sample magnetometry (VSM), respectively. The results indicate that the structure of ZnFe{sub 2}O{sub 4} ferrites is a pure cubic spinel structure with a particle size of 5–8 nm. The dispersion of the synthesized ZnFe{sub 2}O{sub 4} is enhanced when the mole ratio of Fe(acac){sub 3} to sodium citrate decreases. The synthesized particles present ferrimagnetic behavior with a small hysteresis at room temperature. The increase of surfactant amount conversely leads to the decrease in the saturation magnetization value (Ms) especially when the mole ratio of Fe(acac){sub 3} to sodium citrate decreases to 8:3. Its Ms value is drastically reduced to 18.97 emu/g.

  11. Novel Schiff base (DBDDP) selective detection of Fe (III): Dispersed in aqueous solution and encapsulated in silica cross-linked micellar nanoparticles in living cell.

    Science.gov (United States)

    Gai, Fangyuan; Yin, Li; Fan, Mengmeng; Li, Ling; Grahn, Johnny; Ao, Yuhui; Yang, Xudong; Wu, Xuming; Liu, Yunling; Huo, Qisheng

    2018-03-15

    This work demonstrated the synthesis of (4E)-4-(4-(diphenylamino)benzylideneamino)-1,2-dihydro-1,5- dimethyl-2-phenylpyrazol-3-one (DBDDP) for Fe (III) detection in aqueous media and in the core of silica cross-linked micellar nanoparticles in living cells. The free DBDDP performed fluorescence enhancement due to Fe (III)-promoted hydrolysis in a mixed aqueous solution, while the DBDDP-doped silica cross-linked micellar nanoparticles (DBDDP-SCMNPs) performed an electron-transfer based fluorescence quenching of Fe (III) in living cells. The quenching fluorescence of DBDDP-SCMNPs and the concentration of Fe (III) exhibited a linear correlation, which was in accordance with the Stern-Volmer equation. Moreover, DBDDP-SCMNPs showed a low limit of detection (LOD) of 0.1 ppm and an excellent selectivity against other metal ions. Due to the good solubility and biocompatibility, DBDDP-SCMNPs could be applied as fluorescence quenching nanosensors in living cells. Copyright © 2017 Elsevier Inc. All rights reserved.

  12. STABILITY OF SYNTHESIZED SILVER NANOPARTICLES IN CITRATE AND MIXED GELATIN/CITRATE SOLUTION

    Directory of Open Access Journals (Sweden)

    Jana Kavuličová

    2018-04-01

    Full Text Available The study focuses on an investigation of the influence of both citrate and mixed gelatin/citrate as a reductant and stabilizer on the colloidal stability of silver nanoparticles (AgNPssynthesized by a chemical reduction of Ag+ ions after a short - (7th day - and long - (118th day - term storage. Formed AgNPs were characterized by a UV–vis Spectroscopy, Transmission Electron Microscope (TEM, Dynamic light scattering (DLS and Zeta-potential (ZP. The obtained results revealed that a short-term stability of the synthesized AgNPs was greatly influenced by a citrate stabilizer with the absence of gelatin. Smaller-sized AgNPs (average particle diameter of 3 nm, roughly spherical in a shape, were obtained with a narrow size distribution. The very negative value of the Zeta-potential confirmed a strong stability of the citrate capped AgNPs. However, a surface coating of the AgNPs by a gelatin/citrate stabilizer was found to be a dominant contributor in improving a long-term stability of the AgNPs (average particle diameter of 26 nm. The use of gelatin in mixed stabilizer solution provided the AgNPs with higher monodispersity and a controllable size after both the short and long-term storage.

  13. On the nature of citrate-derived surface species on Ag nanoparticles: Insights from X-ray photoelectron spectroscopy

    Science.gov (United States)

    Mikhlin, Yuri L.; Vorobyev, Sergey A.; Saikova, Svetlana V.; Vishnyakova, Elena A.; Romanchenko, Alexander S.; Zharkov, Sergey M.; Larichev, Yurii V.

    2018-01-01

    Citrate is an important stabilizing, reducing, and complexing reagent in the wet chemical synthesis of nanoparticles of silver and other metals, however, the exact nature of adsorbates, and its mechanism of action are still uncertain. Here, we applied X-ray photoelectron spectroscopy, soft X-ray absorption near-edge spectroscopy, and other techniques in order to determine the surface composition and to specify the citrate-related species at Ag nanoparticles immobilized from the dense hydrosol prepared using room-temperature reduction of aqueous Ag+ ions with ferrous ions and citrate as stabilizer (Carey Lea method). It was found that, contrary to the common view, the species adsorbed on the Ag nanoparticles are, in large part, products of citrate decomposition comprising an alcohol group and one or two carboxylate bound to the surface Ag, and minor unbound carboxylate group; these may also be mixtures of citrate with lower molecular weight anions. No ketone groups were specified, and very minor surface Ag(I) and Fe (mainly, ferric oxyhydroxides) species were detected. Moreover, the adsorbates were different at AgNPs having various size and shape. The relation between the capping and the particle growth, colloidal stability of the high-concentration sol and properties of AgNPs is briefly considered.

  14. Investigations on FCAM-III (Ca2.38Mg2.09Fe3+10.61Fe2+1.59Al9.33O36): A new homologue of the aenigmatite structure-type in the system CaO-MgO-Fe2O3-Al2O3

    Science.gov (United States)

    Zöll, Klaus; Kahlenberg, Volker; Krüger, Hannes; Tropper, Peter

    2018-02-01

    In the course of a systematic study of a part of the quaternary system Fe2O3-CaO-Al2O3-MgO (FCAM) the previously unknown compound Ca2.38Mg2.09Fe3+10.61Fe2+1.59Al9.33O36 (FCAM-III) has been synthesized. By analogy with the so-called SFCA series [1-5], our investigation in the system of FCAM shows the existence of a stoichiometric homologous series M14+6nO20+8n, where M = Fe, Ca, Al, Mg and n = 1 or 2. In air, we can prove the formation of coexisting FCAM-III and FCAM-I solid solutions at 1400 °C. By increasing the temperature up to 1425 °C FCAM-I disappears completely and FCAM-III co-exists with magnesiumferrite and a variety of calcium iron oxides. At 1450 °C FCAM-III breaks down to a mixture of FCAM-I again as well as magnesioferrite and melt. Small single-crystals of FCAM-III up to 35 μm in size could be retrieved from the 1425 °C experiment and were subsequently characterized using electron microprobe analysis and synchroton X-ray single-crystal diffraction. Finally the Fe2+/Fetot ratio was calculated from the total iron content based on the crystal-chemical formula obtained from EMPA measurements and charge balance considerations. FCAM-III or Ca2.38Mg2.09Fe3+10.61Fe2+1.59Al9.33O36 has a triclinic crystal structure (space group P 1 ̅). The basic crystallographic data are: a = 10.223(22) Å, b = 10.316(21) Å, c = 14.203(15) Å, α = 93.473(50)°, β = 107.418(67)°, γ = 109.646(60)°, V = 1323.85(2) ų, Z = 1. Using Schreinemaker's technique to analyze the phase relations in the system Fe2O3-CaO-Al2O3-MgO it was possible to obtain the semi-quantitative stability relations between the participating phases and construct a topologically correct phase sequence as a function of T and fO2. The analysis shows that Ca2Al0.5Fe1.5O5 (C2A0.25F0.75) and CaAl1.5Fe2.5O7 (CA0.75F1.25) with higher calculated Fe2+ contents are preferably formed at lower oxygen fugacity and react to CaAl0.5Fe1.5O4 (CA0.25F0.75) by increasing fO2. Spinel-type magnesium

  15. Contributions of citrate in redox potential maintenance and ATP production: metabolic pathways and their regulation in Lactobacillus panis PM1.

    Science.gov (United States)

    Kang, Tae Sun; Korber, Darren R; Tanaka, Takuji

    2013-10-01

    Lactobacillus panis PM1 belongs to the group III heterofermentative lactobacilli and can utilize various NADH-reoxidizing routes (e.g., citrate, glycerol, and oxygen) according to environmental conditions. In this study, we investigated the ability of L. panis PM1 to produce succinate, acetate, and lactate via citrate utilization. Possible pathways, as well as regulation, for citrate metabolism were examined on the basis of the genome sequence data and metabolic profiles of L. panis PM1. The presence of citrate led to the up-regulation, at the transcriptional level, of the genes encoding for citrate lyase, malate dehydrogenase, and malic enzyme of the citrate pathways by 10- to 120-fold. The transcriptional regulator of the dha operon coding for glycerol dehydratase of L. panis PM1 repressed the expression of the citrate lyase gene (10-fold). Metabolite analyses indicated that the transcriptional enhancement by citrate stimulated succinate yield. Citrate metabolism contributed to energy production by providing a major alternate pathway for NAD(+) regeneration and allowed acetyl phosphate to yield acetate/ATP instead of ethanol/NAD(+). Additionally, a branching pathway from oxaloacetate to pyruvate increased the pool of lactate, which was then used to produce ATP during stationary phase. However, the redirection of NADH-to-citrate utilization resulted in stress caused by end-products (i.e., succinate and acetate). This stress reduced succinate production by up to 50 % but did not cause significant changes at transcriptional level. Overall, citrate utilization was beneficial for the growth of L. panis PM1 by providing a NAD(+) regeneration route and producing extra ATP.

  16. Removal of Organic Dyes from Industrial Wastewaters Using UV/H2O2, UV/H2O2/Fe (II, UV/H2O2/Fe (III Processes

    Directory of Open Access Journals (Sweden)

    Nezamaddin Daneshvar

    2007-03-01

    Full Text Available UV/H2O2, UV/H2O2/Fe (II and UV/H2O2/Fe (III processes are very effective in removing pollutants from wastewater and can be used for treatment of dyestuff units wastewaters. In this study, Rhodamine B was used as a typical organic dye. Rhodamine B has found wide applications in wax, leather, and paper industries. The results from this study showed that this dye was degradable in the presence of hydrogen peroxide under UV-C irradiation (30W mercury light and Photo-Fenton process. The dye was resistant to UV irradiation. In the absence of UV irradiation, the decolorization efficiency was very negligible in the presence of hydrogen. The effects of different system variables such as initial dye concentration, duration of UV irradiation, and initial hydrogen peroxide concentration were investigated in the UV/H2O2 process. Investigation of the kinetics of the UV/H2O2 process showed that the semi-log plot of the dye concentration versus time was linear, suggesting a first order reaction. It was found that Rhodamine B decolorization efficiencies in the UV/H2O2/Fe (II and UV/H2O2/Fe (III processes were higher than that in the UV/H2O2 process. Furthermore, a solution containing 20 ppm of Rhodamine B was decolorized in the presence 18 mM of H2O2 under UV irradiation for 15 minutes. It was also found that addition of 0.1 mM Fe(II or Fe(III to the solution containing  20  ppm of the dye and 5 mM H2O2 under UV light  illumination decreased removal time to 10 min.

  17. Fe doped TiO2 photocatalyst for the removal of As(III) under visible radiation and its potential application on the treatment of As-contaminated groundwater

    International Nuclear Information System (INIS)

    Garza-Arévalo, J.I.; García-Montes, I.; Reyes, M.Hinojosa; Guzmán-Mar, J.L.; Rodríguez-González, V.

    2016-01-01

    Highlights: • Incorporation of Fe in TiO 2 lattice extended absorption to visible light region. • TiO 2 –Fe 1.0 in anatase crystalline form was synthesized by sol–gel method. • TiO 2 –Fe 1.0 showed the highest photocatalytic activity for As(III) oxidation. • TiO 2 –Fe 1.0 had the highest adsorption capacity for the removal of generated As(V). • TiO 2 –Fe is a promising material on the treatment of As contaminated groundwater. - Abstract: The Fe doped TiO 2 catalyst was evaluated under visible radiation for As(III) removal. The TiO 2 –Fe was synthesized by sol–gel technique at 0.0, 1.0, 2.5, 5.0 and 10.0 wt% iron doping concentrations. The semiconductors were characterized by X-ray diffraction, diffuse reflectance UV–vis, Raman spectroscopy, nitrogen physisorption, SEM–EDS and potentiometric titration for point of zero charge determination. The photocatalytic oxidation of As(III) was assessed in aqueous suspension contained 5 mg L −1 As(III) at pH 7 with 0.25 g L −1 catalyst loading. The incorporation of iron ions in TiO 2 lattice extended the absorption to visible light region and create surface oxygen vacancies which favor photocatalytic oxidation reaction of As(III) using a small doping amount of Fe (1.0 wt%) in TiO 2 powder. Additionally, TiO 2 –Fe 1.0 showed the highest adsorption capacity for As(V) removal compared to sol–gel TiO 2 and P25 indicating that this catalyst is a promising material for As contaminated groundwater treatment.

  18. Photooxidation of different organic dyes (RB, MO, TB, and BG) using Fe(III)-doped TiO{sub 2} nanophotocatalyst prepared by novel chemical method

    Energy Technology Data Exchange (ETDEWEB)

    Ghorai, Tanmay K. [Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur 721302 (India); Department of Chemistry, Bajkul Milani Mahavidyalaya, Kismat Bajkul, Purba Medinipur 721655 (India)], E-mail: tanmay_ghorai@yahoo.co.in; Biswas, Soumya K. [Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur 721302 (India); Pramanik, Panchanan [Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur 721302 (India)], E-mail: pramanik@chem.iitkgp.ernet.in

    2008-09-15

    The nano-structured Fe(III)-doped TiO{sub 2} photocatalysts with anatase phase have been developed for the oxidation of non-biodegradable different organic dyes like methyl orange (MO), rhodamine B (RB), thymol blue (TB) and bromocresol green (BG) using UV-Hg-lamp. The different compositions of Fe{sub x}Ti{sub 1-x}O{sub 2} (x = 0.005, 0.01, 0.05, and 0.1) nanocatalysts synthesized by chemical method (CM), have been characterized by X-ray diffraction (XRD), UV-vis diffuse reflectance spectra, specific surface area (BET), transmission electronic microscopy (TEM) analysis, XPS, ESR and zeta potential. From XRD analysis, the results indicate that all the compositions of Fe(III) doped in TiO{sub 2} catalysts gives only anatase phase not rutile phase. For complete degradation of all the solutions of the dyes (MO, RB, TB, and BG), the composition with x = 0.005 is more photoactive compared all other compositions of Fe{sub x}Ti{sub 1-x}O{sub 2}, and degussa P25. The decolorization rate of different dyes decreases as Fe(III) concentration in TiO{sub 2} increases. The energy band gap of Fe(III)-doped TiO{sub 2} is found to be 2.38 eV. The oxidation state of iron has been found to be 3+ from XPS and ESR show that Fe{sup 3+} is in low spin state.

  19. Redox topotactic reactions in FeII − III (oxy)hydroxycarbonate new minerals related to fougèrite in gleysols: “trébeurdenite and mössbauerite”

    International Nuclear Information System (INIS)

    Génin, Jean-Marie R.; Guérin, O.; Herbillon, A. J.; Kuzmann, E.; Mills, S. J.; Morin, G.; Ona-Nguema, G.; Ruby, C.; Upadhyay, C.

    2012-01-01

    Fougèrite mineral responsible for the bluish-green shade of gleysols in aquifers was identified as Fe II − III oxyhydroxycarbonate, [Fe 6 ( 1-x) II Fe 6x III O 12 H 2(7 − 3x) ] 2 +  · [CO 3 2- · 3H 2 O] 2 −  where the average ferric molar fraction x = [Fe III /Fe total ] was restricted to the [1/3–2/3] range, up till now. In this paper, Mössbauer spectra of gleys extracted from the schorre of maritime marshes have values of x in the [2/3–1] range. Magnetic properties of homologous chemical compounds studied by Mössbauer spectroscopy are explained with long range order of Fe III ions within Fe cation layers for x = 1/3, 2/3 and 1. Observed values are mixtures of topotactic domains that are in fact minerals with names proposed to IMA: fougèrite for x = 1/3, trébeurdenite for x = 2/3 and mössbauerite for x = 1.

  20. Surface decoration of amine-rich carbon nitride with iron nanoparticles for arsenite (As{sup III}) uptake: The evolution of the Fe-phases under ambient conditions

    Energy Technology Data Exchange (ETDEWEB)

    Georgiou, Y., E-mail: yiannisgeorgiou@hotmail.com [Physics Department, University of Ioannina, Ioannina 45110 (Greece); Mouzourakis, E., E-mail: emouzou@cc.uoi.gr [Physics Department, University of Ioannina, Ioannina 45110 (Greece); Bourlinos, A.B., E-mail: bourlino@cc.uoi.gr [Physics Department, University of Ioannina, Ioannina 45110 (Greece); Regional Centre of Advanced Technologies and Materials, Faculty of Science, Department of Physical Chemistry and Experimental Physics, Palacky University in Olomouc, 77146 (Czech Republic); Zboril, R., E-mail: radek.zboril@upol.cz [Regional Centre of Advanced Technologies and Materials, Faculty of Science, Department of Physical Chemistry and Experimental Physics, Palacky University in Olomouc, 77146 (Czech Republic); Karakassides, M.A., E-mail: mkarakas@cc.uoi.gr [Department of Materials Science and Engineering, University of Ioannina, Ioannina 45110 (Greece); Douvalis, A.P., E-mail: adouval@uoi.gr [Physics Department, University of Ioannina, Ioannina 45110 (Greece); Bakas, Th., E-mail: tbakas@cc.uoi.gr [Physics Department, University of Ioannina, Ioannina 45110 (Greece); Deligiannakis, Y., E-mail: ideligia@cc.uoi.gr [Physics Department, University of Ioannina, Ioannina 45110 (Greece)

    2016-07-15

    Highlights: • Novel hybrid based on carbon nitride and iron nanoparticles (gC{sub 3}N{sub 4}-rFe). • gC{sub 3}N{sub 4}-rFe superior As{sup III} sorbent(76.5 mg g{sup −1}). • Surface complexation modeling of As{sup III} adsorption. • Dual mode EPR,monitoring of Fe{sup 2+} and Fe{sup 3+} evolution. - Abstract: A novel hybrid material (gC{sub 3}N{sub 4}-rFe) consisting of amine-rich graphitic carbon nitride (gC{sub 3}N{sub 4}), decorated with reduced iron nanoparticles (rFe) is presented. XRD and TEM show that gC{sub 3}N{sub 4}-rFe bears aggregation-free Fe-nanoparticles (10 nm) uniformly dispersed over the gC{sub 3}N{sub 4} surface. In contrast, non-supported iron nanoparticles are strongly aggregated, with non-uniform size distribution (20–100 nm). {sup 57}Fe-Mössbauer spectroscopy, dual-mode electron paramagnetic resonance (EPR) and magnetization measurements, allow a detailed mapping of the evolution of the Fe-phases after exposure to ambient O{sub 2}. The as-prepared gC{sub 3}N{sub 4}-rFe bears Fe{sup 2+} and Fe° phases, however only after long exposure to ambient O{sub 2}, a Fe-oxide layer is formed around the Fe° core. In this [Fe°/Fe-oxide] core-shell configuration, the gC{sub 3}N{sub 4}-rFe hybrid shows enhanced As{sup III} uptake capacity of 76.5 mg g{sup −1}, i.e., ca 90% higher than the unmodified carbonaceous support, and 300% higher than the non-supported Fe-nanoparticles. gC{sub 3}N{sub 4}-rFe is a superior As{sup III} sorbent i.e., compared to its single counterparts or vs. graphite/graphite oxide or activated carbon analogues (11–36 mg g{sup −1}). The present results demonstrate that the gC{sub 3}N{sub 4} matrix is not simply a net that holds the particles, but rather an active component that determines particle formation dynamics and ultimately their redox profile, size and surface dispersion homogeneity.

  1. Nickel incorporation in Fe(II, III hydroxysulfate Green Rust: effect on crystal lattice spacing and oxidation products Incorporação de níquel em Fe (II-III Grenn Rust hidroxisulfato: efeito sobre a estrutura cristalina e produtos de oxidação

    Directory of Open Access Journals (Sweden)

    Lucia Helena Garófalo Chaves

    2009-10-01

    Full Text Available Ni(II-Fe(II-Fe(III layered double hydroxides (LDH or Ni-containing sulfate green rust (GR2 samples were prepared from Ni(II, Fe(II and Fe(III sulfate salts and analyzed with X ray diffraction. Nickel is readily incorporated in the GR2 structure and forms a solid solution between GR2 and a Ni(II-Fe(III LDH. There is a correlation between the unit cell a-value and the fraction of Ni(II incorporated into the Ni(II-GR2 structure. Since there is strong evidence that the divalent/trivalent cation ratio in GR2 is fixed at 2, it is possible in principle to determine the extent of divalent cation substitution for Fe(II in GR2 from the unit cell a-value. Oxidation forms a mixture of minerals but the LDH structure is retained if at least 20 % of the divalent cations in the initial solution are Ni(II. It appears that Ni(II is incorporated in a stable LDH structure. This may be important for two reasons, first for understanding the formation of LDHs, which are anion exchangers, in the natural environment. Secondly, this is important for understanding the fate of transition metals in the environment, particularly in the presence of reduced Fe compounds.Amostras de hidróxidos de dupla camada (HDC, ou "sulfate green rust" (GR2, contendo Ni foram preparadas utilizando-se sulfatos de Ni(II, Fe(II e Fe(III e analisadas por difração de raios X. O Ni está incorporado na estrutura do GR2 e forma um sólido entre GR2 e um HDC contendo Ni(II-Fe(III. Há correlação entre os valores de "a" da célula unitária e os da fração de Ni(II incorporado na estrutura do Ni(II-GR2. Desde que haja forte evidência de que a razão entre os cátions divalente/trivalente no GR2 seja igual a 2, é possível, a princípio, determinar a extensão da substituição do cátion divalente por Fe(II no GR2 a partir dos valores de "a" da célula unitária do cristal. Sob o efeito da oxidação, é formada uma mistura de minerais, porém a estrutura do HDC não é alterada se pelo menos

  2. Abrupt spin transition with thermal hysteresis of iron(III) complex [Fe(III)(Him)2(hapen)]AsF6 (Him = imidazole, H2hapen = N,N'-bis(2-hydroxyacetophenylidene)ethylenediamine).

    Science.gov (United States)

    Fujinami, Takeshi; Koike, Masataka; Matsumoto, Naohide; Sunatsuki, Yukinari; Okazawa, Atsushi; Kojima, Norimichi

    2014-02-17

    The solvent-free spin crossover iron(III) complex [Fe(III)(Him)2(hapen)]AsF6 (Him = imidazole, H2hapen = N,N'-bis(2-hydroxyacetophenylidene)ethylenediamine), exhibiting thermal hysteresis, was synthesized and characterized. The Fe(III) ion has an octahedral coordination geometry, with N2O2 donor atoms of the planar tetradentate ligand (hapen) and two nitrogen atoms of two imidazoles at the axial positions. One of two imidazoles is hydrogen-bonded to the phenoxo oxygen atom of hapen of the adjacent unit to give a hydrogen-bonded one-dimensional chain, while the other imidazole group is free from hydrogen bonding. The temperature dependencies of the magnetic susceptibilities and Mössbauer spectra revealed an abrupt spin transition between the high-spin (S = 5/2) and low-spin (S = 1/2) states, with thermal hysteresis.

  3. X-ray Absorption Spectroscopy and Density Functional Theory Studies of [(H3buea)FeIII-X]n1 (X= S2-, O2-,OH-): Comparison of Bonding and Hydrogen Bonding in Oxo and Sulfido Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Dey, Abhishek; Hocking, Rosalie K.; /Stanford U., Chem. Dept.; Larsen, Peter; Borovik, Andrew S.; /Kansas U.; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.; /SLAC,

    2006-09-27

    Iron L-edge, iron K-edge, and sulfur K-edge X-ray absorption spectroscopy was performed on a series of compounds [Fe{sup III}H{sub 3}buea(X)]{sup n-} (X = S{sup 2-}, O{sup 2-}, OH{sup -}). The experimentally determined electronic structures were used to correlate to density functional theory calculations. Calculations supported by the data were then used to compare the metal-ligand bonding and to evaluate the effects of H-bonding in Fe{sup III}-O vs Fe{sup III-}S complexes. It was found that the Fe{sup III-}O bond, while less covalent, is stronger than the FeIII-S bond. This dominantly reflects the larger ionic contribution to the Fe{sup III-}O bond. The H-bonding energy (for three H-bonds) was estimated to be -25 kcal/mol for the oxo as compared to -12 kcal/mol for the sulfide ligand. This difference is attributed to the larger charge density on the oxo ligand resulting from the lower covalency of the Fe-O bond. These results were extended to consider an Fe{sup IV-}O complex with the same ligand environment. It was found that hydrogen bonding to Fe{sup IV-}O is less energetically favorable than that to Fe{sup III-}O, which reflects the highly covalent nature of the Fe{sup IV-}O bond.

  4. 21 CFR 582.6195 - Calcium citrate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Calcium citrate. 582.6195 Section 582.6195 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Calcium citrate. (a) Product. Calcium citrate. (b) Conditions of use. This substance is generally...

  5. Physiological effects of magnetite (Fe3O4) nanoparticles on perennial ryegrass (Lolium perenne L.) and pumpkin (Cucurbita mixta) plants.

    Science.gov (United States)

    Wang, Huanhua; Kou, Xiaoming; Pei, Zhiguo; Xiao, John Q; Shan, Xiaoquan; Xing, Baoshan

    2011-03-01

    To date, knowledge gaps and associated uncertainties remain unaddressed on the effects of nanoparticles (NPs) on plants. This study was focused on revealing some of the physiological effects of magnetite (Fe(3)O(4)) NPs on perennial ryegrass (Lolium perenne L.) and pumpkin (Cucurbita mixta cv. white cushaw) plants under hydroponic conditions. This study for the first time reports that Fe(3)O(4) NPs often induced more oxidative stress than Fe(3)O(4) bulk particles in the ryegrass and pumpkin roots and shoots as indicated by significantly increased: (i) superoxide dismutase and catalase enzyme activities, and (ii) lipid peroxidation. However, tested Fe(3)O(4) NPs appear unable to be translocated in the ryegrass and pumpkin plants. This was supported by the following data: (i) No magnetization was detected in the shoots of either plant treated with 30, 100 and 500 mg l(-1) Fe(3)O(4) NPs; (ii) Fe K-edge X-ray absorption spectroscopic study confirmed that the coordination environment of Fe in these plant shoots was similar to that of Fe-citrate complexes, but not to that of Fe(3)O(4) NPs; and (iii) total Fe content in the ryegrass and pumpkin shoots treated with Fe(3)O(4) NPs was not significantly increased compared to that in the control shoots.

  6. 21 CFR 582.5195 - Calcium citrate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Calcium citrate. 582.5195 Section 582.5195 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Supplements 1 § 582.5195 Calcium citrate. (a) Product. Calcium citrate. (b) Conditions of use. This substance...

  7. 21 CFR 582.1195 - Calcium citrate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Calcium citrate. 582.1195 Section 582.1195 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1195 Calcium citrate. (a) Product. Calcium citrate. (b) Conditions of use. This substance is...

  8. Fe(III Is Essential for Porcine Embryonic Development via Mitochondrial Function Maintenance.

    Directory of Open Access Journals (Sweden)

    Ming-Hui Zhao

    Full Text Available Iron is an important trace element involved in several biological processes. The role of iron in porcine early embryonic development remains unknown. In the present study, we depleted iron (III, Fe3+ with deferoxamine (DFM, a specific Fe3+ chelator, in cultured porcine parthenotes and monitored embryonic development, apoptosis, mitochondrial membrane potential, and ATP production. Results showed biphasic function of Fe3+ in porcine embryo development. 0.5 μM DFM obviously increased blastocyst formation (57.49 ± 2.18% vs. control, 43.99 ± 1.72%, P < 0.05 via reduced (P < 0.05 production of reactive oxygen species (ROS, further increased mitochondrial membrane potential and ATP production in blastocysts (P < 0.05. 0.5 μM DFM decreased mRNA expression of Caspase 3 (Casp3 and increased Bcl-xL. However, results showed a significant reduction in blastocyst formation in the presence of 5.0 μM DFM compared with the control group (DFM, 21.62 ± 3.92% vs. control, 43.99 ± 1.73%, P < 0.05. Fe3+ depletion reduced the total (DFM, 21.10 ± 8.78 vs. control, 44.09 ± 13.65, P < 0.05 and increased apoptotic cell number (DFM, 11.10 ± 5.24 vs. control, 2.64 ± 1.43, P < 0.05 in the blastocyst. An obvious reduction in mitochondrial membrane potential and ATP level after 5.0 μM DFM treatment was observed. Co-localization between mitochondria and cytochrome c was reduced after high concentration of DFM treatment. In conclusion, Fe3+ is essential for porcine embryonic development via mitochondrial function maintenance, but redundant Fe3+ impairs the function of mitochondria.

  9. A voltammetric method for Fe(iii) in blood serum using a screen-printed electrode modified with a Schiff base ionophore.

    Science.gov (United States)

    Mittal, Susheel K; Rana, Sonia; Kaur, Navneet; Banks, Craig E

    2018-05-23

    Herein, a potent electrochemical ionophore (SMS-2) based on a Schiff base has been used for the modification of a screen-printed electrode (SPE). The modified disposable electrode can selectively detect ferric ions in an aqueous medium. Redox behavior of the proposed strip was characterized using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Incorporation of the ligand in the ink of the SPE enhanced the analytical performance of the electrode, and its surface modification was confirmed by SEM and EDX analysis. Shifting/quenching of the cathodic peak potential of the ionophore after binding with Fe(iii) ions was used to detect and measure the ferric ion concentration. This sensor can identify Fe(iii) in the detection range from 0.625 μM to 7.5 μM. The modified SPE can selectively detect ferric ions in the presence of many other interfering ions and has been successfully used to determine the Fe(iii) content in blood serum samples. The metal-ionophore complex structure was optimized using DFT calculations to study the energetics of the metal-ionophore interactions.

  10. Dependence of magnetic and structural properties of Ni 0.5 M 0.5 Fe ...

    African Journals Online (AJOL)

    Ni0.5M0.5Fe2O4 (M = Co, Cu) ferrite nanoparticles were synthesized using citrate precursor method. The citrate precursor was annealed at temperatures 400oC, 450oC, 500oC and 550oC. The annealed powders were characterized using X-ray diffractometer (XRD) and vibrating sample magnetometer (VSM). Observed ...

  11. Cacotheline as an oxidimetric reagent. Determination of Sn(II), Cu(I), Ti(III), Fe(II), V(II) and V(III)

    International Nuclear Information System (INIS)

    Nemani Murty, K.; Yedluri Rao, P.; Geddada Chalam, K.

    1982-01-01

    Sn(II), Ti(III), Cu(I),Fe(II), V(III) and V(II) can be titrated potentiometrically with cacotheline in 1-4 M hydrochloric acid, 0.5-2 M hydrochloric acid, 0.5-1.5 M sulphuric acid in presence of 4 ml of 10% EDTA solution in a total volume of 50 ml, 9-10 M phosphoric acid, 4-8 M acetic acid and 3-8 M acetic acid respectively. Cacotheline can be used for the assay of tin plate and solder. The cacotheline undergoes a 2-electron reduction reaction. A cacotheline solution (0.005 M) in 0.02 M hydrochloric acid is fairly stable for several months. The conditional redox potentials of cacotheline have been determined in sulphuric, phosphoric and acetic acid medium. (Author)

  12. Recyclable UV and visible light photocatalytically active amorphous TiO2 doped with M (III) ions (M = Cr and Fe)

    International Nuclear Information System (INIS)

    Buddee, Supat; Wongnawa, Sumpun; Sirimahachai, Uraiwan; Puetpaibool, Walailak

    2011-01-01

    Research highlights: → The low photocatalytic activity of amorphous TiO2 was enhanced by doping with Cr(III) or Fe(III) ions. → The doped catalysts performed close to P25 under UV light and better with visible light. → The doped catalysts can be recycled. - Abstract: Samples of amorphous TiO 2 doped with Cr(III) and Fe(III), designated as Cr-TiO 2 and Fe-TiO 2 , were prepared via modified impregnation method. The resulting products were characterized by X-ray diffraction, scanning electron microscopy, specific surface area by the Brunauer, Emmett and Teller method, UV-vis absorption and diffuse reflectance spectroscopy, and electron spin resonance spectroscopy. Experimental results revealed that the concentrations of dopants under studied, from 0.05 to 0.2 mol%, had no effect on the phase of products. The band gap energies shifted from 3.28 eV in the undoped amorphous TiO 2 to 2.50 eV and 2.86 eV for Fe-TiO 2 and Cr-TiO 2 , respectively. The doped amorphous TiO 2 showed photocatalytic activities under both UV and visible light with optimal results at 0.1 mol% dopants. Under UV irradiation, the 0.1 mol% doped samples decolorized methylene blue solutions to the same extent as the commercial TiO 2 samples (P25 and anatase) in 5 h. Under visible light, the doped samples decolorized dye solutions in 12 h while the commercial ones were much less active. The used catalysts can be recycled many times without any special treatment.

  13. Dependence of electrical property on the applied magnetic fields in spin coated Fe(III)-Phorphyrin films

    International Nuclear Information System (INIS)

    Utari; Kusumandari; Purnama, B.; Mudasir; Abraha, K.

    2016-01-01

    We report here on the experimental results of the effect of external magnetic field on the current flow in plane surface of Fe(III)-porphyrin thin layer. The deposition of the Fe(III)- porphyrin thin layer was done by spin coating method. The I-V characteristics of film were measured by means of two point probes. The sample of layer number N = 4 was used to evaluate the magnetic effect on the electrical currents. The ohmic characteristics of the I-V film measurement were obtained. The current decreases when magnetic field is applied to the system and saturated current is obtained at a given magnetic field. Here, the decrease in the current can be attributed to the recombination of carrier charge under the magnetic field. In addition, the magnitude of the saturated current is found to increase with the increase in the voltage used. (paper)

  14. Biogeochemistry of Fe and Tc Reduction and Oxidation in FRC Sediment

    International Nuclear Information System (INIS)

    John M, Zachara; James K, Fredrickson; Ravi K, Kukkadapu; Steven C, Smith; David W, Kennedy

    2004-01-01

    The objectives are: (1) To rigorously characterize the distribution of Fe(II) and Fe(III) in FRC sediment. (2) To identify changes to Fe(II)/Fe(III) distribution and concentration resulting from DIRB activity. (3) To determine the dependence of Tc(VII) reduction rate on biogenic Fe(II) and it's forms. (4) To establish tendency of Tc(IV) and biogenic Fe(II) to oxidize and their effects on Tc immobilization. The mineralogic and chemical properties of the pristine, bioreduced, and chemically extracted FRC sediments were characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), X-ray microscopy (XRM, at the PNC-CAT beamline at APS), Moessbauer spectroscopy, and scanning and transmission electron microscopy with lattice fringe imaging. Chemical extraction included dithionite-citrate-bicarbonate (DCB), acid ammonium oxalate (AAO), and hydroxylamine hydrochloride (HAH). The FRC sediment was incubated under anoxic conditions with the facultative dissimilatory metal-reducing bacterium Shewanella putrefaciens, strain CN32 in defined aqueous solutions/media with bicarbonate and PIPES buffers for time periods exceeding 75 d. Lactate was used as the electron donor. Aqueous and sorbed Fe(II) (ferrozine assay and 0.5 N HCl extraction) and Mn(II) (ICP-MS and 10 mM CuSO 4 extraction), and pH were monitored to define the reduction progress and extent. The bioreduced materials were characterized using the abovementioned techniques. Bioreduced (pasteurized) sediment or chemically extracted/reduced sediment spiked with Fe(II) was washed with a PIPES buffer/electrolyte solution, and spiked with NaTc(VII)O 4 to yield a concentration of 20 (micro)M. The Tc(VII)-spiked samples were agitated and equilibrated at 25 C and sampled over time to assess the Tc(VII) reduction rate. Selected sediment samples containing 20 (micro)M of reduced Tc [Tc(IV)] were subjected to oxidation by: (1) successive headspace replacements of air, and (2) open system equilibration with air. Removed aqueous

  15. LiFePO4 Nanostructures Fabricated from Iron(III) Phosphate (FePO4 x 2H2O) by Hydrothermal Method.

    Science.gov (United States)

    Saji, Viswanathan S; Song, Hyun-Kon

    2015-01-01

    Electrode materials having nanometer scale dimensions are expected to have property enhancements due to enhanced surface area and mass/charge transport kinetics. This is particularly relevant to intrinsically low electronically conductive materials such as lithium iron phosphate (LiFePO4), which is of recent research interest as a high performance intercalation electrode material for Li-ion batteries. Many of the reported works on LiFePO4 synthesis are unattractive either due to the high cost of raw materials or due to the complex synthesis technique. In this direction, synthesis of LiFePO4 directly from inexpensive FePO4 shows promise.The present study reports LiFePO4 nanostructures prepared from iron (III) phosphate (FePO4 x 2H2O) by precipitation-hydrothermal method. The sintered powder was characterized by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), Inductive coupled plasma-optical emission spectroscopy (ICP-OES), and Electron microscopy (SEM and TEM). Two synthesis methods, viz. bulk synthesis and anodized aluminum oxide (AAO) template-assisted synthesis are reported. By bulk synthesis, micro-sized particles having peculiar surface nanostructuring were formed at precipitation pH of 6.0 to 7.5 whereas typical nanosized LiFePO4 resulted at pH ≥ 8.0. An in-situ precipitation strategy inside the pores of AAO utilizing the spin coating was utilized for the AAO-template-assisted synthesis. The template with pores filled with the precipitate was subsequently subjected to hydrothermal process and high temperature sintering to fabricate compact rod-like structures.

  16. Fe doped TiO{sub 2} photocatalyst for the removal of As(III) under visible radiation and its potential application on the treatment of As-contaminated groundwater

    Energy Technology Data Exchange (ETDEWEB)

    Garza-Arévalo, J.I.; García-Montes, I. [Universidad Autónoma de Nuevo León, UANL, Facultad de Ciencias Químicas, Cd. Universitaria, San Nicolás de los Garza, Nuevo León C.P. 66451, México (Mexico); Reyes, M.Hinojosa [Instituto Potosino de Investigación Científica y Tecnológica, IPICYT, División de Materiales Avanzados, Camino a la Presa San José 2055, Col. Lomas 4a. sección, San Luis Potosí, SLP 78216, México (Mexico); Guzmán-Mar, J.L. [Universidad Autónoma de Nuevo León, UANL, Facultad de Ciencias Químicas, Cd. Universitaria, San Nicolás de los Garza, Nuevo León C.P. 66451, México (Mexico); Rodríguez-González, V. [Instituto Potosino de Investigación Científica y Tecnológica, IPICYT, División de Materiales Avanzados, Camino a la Presa San José 2055, Col. Lomas 4a. sección, San Luis Potosí, SLP 78216, México (Mexico); and others

    2016-01-15

    Highlights: • Incorporation of Fe in TiO{sub 2} lattice extended absorption to visible light region. • TiO{sub 2}–Fe 1.0 in anatase crystalline form was synthesized by sol–gel method. • TiO{sub 2}–Fe 1.0 showed the highest photocatalytic activity for As(III) oxidation. • TiO{sub 2}–Fe 1.0 had the highest adsorption capacity for the removal of generated As(V). • TiO{sub 2}–Fe is a promising material on the treatment of As contaminated groundwater. - Abstract: The Fe doped TiO{sub 2} catalyst was evaluated under visible radiation for As(III) removal. The TiO{sub 2}–Fe was synthesized by sol–gel technique at 0.0, 1.0, 2.5, 5.0 and 10.0 wt% iron doping concentrations. The semiconductors were characterized by X-ray diffraction, diffuse reflectance UV–vis, Raman spectroscopy, nitrogen physisorption, SEM–EDS and potentiometric titration for point of zero charge determination. The photocatalytic oxidation of As(III) was assessed in aqueous suspension contained 5 mg L{sup −1} As(III) at pH 7 with 0.25 g L{sup −1} catalyst loading. The incorporation of iron ions in TiO{sub 2} lattice extended the absorption to visible light region and create surface oxygen vacancies which favor photocatalytic oxidation reaction of As(III) using a small doping amount of Fe (1.0 wt%) in TiO{sub 2} powder. Additionally, TiO{sub 2}–Fe 1.0 showed the highest adsorption capacity for As(V) removal compared to sol–gel TiO{sub 2} and P25 indicating that this catalyst is a promising material for As contaminated groundwater treatment.

  17. 21 CFR 184.1625 - Potassium citrate.

    Science.gov (United States)

    2010-04-01

    ... acid with potassium hydroxide or potassium carbonate. It occurs as transparent crystals or a white... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Potassium citrate. 184.1625 Section 184.1625 Food... Specific Substances Affirmed as GRAS § 184.1625 Potassium citrate. (a) Potassium citrate (C6H5K3O7·H2O, CAS...

  18. Efficiency of a new strategy involving a new class of natural hetero-ligand iron(III) chelates (Fe(III)-NHL) to improve fruit tree growth in alkaline/calcareous soils.

    Science.gov (United States)

    Fuentes, Marta; Ortuño, María F; Pérez-Sarmiento, Francisco; Bacaicoa, Eva; Baigorri, Roberto; Conejero, Wenceslao; Torrecillas, Arturo; García-Mina, José M

    2012-12-01

    Iron (Fe) chlorosis is a serious problem affecting the yield and quality of numerous crops and fruit trees cultivated in alkaline/calcareous soils. This paper describes the efficiency of a new class of natural hetero-ligand Fe(III) chelates (Fe-NHL) to provide available Fe for chlorotic lemon trees grown in alkaline/calcareous soils. These chelates involve the participation in the reaction system of a partially humified lignin-based natural polymer and citric acid. First results showed that Fe-NHL was adsorbed on the soil matrix while maintaining available Fe for plants in alkaline/calcareous solution. The effects of using three different sources as Fe fertilisers were also compared: two Fe-NHL formulations (NHL1, containing 100% of Fe as Fe-NHL, and NHL2, containing 80% of Fe as Fe-NHL and 20% of Fe as Fe-ethylenediamine-N,N'-bis-(o-hydroxyphenylacetic) acid (Fe-EDDHA)) and Fe-EDDHA. Both Fe-NHL formulations increased fruit yield without negative effects on fruit quality in comparison with Fe-EDDHA. In the absence of the Fe-starter fraction (NHL1), trees seemed to optimise Fe assimilation and translocation from Fe-NHL, directing it to those parts of the plant more involved in development. The field assays confirmed that Fe-NHL-based fertilisers are able to provide Fe to chlorotic trees, with results comparable to Fe-EDDHA. Besides, this would imply a more sustainable and less expensive remediation than synthetic chelates. Copyright © 2012 Society of Chemical Industry.

  19. Interaction of Vimang (Mangifera indica L. extract) with Fe(III) improves its antioxidant and cytoprotecting activity.

    Science.gov (United States)

    Pardo-Andreu, Gilberto L; Sánchez-Baldoquín, Carlos; Avila-González, Rizette; Yamamoto, Edgar T Suzuki; Revilla, Andrés; Uyemura, Sérgio Akira; Naal, Zeki; Delgado, René; Curti, Carlos

    2006-11-01

    A standard aqueous stem bark extract from selected species of Mangifera indica L. (Anacardiaceae)--Vimang, whose major polyphenolic component is mangiferin, displays potent in vitro and in vivo antioxidant activity. The present study provides evidence that the Vimang-Fe(III) mixture is more effective at scavenging 2,2-diphenyl-1-picrylhydrazyl (DPPH) and superoxide radicals, as well as in protecting against t-butyl hydroperoxide-induced mitochondrial lipid peroxidation and hypoxia/reoxygenation-induced hepatocytes injury, compared to Vimang alone. Voltammetric assays demonstrated that Vimang, in line with the high mangiferin content of the extract, behaves electrochemically like mangiferin, as well as interacts with Fe(III) in close similarity with mangiferin's interaction with the cation. These results justify the high efficiency of Vimang as an agent protecting from iron-induced oxidative damage. We propose Vimang as a potential therapy against the deleterious action of reactive oxygen species generated during iron-overload, such as that occurring in diseases like beta-thalassemia, Friedreich's ataxia and haemochromatosis.

  20. Disproportionation of hydroxylamine by water-soluble iron(III) porphyrinate compounds.

    Science.gov (United States)

    Bari, Sara E; Amorebieta, Valentín T; Gutiérrez, María M; Olabe, José A; Doctorovich, Fabio

    2010-01-01

    The reactions of hydroxylamine (HA) with several water-soluble iron(III) porphyrinate compounds, namely iron(III) meso-tetrakis-(N-ethylpyridinium-2yl)-porphyrinate ([Fe(III)(TEPyP)](5+)), iron(III) meso-tetrakis-(4-sulphonatophenyl)-porphyrinate ([Fe(III)(TPPS)](3-)), and microperoxidase 11 ([Fe(III)(MP11)]) were studied for different [Fe(III)(Porph)]/[HA] ratios, under anaerobic conditions at neutral pH. Efficient catalytic processes leading to the disproportionation of HA by these iron(III) porphyrinates were evidenced for the first time. As a common feature, only N(2) and N(2)O were found as gaseous, nitrogen-containing oxidation products, while NH(3) was the unique reduced species detected. Different N(2)/N(2)O ratios obtained with these three porphyrinates strongly suggest distinctive mechanistic scenarios: while [Fe(III)(TEPyP)](5+) and [Fe(III)(MP11)] formed unknown steady-state porphyrinic intermediates in the presence of HA, [Fe(III)(TPPS)](3-) led to the well characterized soluble intermediate, [Fe(II)(TPPS)NO](4-). Free-radical formation was only evidenced for [Fe(III)(TEPyP)](5+), as a consequence of a metal centered reduction. We discuss the catalytic pathways of HA disproportionation on the basis of the distribution of gaseous products, free radicals formation, the nature of porphyrinic intermediates, the Fe(II)/Fe(III) redox potential, the coordinating capabilities of each complex, and the kinetic analysis. The absence of NO(2)(-) revealed either that no HAO-like activity was operative under our reaction conditions, or that NO(2)(-), if formed, was consumed in the reaction milieu.

  1. Microbial Reduction of Fe(III) and SO42- and Associated Microbial Communities in the Alluvial Aquifer Groundwater and Sediments.

    Science.gov (United States)

    Lee, Ji-Hoon; Lee, Bong-Joo

    2017-11-25

    Agricultural demands continuously increased use of groundwater, causing drawdown of water table and need of artificial recharge using adjacent stream waters. River water intrusion into groundwater can alter the geochemical and microbiological characteristics in the aquifer and subsurface. In an effort to investigate the subsurface biogeochemical activities before operation of artificial recharge at the test site, established at the bank of Nakdong River, Changwon, South Korea, organic carbon transported from river water to groundwater was mimicked and the effect on the indigenous microbial communities was investigated with the microcosm incubations of the groundwater and subsurface sediments. Laboratory incubations indicated microbial reduction of Fe(III) and sulfate. Next-generation Illumina MiSeq sequences of V4 region of 16S rRNA gene provided that the shifts of microbial taxa to Fe(III)-reducing and/or sulfate-reducing microorganisms such as Geobacter, Albidiferax, Desulfocapsa, Desulfuromonas, and Desulfovibrio were in good correlation with the sequential flourishment of microbial reduction of Fe(III) and sulfate as the incubations progressed. This suggests the potential role of dissolved organic carbons migrated with the river water into groundwater in the managed aquifer recharge system on the indigenous microbial community composition and following alterations of subsurface biogeochemistry and microbial metabolic activities.

  2. Incompatibility of Contrast Medium and Trisodium Citrate

    International Nuclear Information System (INIS)

    Delcour, Christian; Bruninx, Guy

    2013-01-01

    To test the compatibility of trisodium citrate, a catheter lock solution, with iodinated contrast medium. Iohexol, iobitridol, iodixanol, ioxaglate, ioxithalamate, iomeprol, and iopromide were tested. In all tests, 2 ml of contrast medium were mixed with 2 ml of trisodium citrate solution. Iodixanol and ioxaglate provoked a highly viscous gluelike precipitation when mixed with trisodium citrate. A brief transient precipitate was observed with iohexol, iomeprol, and ioxithalamate. Permanent precipitation occurred with iobitridol and iopromide. One must be aware of the potential for precipitation when contrast medium is mixed with trisodium citrate solution. Before trisodium citrate solution is injected, the catheter should be thoroughly flushed with saline if a contrast medium has previously been injected through it.

  3. IR, UV-Vis, magnetic and thermal characterization of chelates of some catecholamines and 4-aminoantipyrine with Fe(III) and Cu(II)

    Science.gov (United States)

    Mohamed, Gehad G.; Zayed, M. A.; El-Dien, F. A. Nour; El-Nahas, Reham G.

    2004-07-01

    The dopamine derivatives participate in the regulation of wide variety of physiological functions in the human body and in medication life. Increase and/or decrease in the concentration of dopamine in human body reflect an indication for diseases such as Schizophrenia and/or Parkinson diseases. α-Methyldopa (α-MD) in tablets is used in medication of hypertension. The Fe(III) and Cu(II) chelates with coupled products of adrenaline hydrogen tartarate (AHT), levodopa (LD), α-MD and carbidopa (CD) with 4-aminoantipyrine (4-AAP) are prepared and characterized. Different physico-chemical methods like IR, magnetic and UV-Vis spectra are used to investigate the structure of these chelates. Fe(III) form 1:2 (M:catecholamines) chelates while Cu(II) form 1:1 chelates. Catecholamines behave as a bidentate mono- or dibasic ligands in binding to the metal ions. IR spectra show that the catecholamines are coordinated to the metal ions in a bidentate manner with O,O donor sites of the phenolic - OH. Magnetic moment measurements reveal the presence of Fe(III) chelates in octahedral geometry while the Cu(II) chelates are square planar. The thermal decomposition of Fe(III) and Cu(II) complexes is studied using thermogravimetric (TGA) and differential thermal analysis (DTA) techniques. The water molecules are removed in the first step followed immediately by decomposition of the ligand molecules. The activation thermodynamic parameters, such as, energy of activation, enthalpy, entropy and free energy change of the complexes are evaluated and the relative thermal stability of the complexes are discussed.

  4. 21 CFR 184.1195 - Calcium citrate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Calcium citrate. 184.1195 Section 184.1195 Food and... Substances Affirmed as GRAS § 184.1195 Calcium citrate. (a) Calcium citrate (Ca3(C6H5O7)2·4H2O, CAS Reg. No. 813-0994-095) is the calcium salt of citric acid. It is prepared by neutralizing citric acid with...

  5. Synergic effect of tribenzylamine on the extraction of Fe(III) with 2-thenoyltrifluoroacetone in chloroform

    International Nuclear Information System (INIS)

    Cheema, M.N.; Saeed, M.M.; Qureshi, I.H.

    1980-01-01

    Synergic effect of tribenzylamine (TBA) on the solvent extraction of Fe(III), Co(II) and Cu(II), by thenoyltrifluoracetone (HTTA) in chloroform from aqueous medium of ionic strength 0.33 M (H + ,NaClO 4 ) has been studied. For trivalent iron an enhanced extraction > 98% was observed at pH 2.5 and the equilibrium was attained within 5 minutes. Extraction parameters such as concentrations of HTTA, TBA and pH were optimised by a triangular co-ordinate graph. The stoichiometry of the extractable adduct Fe (TTA) 3 TBA was established by slope analysis. Extraction and formation constants of extractable species were computed. (orig.) [de

  6. Electron collisions with Fe-peak elements: Forbidden transitions between the low lying valence states 3d6, 3d54s, and 3d54p of Fe III

    International Nuclear Information System (INIS)

    McLaughlin, B.M.; Scott, M.P.; Sunderland, A.G.; Noble, C.J.; Burke, V.M.; Ramsbottom, C.A.; Reid, R.H.G.; Hibbert, A.; Bell, K.L.; Burke, P.G.

    2007-01-01

    Effective collision strengths are presented for the Fe-peak element Fe III at electron temperatures (T e in degrees Kelvin) in the range 2 x 10 3 to 1 x 10 6 . Forbidden transitions results are given between the 3d 6 , 3d 5 4s, and the 3d 5 4p manifolds applicable to the modeling of laboratory and astrophysical plasmas

  7. Otimização do banho eletrolítico da liga Fe-W-B resistente à corrosão Optimization of the electrolytic bath for electrodeposition of corrosion resistant Fe-W-B alloys

    Directory of Open Access Journals (Sweden)

    Renato Alexandre Costa de Santana

    2007-04-01

    Full Text Available A study on optimization of bath parameters for electrodeposition of Fe-W-B alloys from plating baths containing ammonia and citrate is reported. A 2³ full factorial design was successfully employed for experimental design analysis of the results. The corrosion resistance and amorphous character were evaluated. The bath conditions obtained for depositing the alloy with good corrosion resistance were: 0.01 M iron sulfate, 0.10 M sodium tungstate and 0.60 M ammonium citrate. The alloy was deposited at 12% current efficiency. The alloy obtained had Ecorr -0.841 V and Rp 1.463 x 10(4 Ohm cm². The deposit obtained under these conditions had an amorphous character and no microcracks were observed on its surface. Besides this, the bath conditions obtained for depositing the alloy with the highest deposition efficiency were: 0.09 M iron sulfate, 0.30 M sodium tungstate and 0.50 M ammonium citrate. The alloy was deposited at 50% current efficiency, with an average composition of 34 wt% W, 66 wt% Fe and traces of boron. The alloy obtained had Ecorr -0.800 V and Rp 1.895 x 10³ Ohm cm². Electrochemical corrosion tests verified that the Fe-W-B alloy deposited under both conditions had better corrosion resistance than Fe-Mo-B.

  8. Uptake and Release of Cerium During Fe-Oxide Formation and Transformation in Fe(II) Solutions

    DEFF Research Database (Denmark)

    Nedel, Sorin; Dideriksen, Knud; Christiansen, Bo C.

    2010-01-01

    Fe-oxides are ubiquitous in soils and sediments and form during Fe(0) corrosion. Depending on redox conditions and solution composition, Fe-oxides such as ferrihydrite, goethite, magnetite, and green rust (GR) may form. These phases typically have high surface area and large affinity for adsorption......(III) release. X-ray photoelectron spectroscopy revealed Ce(III) adsorbed on magnetite. When Fe-oxides were synthesized by air oxidation of Fe(II) solutions at pH 7, GR(Na,SO4) played a catalytic role in the oxidation of Ce(III) to Ce(IV) by O-2, removing more than 90% of the dissolved Ce. Transmission electron...

  9. The catalytic ozonization of model lignin compounds in the presence of Fe(III) ions

    Science.gov (United States)

    Ben'ko, E. M.; Mukovnya, A. V.; Lunin, V. V.

    2007-05-01

    The ozonization of several model lignin compounds (guaiacol, 2,6-dimethoxyphenol, phenol, and vanillin) was studied in acid media in the presence of iron(III) ions. It was found that Fe3+ did not influence the initial rate of the reactions between model phenols and ozone but accelerated the oxidation of intermediate ozonolysis products. The metal concentration dependences of the total ozone consumption and effective rate constants of catalytic reaction stages were determined. Data on reactions in the presence of oxalic acid as a competing chelate ligand showed that complex formation with Fe3+ was the principal factor that accelerated the ozonolysis of model phenols at the stage of the oxidation of carboxylic dibasic acids and C2 aldehydes formed as intermediate products.

  10. Na7 [Fe2S6 ] , Na2 [FeS2 ] and Na2 [FeSe2 ] : New 'reduced' sodium chalcogenido ferrates

    Science.gov (United States)

    Stüble, Pirmin; Peschke, Simon; Johrendt, Dirk; Röhr, Caroline

    2018-02-01

    Three new 'reduced' FeII containing sodium chalcogenido ferrates were obtained applying a reductive synthetic route. The mixed-valent sulfido ferrate Na7 [Fe2S6 ] , which forms bar-shaped crystals with metallic greenish luster, was synthesized in pure phase from natural pyrite and elemental sodium at a maximum temperature of 800 °C. Its centrosymmetric triclinic structure (SG P 1 bar , a = 764.15(2), b = 1153.70(2), c = 1272.58(3) pm, α = 62.3325 (7) , β = 72.8345 (8) , γ = 84.6394 (8) ° , Z = 3, R1 = 0.0185) exhibits two crystallographically different [Fe2S6 ] 7 - dimers of edge-sharing [FeS4 ] tetrahedra, with somewhat larger Fe-S distances than in the fully oxidized FeIII dimers of e.g. Na6 [Fe2III S6 ] . In contrast to the localized AFM ordered pure di-ferrates(III), the Curie-Weiss behavior of the magnetic susceptibility proves the rarely observed valence-delocalized S = 9/2 state of the mixed-valent FeIII /FeII dimer. The nearly spin-only value of the magnetic moment combined with the chemical bonding not generally differing from that in pure ferrates(II) and (III), provides a striking argument, that the reduction of the local Fe spin moments observed in all condensed sulfido ferrate moieties is connected with the AFM spin ordering. The two isotypic ferrates(II) Na2 [FeS2 ] and Na2 [FeSe2 ] with chain-like structural units (SG Ibam, a = 643.54(8)/ 660.81(1), b = 1140.2(2)/1190.30(2) c = 562.90(6)/585.59(1) pm, Z = 4, R1 = 0.0372/0.0466) crystallize in the K2 [ZnO2 ] -type structure. Although representing merely further members of the common series of chalcogenido metallates(II) Na2 [MIIQ2 ] , these two new phases, together with Na6 [FeS4 ] and Li2 [FeS2 ] , are the only examples of pure FeII alkali chalcogenido ferrates. The new compounds allow for a general comparison of di- and chain ferrates(II) and (III) and mixed-valent analogs concerning the electronic and magnetic properties (including Heisenberg super-exchange and double-exchange interactions

  11. Inducible transport of citrate in Lactobacillus rhamnosus ATCC 7469.

    Science.gov (United States)

    de Figueroa, R M; Benito de Cárdenas, I L; Sesma, F; Alvarez, F; de Ruiz Holgado, A P; Oliver, G

    1996-10-01

    Lactobacillus rhamnosus ATCC 7469 exhibited diauxie when grown in a medium containing both glucose and citrate as energy source. Glucose was used as the primary energy source during the glucose-citrate diauxie. Uptake of citrate was carried out by an inducible citrate transport system. The induction of citrate uptake system was repressed in the presence of glucose. This repression was reversible and mediated by cAMP.

  12. A Polycarboxyl-Decorated FeIII -Based Xerogel-Derived Multifunctional Composite (Fe3 O4 /Fe/C) as an Efficient Electrode Material towards Oxygen Reduction Reaction and Supercapacitor Application.

    Science.gov (United States)

    Devi, Bandhana; Venkateswarulu, Mangili; Kushwaha, Himmat Singh; Halder, Aditi; Koner, Rik Rani

    2018-05-02

    Low cost, non-noble metal catalysts with a good oxygen reduction reaction (ORR) activity comparable to that of platinum and also having good energy storage properties are highly desirable but challenging. Several challenges are associated with the development of such materials. Herein, we demonstrate a new polycarboxyl-functionalised Fe III -based gel material, synthesised following a solvothermal method and the development of its composite (Fe 3 O 4 /Fe/C) by annealing at optimised temperature. The developed composite displayed excellent electrocatalytic activity for the oxygen reduction reaction with an onset potential of 0.87 V (vs. RHE) and a current density value of -5 mA cm -2 , which are comparable with commercial 20 wt % Pt/C. In addition, as one of the most desirable properties, the composite exhibits a better methanol tolerance and greater durability than Pt/C. The same material was explored as an energy storage material for supercapacitors, which showed a specific capacitance of 245 F g -1 at a current density of 1 A g -1 . It is expected that this Fe 3 O 4 /Fe/C composite with a disordered graphitised carbon matrix will pave a horizon for developing energy conversion and energy storage devices. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Rates of cuticular penetration of chelated Fe(III): role of humidity, concentration, adjuvants, temperature, and type of chelate.

    Science.gov (United States)

    Schönherr, Jörg; Fernández, Victoria; Schreiber, Lukas

    2005-06-01

    Time courses of cuticular penetration of FeCl3 and Fe(III) complexes of citric acid, EDTA, EDDHA (Sequestrene 138Fe), imidodisuccinic acid (IDHA), and ligninsulfonic acid (Natrel) were studied using astomatous cuticular membranes (CMs) isolated from Populus x canescens leaves. At 100% relative humidity, the Fe(III) chelates disappeared exponentially with time from the surface of the CMs; that is, penetration was a first-order process that can be described using rate constants or half-times of penetration (t(1/2)). Half-times ranged from 20 to 30 h. At 90% humidity, penetration rates were insignificant with the exception of Natrel, for which t(1/2) amounted to 58 h. Rate constants were independent of temperature (15, 25, and 35 degrees C). Permeability decreased with increasing Fe chelate concentration (IDHA and EDTA). At 100% humidity, half-times measured with FeIDHA were 11 h (2 mmol L(-1)), 17 h (10 mmol L(-1)) and 36 h (20 mmol L(-1)), respectively. In the presence of FeEDTA, penetration of CaCl2 was slowed greatly. Half-times for penetration of CaCl2, which were 1.9 h in the absence of FeEDTA, rose to 3.12 h in the presence of an equimolar concentration of EDTA and 13.3 h when the FeEDTA concentration was doubled. Hence, Fe chelates reduced permeability of CMs to CaCl2 and to the Fe chelates themselves. It is suggested that Fe chelates reduced the size of aqueous pores. This view is supported by the fact that rate constants for calcium salts were about 5 times higher than for Fe chelates with the same molecular weights. Adding Tween 20 (5 g L(-1)) as a humectant did not increase permeability to FeIDHA at 90% humidity and below, while addition of glycine betaine did. Penetration of FeCl3 applied at 5 g L(-1) (pH 1.5) was not a first order process as rate constants decreased rapidly with time. Only 2% of the dose penetrated during the first 2 h and less than that in the subsequent 8 h. Recovery was only 70%. This was attributed to the formation of insoluble Fe

  14. Citrate Anticoagulation for CRRT in Children: Comparison with Heparin

    Directory of Open Access Journals (Sweden)

    Sara Nicole Fernández

    2014-01-01

    Full Text Available Regional anticoagulation with citrate is an alternative to heparin in continuous renal replacement therapies, which may prolong circuit lifetime and decrease hemorrhagic complications. A retrospective comparative cohort study based on a prospective observational registry was conducted including critically ill children undergoing CRRT. Efficacy, measured as circuit survival, and secondary effects of heparin and citrate were compared. 12 patients on CRRT with citrate anticoagulation and 24 patients with heparin anticoagulation were analyzed. Median citrate dose was 2.6 mmol/L. Median calcium dose was 0.16 mEq/kg/h. Median heparin dose was 15 UI/kg/h. Median circuit survival was 48 hours with citrate and 31 hours with heparin (P=0.028. 66.6% of patients treated with citrate developed mild metabolic alkalosis, which was directly related to citrate dose. There were no cases of citrate intoxication: median total calcium/ionic calcium index (CaT/I of 2.16 and a maximum CaT/I of 2.33, without metabolic acidosis. In the citrate group, 45.5% of patients developed hypochloremia and 27.3% hypomagnesemia. In the heparin group, 27.8% developed hypophosphatemia. Three patients were moved from heparin to citrate to control postoperatory bleeding. In conclusion citrate is a safe and effective anticoagulation method for CRRT in children and it achieves longer circuit survival than heparin.

  15. Nanosized LaCo0.6Fe0.4O3 perovskites synthesized by citrate sol gel auto combustion method

    Directory of Open Access Journals (Sweden)

    Unikoth Megha

    2014-06-01

    Full Text Available LaCo0.6 Fe0.4 O3 (LCFO nanopowder was synthesized from constituent metal nitrates, citric acid and ethylene glycol by citrate sol gel autocombustion method and calcined at different temperatures. The powders were characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM, energy dispersive X-ray analysis (EDAX and Fourier transform infrared spectra (FTIR, whereas dielectric properties were investigated with LCR-meter. The FTIR spectra, taken for the xerogel and the sample calcined at 1000 °C, confirm that the organic groups were removed during calcination and oxide structure was formed. The XRD result shows that LCFO has rhombhohedral crystal structure with R-3C space group and forms single phase after calcination at 600 °C. The activation energy of crystallite growth, determined from the Arrhenius plot, was 17±2 kJ/mol. Surface feature studies of the powders were obtained from SEM. At 1000 °C, dense microstructure with well-shaped grain boundaries was obtained and the average grain size was around 400 nm. EDAX confirms the elemental composition. Finally, from the dielectric studies, it was found that the dielectric constant (εr as well as dielectric loss tangent (tan δ decreases with increase in frequency.

  16. Moessbauer spectroscopic studies of the chemical effects associated with 57Co(electron capture)57Fe decay in tris-β-diketonatocobalt(III) compounds

    International Nuclear Information System (INIS)

    Sakai, Yoichi; Endo, Kazutoyo; Sano, Hirotoshi

    1980-01-01

    Magnetic hyperfine structures (hfs) were found in the absorption Moessbauer spectra at 78 K of a paramagnetic iron(III) complex diluted in a diamagnetic cobalt(III) or aluminium(III) complex such as 57 Fe(acac) 3 in Co(acac) 3 , 57 Fe(oxin) 3 in Al(oxin) 3 , and 57 Fe(dbm) 3 in Co(dbm) 3 (acac=acetylacetonato, oxin=8-quinolinolato, and dbm=dibenzoylmethanato), showing that the magnetic hfs is caused by the spin-spin relaxation through the surrounding diamagnetic species. In the emission Moessbauer experiments, magnetic hfs was observed at 78 K in 57 Co-labelled Co(dbm) 3 , Co(oxin) 3 , and polystyrene-diluted Co(acac) 3 , while it was not observed in 57 Co-labelled Co(acac) 3 and Co(dpm) 3 (dpm=dipivaloylmethanato). The former possess pi -conjugated systems to a greater extent than the latter, either in the ligands or in the vicinity of the 57 Co-labelled Co(III) species. These results were explained in terms of the radiolytic stabilities of the matrices as well as those of 57 Co-labelled compounds by showing that the paramagnetic radicals produced in a diamagnetic matrix quench the magnetic hfs because of the increased spin-spin interaction, as a consequence of the local radiolysis by EC-decay. (author)

  17. Effect of Organic Substances on the Efficiency of Fe(Ii to Fe(Iii Oxidation and Removal of Iron Compounds from Groundwater in the Sedimentation Process

    Directory of Open Access Journals (Sweden)

    Krupińska Izabela

    2017-09-01

    Full Text Available One of the problems with iron removal from groundwater is organic matter. The article presents the experiments involved groundwater samples with a high concentration of total iron - amounting to 7.20 mgFe/dm3 and an increased amount of organic substances (TOC from 5.50 to 7.50 mgC/dm3. The water samples examined differed in terms of the value of the ratio of the TOC concentration and the concentration of total iron (D. It was concluded that with increase in the coexistence ratio of organic substances and total iron in water (D = [TOC]/[Fetot], efficiency of Fe(II to Fe(III oxidization with dissolved oxygen decreased, while the oxidation time was increasing. This rule was not demonstrated for potassium manganate (VII when used as an oxidizing agent. The application of potassium manganate (VII for oxidation of Fe(II ions produced the better results in terms of total iron concentration reduction in the sedimentation process than the oxidation with dissolved oxygen.

  18. Effect of Organic Substances on the Efficiency of Fe(Ii) to Fe(Iii) Oxidation and Removal of Iron Compounds from Groundwater in the Sedimentation Process

    Science.gov (United States)

    Krupińska, Izabela

    2017-09-01

    One of the problems with iron removal from groundwater is organic matter. The article presents the experiments involved groundwater samples with a high concentration of total iron - amounting to 7.20 mgFe/dm3 and an increased amount of organic substances (TOC from 5.50 to 7.50 mgC/dm3). The water samples examined differed in terms of the value of the ratio of the TOC concentration and the concentration of total iron (D). It was concluded that with increase in the coexistence ratio of organic substances and total iron in water (D = [TOC]/[Fetot]), efficiency of Fe(II) to Fe(III) oxidization with dissolved oxygen decreased, while the oxidation time was increasing. This rule was not demonstrated for potassium manganate (VII) when used as an oxidizing agent. The application of potassium manganate (VII) for oxidation of Fe(II) ions produced the better results in terms of total iron concentration reduction in the sedimentation process than the oxidation with dissolved oxygen.

  19. Biomineralization associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals

    Science.gov (United States)

    Zhang, G.; Dong, H.; Jiang, H.; Kukkadapu, R.K.; Kim, J.; Eberl, D.; Xu, Z.

    2009-01-01

    Iron-reducing and oxidizing microorganisms gain energy through reduction or oxidation of iron, and by doing so play an important role in the geochemical cycling of iron. This study was undertaken to investigate mineral transformations associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals. A fluid sample from the 2450 m depth of the Chinese Continental Scientific Drilling project was collected, and Fe3+-reducing and Fe2+-oxidizing microorganisms were enriched. The enrichment cultures displayed reduction of Fe3+ in nontronite and ferric citrate, and oxidation of Fe2+ in vivianite, siderite, and monosulfide (FeS). Additional experiments verified that the iron reduction and oxidation was biological. Oxidation of FeS resulted in the formation of goethite, lepidocrocite, and ferrihydrite as products. Although our molecular microbiological analyses detected Thermoan-aerobacter ethanolicus as a predominant organism in the enrichment culture, Fe3+ reduction and Fe2+ oxidation may be accomplished by a consortia of organisms. Our results have important environmental and ecological implications for iron redox cycling in solid minerals in natural environments, where iron mineral transformations may be related to the mobility and solubility of inorganic and organic contaminants.

  20. Comparative ligational, optical band gap and biological studies on Cr(III) and Fe(III) complexes of hydrazones derived from 2-hydrazinyl-2-oxo-N-phenylacetamide with both vanillin and O-vanillin

    Science.gov (United States)

    Yousef, T. A.; Abu El-Reash, G. M.; Attia, M. I.; El-Tabai, M. N.

    2015-09-01

    The Cr(III) and Fe(III) complexes of hydrazones derived from the condensation of 2-hydrazinyl-2-oxo-N-phenylacetamide with both vanillin and o-vanillin synthesized and characterized by different conventional physicochemical techniques. The kinetic and thermodynamic parameters for the different decomposition steps were calculated using Coats-Redfern and Horowitz-Metzger equations. The bond lengths, bond angles, HOMO, LUMO, dipole moment and binding energy calculated by DFT calculations. The optical band gap (Eg) values equal 3.28, 3.03, 3.58 and 3.57 eV for [Cr(HL1)Cl2(H2O)2](0.75H2O), [Cr(HL2)Cl2(H2O)](H2O), [Fe(HL1)Cl2(H2O)2](0.5H2O) and [Fe(HL2)2Cl(H2O)](3H2O) complexes, respectively. The antibacterial activities tested against Bacillus subtilis and Escherichia coli bacteria.

  1. An FeIII Azamacrocyclic Complex as a pH-Tunable Catholyte and Anolyte for Redox-Flow Battery Applications.

    Science.gov (United States)

    Tsitovich, Pavel B; Kosswattaarachchi, Anjula M; Crawley, Matthew R; Tittiris, Timothy Y; Cook, Timothy R; Morrow, Janet R

    2017-11-02

    A reversible Fe 3+ /Fe 2+ redox couple of an azamacrocyclic complex is evaluated as an electrolyte with a pH-tunable potential range for aqueous redox-flow batteries (RFBs). The Fe III complex is formed by 1,4,7-triazacyclononane (TACN) appended with three 2-methyl-imidazole donors, denoted as Fe(Tim). This complex exhibits pH-sensitive redox couples that span E 1/2 (Fe 3+ /Fe 2+ )=317 to -270 mV vs. NHE at pH 3.3 and pH 12.8, respectively. The 590 mV shift in potential and kinetic inertness are driven by ionization of the imidazoles at various pH values. The Fe 3+ /Fe 2+ redox is proton-coupled at alkaline conditions, and bulk electrolysis is non-destructive. The electrolyte demonstrates high charge/discharge capacities at both acidic and alkaline conditions throughout 100 cycles. Given its tunable redox, fast electrochemical kinetics, exceptional stability/cyclability, this complex is promising for the design of aqueous RFB catholytes and anolytes that utilize the earth-abundant element iron. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Changes in phosphorylation of adenosine phosphate and redox state of nicotinamide-adenine dinucleotide (phosphate) in Geobacter sulfurreducens in response to electron acceptor and anode potential variation

    KAUST Repository

    Rose, Nicholas D.; Regan, John M.

    2015-01-01

    © 2015 Elsevier B.V. Geobacter sulfurreducens is one of the dominant bacterial species found in biofilms growing on anodes in bioelectrochemical systems. The intracellular concentrations of reduced and oxidized forms of nicotinamide-adenine dinucleotide (NADH and NAD+, respectively) and nicotinamide-adenine dinucleotide phosphate (NADPH and NADP+, respectively) as well as adenosine triphosphate (ATP), adenosine diphosphate (ADP), and adenosine monophosphate (AMP) were measured in G. sulfurreducens using fumarate, Fe(III)-citrate, or anodes poised at different potentials (110, 10, -90, and -190mV (vs. SHE)) as the electron acceptor. The ratios of CNADH/CNAD+ (0.088±0.022) and CNADPH/CNADP+ (0.268±0.098) were similar under all anode potentials tested and with Fe(III)-citrate (reduced extracellularly). Both ratios significantly increased with fumarate as the electron acceptor (0.331±0.094 for NAD and 1.96±0.37 for NADP). The adenylate energy charge (the fraction of phosphorylation in intracellular adenosine phosphates) was maintained near 0.47 under almost all conditions. Anode-growing biofilms demonstrated a significantly higher molar ratio of ATP/ADP relative to suspended cultures grown on fumarate or Fe(III)-citrate. These results provide evidence that the cellular location of reduction and not the redox potential of the electron acceptor controls the intracellular redox potential in G. sulfurreducens and that biofilm growth alters adenylate phosphorylation.

  3. Changes in phosphorylation of adenosine phosphate and redox state of nicotinamide-adenine dinucleotide (phosphate) in Geobacter sulfurreducens in response to electron acceptor and anode potential variation

    KAUST Repository

    Rose, Nicholas D.

    2015-12-01

    © 2015 Elsevier B.V. Geobacter sulfurreducens is one of the dominant bacterial species found in biofilms growing on anodes in bioelectrochemical systems. The intracellular concentrations of reduced and oxidized forms of nicotinamide-adenine dinucleotide (NADH and NAD+, respectively) and nicotinamide-adenine dinucleotide phosphate (NADPH and NADP+, respectively) as well as adenosine triphosphate (ATP), adenosine diphosphate (ADP), and adenosine monophosphate (AMP) were measured in G. sulfurreducens using fumarate, Fe(III)-citrate, or anodes poised at different potentials (110, 10, -90, and -190mV (vs. SHE)) as the electron acceptor. The ratios of CNADH/CNAD+ (0.088±0.022) and CNADPH/CNADP+ (0.268±0.098) were similar under all anode potentials tested and with Fe(III)-citrate (reduced extracellularly). Both ratios significantly increased with fumarate as the electron acceptor (0.331±0.094 for NAD and 1.96±0.37 for NADP). The adenylate energy charge (the fraction of phosphorylation in intracellular adenosine phosphates) was maintained near 0.47 under almost all conditions. Anode-growing biofilms demonstrated a significantly higher molar ratio of ATP/ADP relative to suspended cultures grown on fumarate or Fe(III)-citrate. These results provide evidence that the cellular location of reduction and not the redox potential of the electron acceptor controls the intracellular redox potential in G. sulfurreducens and that biofilm growth alters adenylate phosphorylation.

  4. Crystal structure of the coordination polymer [FeIII2{PtII(CN4}3

    Directory of Open Access Journals (Sweden)

    Maksym Seredyuk

    2015-01-01

    Full Text Available The title complex, poly[dodeca-μ-cyanido-diiron(IIItriplatinum(II], [FeIII2{PtII(CN4}3], has a three-dimensional polymeric structure. It is built-up from square-planar [PtII(CN4]2− anions (point group symmetry 2/m bridging cationic [FeIIIPtII(CN4]+∞ layers extending in the bc plane. The FeII atoms of the layers are located on inversion centres and exhibit an octahedral coordination sphere defined by six N atoms of cyanide ligands, while the PtII atoms are located on twofold rotation axes and are surrounded by four C atoms of the cyanide ligands in a square-planar coordination. The geometrical preferences of the two cations for octahedral and square-planar coordination, respectively, lead to a corrugated organisation of the layers. The distance between neighbouring [FeIIIPtII(CN4]+∞ layers corresponds to the length a/2 = 8.0070 (3 Å, and the separation between two neighbouring PtII atoms of the bridging [PtII(CN4]2− groups corresponds to the length of the c axis [7.5720 (2 Å]. The structure is porous with accessible voids of 390 Å3 per unit cell.

  5. Predictive modelling of Fe(III) precipitation in iron removal process for bioleaching circuits.

    Science.gov (United States)

    Nurmi, Pauliina; Ozkaya, Bestamin; Kaksonen, Anna H; Tuovinen, Olli H; Puhakka, Jaakko A

    2010-05-01

    In this study, the applicability of three modelling approaches was determined in an effort to describe complex relationships between process parameters and to predict the performance of an integrated process, which consisted of a fluidized bed bioreactor for Fe(3+) regeneration and a gravity settler for precipitative iron removal. Self-organizing maps were used to visually evaluate the associations between variables prior to the comparison of two different modelling methods, the multiple regression modelling and artificial neural network (ANN) modelling, for predicting Fe(III) precipitation. With the ANN model, an excellent match between the predicted and measured data was obtained (R (2) = 0.97). The best-fitting regression model also gave a good fit (R (2) = 0.87). This study demonstrates that ANNs and regression models are robust tools for predicting iron precipitation in the integrated process and can thus be used in the management of such systems.

  6. The influence of reaction time on hydrogen sulphide removal from air by means of Fe(III)-EDTA/Fiban catalysts

    Science.gov (United States)

    Wasag, H.; Cel, W.; Chomczynska, M.; Kujawska, J.

    2018-05-01

    The paper deals with a new method of hydrogen sulphide removal from air by its filtration and selective catalytic oxidation with the use of fibrous carriers of Fe(III)-EDTA complex. The basis of these filtering materials includes fibrous ion exchangers with the complex immobilized on their functional groups. It has been established that the degree of catalytic hydrogen sulphide decomposition depends on the reaction time. Thus, the required degree of hydrogen sulphide removal from air could be easily controlled by applying appropriate thickness of the filtering layer under a given filtering velocity. It allows applying very thin filtering layers of the Fe(III)-EDTA/Fiban AK-22 or Fiban A-6 catalysts. The obtained results of the research confirm the applicability of these materials for deep air purification from hydrogen sulphide.

  7. 21 CFR 522.800 - Droperidol and fentanyl citrate injection.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Droperidol and fentanyl citrate injection. 522.800... § 522.800 Droperidol and fentanyl citrate injection. (a) Specifications. Droperidol and fentanyl citrate injection is a sterile solution containing 20 milligrams of droperidol and 0.4 milligram of fentanyl citrate...

  8. Kinetics and Mechanism of the Iron(II-Iron(III) Electron-Exchange Reaction in Mixed Solvent Media; Cinetique et Mecanisme de l'Echange d'Electrons entre Fer (II) et Fer (III), dans des Melanges de Solvants; Ikinetika i mekhanizm reaktsii ehlektronnogo obmena zheleza (I) - zheleza (III) v smeshannoj rastvoryayushchej srede; Cinetica y Mecanismo del Intercambio de Electrones Entre Fe{sup II} Y Fe{sup lII} en Mezclas de Disolventes

    Energy Technology Data Exchange (ETDEWEB)

    Horne, R. A. [Arthur D. Little, Inc. Cambridge, MA (United States)

    1965-10-15

    The specific reaction rate constants of theFe{sup II}-Fe{sup III} electron-exchange reaction have been measured at various temperatures, acidities, and ionic strengths in water-acetone, water-methanol, and water-ethanol media. The reaction rate markedly diminishes as the water concentration in the last system decreases, approaching zero as the water concentration approaches zero. The activation energy of the exchange is the same in mixed solvent as in aqueous solution. The effective dielectric constant which the reactants ''see'' continues to be that of pure water even in water-ethanol solutions quite dilute in water. Alterations in composition of the solvation sheath of Fe{sup III} in mixed media are reflected in both electron-exchange and spectroscopic measurements. These findings in mixed solvent media support the water-bridging theory of electron exchange. (author) [French] Les constantes de vitesse specifiques de l'echange d'electrons entre Fe{sup II} et Fe{sup III} ont ete mesurees a differentes temperatures et pour differentes acidites et forces ioniques, dans des melanges d'eau et d'acetone, d'eau et de methanol et d'eau et d'ethanol. Dans le dernier systeme, la vitesse d'echange diminue considerablement a mesure que la concentration en eau decroit, et tend vers zero en meme temps que cette concentration. L'energie d'activation de l'echange est la meme dans un melange de solvants et dans une solution aqueuse. La constante dielectrique effective qui intervient entre les corps reagissants reste celle de l'eau pure, meme dans des solutions concentrees d'ethanol dans l'eau. Les changements de composition de la gaine de solvatation de Fe{sup III} dans les melanges se manifestent a la fois dans les mesures de l'echange d'electrons et dans les mesures spectroscopiques. Ces observations viennent confirmer la theorie de l'echange d'electrons fondee sur le pontage par l'eau. (author) [Spanish] El autor ha medido las constantes de velocidad especificas de la reaccion

  9. In situ synthesized and embedded silver nanoclusters into poly vinyl alcohol-borax hydrogel as a novel dual mode "on and off" fluorescence sensor for Fe (III) and thiosulfate.

    Science.gov (United States)

    Pourreza, Nahid; Ghomi, Matineh

    2018-03-01

    Herein, a novel method has been developed for in situ synthesis and embedding of silver nanoclusters (AgNCs) into polyvinyl alcohol and borax hydrogel (PBH) without adding any reducing agent. A three-dimensional network of polyvinyl alcohol and borax is formed, and at the same time the silver ions penetrate into the hydrogel, reduced to silver and trapped into the hydrogel bed. The characteristics of this hydrogel nanocomposite were investigated by energy dispersive X-ray spectroscopy and transmission electron microscopy (TEM). It was also observed that the fluorescence intensity of embedded AgNCs into polyvinyl alcohol and borax hydrogel (AgNCs-PBH) was enhanced and quenched in the presence of Fe (III) and thiosulfate, respectively. Therefore a novel dual on-off fluorescence sensor was developed based on polyvinyl alcohol-borax hydrogel for the first time. After preparing this new probe, the effect of Fe (III) and thiosulfate was investigated. The size- depending of label free AgNCs was found to be responsible for the enhancing and quenching of the fluorescence as well as obvious color changing. Under the approved condition, the linear ranges were validated over the concentration of 0.14-27.0µmolL -1 and 0.1-1.0µmolL -1 for Fe (III) and thiosulfate, respectively. The limit of detection based on three times the standard deviation of the blank was 0.045 and 0.060µmolL -1 for Fe (III) and thiosulfate, respectively. The relative standard deviation for intra-day and inter-day determinations of both Fe (III) and thiosulfate were in the range of 3.23-5.17% (n = 10). This sensing probe was used for Fe (III) detection in some food samples and thiosulfate in water samples with acceptable results and good recoveries. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. Mechanochemical synthesis and intercalation of Ca(II)Fe(III)-layered double hydroxides

    Energy Technology Data Exchange (ETDEWEB)

    Ferencz, Zs.; Szabados, M.; Varga, G.; Csendes, Z. [Department of Organic Chemistry, University of Szeged, Dóm tér 8, Szeged H-6720 (Hungary); Materials and Solution Structure Research Group, Institute of Chemistry, University of Szeged, Aradi Vértanúk tere 1, Szeged H-6720 (Hungary); Kukovecz, Á. [Department of Applied and Environmental Chemistry, University of Szeged, Rerrich Béla tér 1, Szeged H-6720 (Hungary); MTA-SZTE “Lendület” Porous Nanocomposites Research Group, Rerrich Béla tér 1, Szeged H-6720 (Hungary); Kónya, Z. [Department of Applied and Environmental Chemistry, University of Szeged, Rerrich Béla tér 1, Szeged H-6720 (Hungary); MTA-SZTE Reaction Kinetics and Surface Chemistry Research Group, Rerrich Béla tér 1, Szeged H-6720 (Hungary); Carlson, S. [MAX IV Laboratory, Ole Römers väg 1, Lund SE-223 63 (Sweden); Sipos, P. [Materials and Solution Structure Research Group, Institute of Chemistry, University of Szeged, Aradi Vértanúk tere 1, Szeged H-6720 (Hungary); Department of Inorganic and Analytical Chemistry, University of Szeged, Dóm tér 7, Szeged H-6720 (Hungary); and others

    2016-01-15

    A mechanochemical method (grinding the components without added water – dry grinding, followed by further grinding in the presence of minute amount of water or NaOH solution – wet grinding) was used in this work for the preparation and intercalation of CaFe-layered double hydroxides (LDHs). Both the pristine LDHs and the amino acid anion (cystinate and tyrosinate) intercalated varieties were prepared by the two-step grinding procedure in a mixer mill. By systematically changing the conditions of the preparation method, a set of parameters could be determined, which led to the formation of close to phase-pure LDH. The optimisation procedure was also applied for the intercalation processes of the amino acid anions. The resulting materials were structurally characterised by a range of methods (X-ray diffractometry, scanning electron microscopy, energy dispersive analysis, thermogravimetry, X-ray absorption and infra-red spectroscopies). It was proven that this simple mechanochemical procedure was able to produce complex organic–inorganic nanocomposites: LDHs intercalated with amino acid anions. - Graphical abstract: Amino acid anion-Ca(II)Fe(III)-LDHs were successfully prepared by a two-step milling procedure. - Highlights: • Synthesis of pristine and amino acid intercalated CaFe-LDHs by two-step milling. • Identifying the optimum synthesis and intercalation parameters. • Characterisation of the samples with a range of instrumental methods.

  11. Abiotic Deposition of Fe Complexes onto Leptothrix Sheaths

    Science.gov (United States)

    Kunoh, Tatsuki; Hashimoto, Hideki; McFarlane, Ian R.; Hayashi, Naoaki; Suzuki, Tomoko; Taketa, Eisuke; Tamura, Katsunori; Takano, Mikio; El-Naggar, Mohamed Y.; Kunoh, Hitoshi; Takada, Jun

    2016-01-01

    Bacteria classified in species of the genus Leptothrix produce extracellular, microtubular, Fe-encrusted sheaths. The encrustation has been previously linked to bacterial Fe oxidases, which oxidize Fe(II) to Fe(III) and/or active groups of bacterial exopolymers within sheaths to attract and bind aqueous-phase inorganics. When L. cholodnii SP-6 cells were cultured in media amended with high Fe(II) concentrations, Fe(III) precipitates visibly formed immediately after addition of Fe(II) to the medium, suggesting prompt abiotic oxidation of Fe(II) to Fe(III). Intriguingly, these precipitates were deposited onto the sheath surface of bacterial cells as the population was actively growing. When Fe(III) was added to the medium, similar precipitates formed in the medium first and were abiotically deposited onto the sheath surfaces. The precipitates in the Fe(II) medium were composed of assemblies of globular, amorphous particles (ca. 50 nm diameter), while those in the Fe(III) medium were composed of large, aggregated particles (≥3 µm diameter) with a similar amorphous structure. These precipitates also adhered to cell-free sheaths. We thus concluded that direct abiotic deposition of Fe complexes onto the sheath surface occurs independently of cellular activity in liquid media containing Fe salts, although it remains unclear how this deposition is associated with the previously proposed mechanisms (oxidation enzyme- and/or active group of organic components-involved) of Fe encrustation of the Leptothrix sheaths. PMID:27271677

  12. Abiotic Deposition of Fe Complexes onto Leptothrix Sheaths

    Directory of Open Access Journals (Sweden)

    Tatsuki Kunoh

    2016-06-01

    Full Text Available Bacteria classified in species of the genus Leptothrix produce extracellular, microtubular, Fe-encrusted sheaths. The encrustation has been previously linked to bacterial Fe oxidases, which oxidize Fe(II to Fe(III and/or active groups of bacterial exopolymers within sheaths to attract and bind aqueous-phase inorganics. When L. cholodnii SP-6 cells were cultured in media amended with high Fe(II concentrations, Fe(III precipitates visibly formed immediately after addition of Fe(II to the medium, suggesting prompt abiotic oxidation of Fe(II to Fe(III. Intriguingly, these precipitates were deposited onto the sheath surface of bacterial cells as the population was actively growing. When Fe(III was added to the medium, similar precipitates formed in the medium first and were abiotically deposited onto the sheath surfaces. The precipitates in the Fe(II medium were composed of assemblies of globular, amorphous particles (ca. 50 nm diameter, while those in the Fe(III medium were composed of large, aggregated particles (≥3 µm diameter with a similar amorphous structure. These precipitates also adhered to cell-free sheaths. We thus concluded that direct abiotic deposition of Fe complexes onto the sheath surface occurs independently of cellular activity in liquid media containing Fe salts, although it remains unclear how this deposition is associated with the previously proposed mechanisms (oxidation enzyme- and/or active group of organic components-involved of Fe encrustation of the Leptothrix sheaths.

  13. Gallium-67 citrate localization in disseminated sporotrichosis

    International Nuclear Information System (INIS)

    Moreno, A.J.; Brazier, J.M.; Baker, F.J.; Fox, B.J.; Pittman, D.L.

    1985-01-01

    A 25-year-old woman demonstrated Ga-67 citrate accumulation within a facial cutaneous lesion and two subcutaneous nodules within the right lower extremity. Cultures of the facial lesion and one of the subcutaneous nodules grew Sporothrix schenckii. Ga-67 citrate uptake has not been reported previously with this fungal infection. Ga-67 citrate scintigraphy was helpful in defining the extent of the disease, following its course, and determining the response to therapy

  14. 57Fe Moessbauer spectroscopic study of the thermal decomposition of Fe(IO3)3

    International Nuclear Information System (INIS)

    Music, S.; Simmons, G.W.; Leidheiser, H. Jr

    1981-01-01

    Thermal decomposition of iron(III) iodate at temperatures up to 600 deg C has been followed by 57 Fe Moessbauer spectroscopy. The 57 Fe Moessbauer spectrum of iron(III) iodate is characterized by a single absorption peak. A magnetic splitting component of small intensity appears after 42 h heating at 370 deg C. Iron(III) iodate is completely decomposed after 1 h heating at 470 deg C. Moessbauer parameters of the component yielding the magnetic hyperfine split spectrum correspond to α-Fe 2 O 3 with crystal defects. Quantitative experimental data are summarized and discussed. (author)

  15. Fixation of Cr(III) traces onto Haro river sand from acidic solution

    International Nuclear Information System (INIS)

    Hasany, S.M.; Chaudhry, M.H.

    1998-01-01

    The sorption of chromium(III) onto Haro river sand has been investigated as a function of sorptive solution composition, amounts of sorbent (10-500 mg) and sorbate (4.33 x 10 -8 -5.17 x 10 -6 M), shaking time (I-60 minutes) and temperature (15-35 deg C). Maximum sorption has been achieved from 0.001M HCl solution using 50 mg of the sand and 20 minutes shaking time. The sorption data followed Freundlich and D-R isotherms. The sorption capacity of 0.4 μmole x g -1 and of sorption energy of 9.9 kJ x mole -1 have been computed from D-R parameters. Thermodynamic parameters ΔH = 84.4 kJ x mole -1 , ΔS 284.5 J x mole -1 x K -1 and ΔG = -3.32 kJ x mole -1 at 298 K have been evaluated. Fe(II), Al(III), citrate, borate, oxalate, tartrate and carbonate ions reduce the sorption significantly. Under similar experimental conditions Tc(VII), Re(VII), Sb(V) and Co(II) have very low sorption (<1%) and trivalent Eu and Sm have large distribution ratios. Haro river sand can be used to preconcentrate or to remove micro or submicro amounts of Cr(III) from very dilute solution and for the separation of Tc, Re and Sb from Cr, Eu and Sm. (author)

  16. Magnetic and catalytic properties of inverse spinel CuFe{sub 2}O{sub 4} nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Anandan, S., E-mail: sanand@nitt.edu [Nanomaterials and Solar Energy Conversion Lab, Department of Chemistry, National Institute of Technology, Trichy 620 015 (India); Department of Environmental Engineering and Science, Feng Chia University, Taichung 407, Taiwan (China); Selvamani, T.; Prasad, G. Guru [Nanomaterials and Solar Energy Conversion Lab, Department of Chemistry, National Institute of Technology, Trichy 620 015 (India); Asiri, A.M. [The Center of Excellence for Advanced Materials Research, King Abdulaziz University, P.O. Box 80203, Jeddah 21413 (Saudi Arabia); Wu, J.J., E-mail: jjwu@fcu.edu.tw [Department of Environmental Engineering and Science, Feng Chia University, Taichung 407, Taiwan (China)

    2017-06-15

    Highlights: • Copper ferrite (CuFe{sub 2}O{sub 4}) nanoparticles were synthesized via citrate-nitrate combustion method. • Spectroscopic information’s have found that CuFe{sub 2}O{sub 4} nanoparticles as an inverse spinel structure. • Magnetic study exhibits CuFe{sub 2}O{sub 4} nanoparticles have ferromagnetic behavior. • CuFe{sub 2}O{sub 4} nanoparticles employed for photocatalytic decolourisation of methylene blue under visible light irradiation. - Abstract: In this research, inverse spinel copper ferrite nanoparticles (CuFe{sub 2}O{sub 4} NPs) were synthesized via citrate-nitrate combustion method. The crystal structure, particle size, morphology and magnetic studies were investigated using various instrumental tools to illustrate the formation of the inverse spinel structure. Mossbauer spectrometry identified Fe is located both in the tetrahedral and octahedral site in the ratio (40:60) and the observed magnetic parameters values such as saturation magnetization (M{sub s} = 20.62 emu g{sup −1}), remnant magnetization (M{sub r} = 11.66 emu g{sup −1}) and coercivity (H{sub c} = 63.1 mTesla) revealed that the synthesized CuFe{sub 2}O{sub 4} NPs have a typical ferromagnetic behaviour. Also tested CuFe{sub 2}O{sub 4} nanoparticles as a photocatalyst for the decolourisation of methylene blue (MB) in the presence of peroxydisulphate as the oxidant.

  17. Anoxic and Oxic Oxidation of Rocks Containing Fe(II)Mg-Silicates and Fe(II)-Monosulfides as Source of Fe(III)-Minerals and Hydrogen. Geobiotropy.

    Science.gov (United States)

    Bassez, Marie-Paule

    2017-12-01

    In this article, anoxic and oxic hydrolyses of rocks containing Fe (II) Mg-silicates and Fe (II)-monosulfides are analyzed at 25 °C and 250-350 °C. A table of the products is drawn. It is shown that magnetite and hydrogen can be produced during low-temperature (25 °C) anoxic hydrolysis/oxidation of ferrous silicates and during high-temperature (250 °C) anoxic hydrolysis/oxidation of ferrous monosulfides. The high-T (350 °C) anoxic hydrolysis of ferrous silicates leads mainly to ferric oxides/hydroxides such as the hydroxide ferric trihydroxide, the oxide hydroxide goethite/lepidocrocite and the oxide hematite, and to Fe(III)-phyllosilicates. Magnetite is not a primary product. While the low-T (25 °C) anoxic hydrolysis of ferrous monosulfides leads to pyrite. Thermodynamic functions are calculated for elementary reactions of hydrolysis and carbonation of olivine and pyroxene and E-pH diagrams are analyzed. It is shown that the hydrolysis of the iron endmember is endothermic and can proceed within the exothermic hydrolysis of the magnesium endmember and also within the exothermic reactions of carbonations. The distinction between three products of the iron hydrolysis, magnetite, goethite and hematite is determined with E-pH diagrams. The hydrolysis/oxidation of the sulfides mackinawite/troilite/pyrrhotite is highly endothermic but can proceed within the heat produced by the exothermic hydrolyses and carbonations of ferromagnesian silicates and also by other sources such as magma, hydrothermal sources, impacts. These theoretical results are confirmed by the products observed in several related laboratory experiments. The case of radiolyzed water is studied. It is shown that magnetite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite are formed in oxic hydrolysis of ferromagnesian silicates at 25 °C and 350 °C. Oxic oxidation of ferrous monosulfides at 25 °C leads mainly to pyrite and ferric oxides/hydroxides such as

  18. Gadopentate interference in gallium-67 tumour imaging: fact or fiction?

    International Nuclear Information System (INIS)

    Baker, R.J.

    1998-01-01

    Full text: Gallium-67-citrate is the most widely used tumour imaging radiopharmaceutical. It is known that the metal ions Sc(III), Au(III), FE(III) and inactive Ga(III), as well as chemotherapy, interfere leading to poor quality scans, characterised by pronounced bone uptake and loss of tumour avidity. In 1990, Hattner and White reported a scan of this nature following administration of the paramagnetic contrast agent gadolinium-DTPA (Gadopentate). Suggestions to account for these changes included in vivo dissociation or the presence of free DTPA in the formulation. Since the use of MRI is increasing dramatically, this potential interference is a vital issue for nuclear medicine. To investigate this phenomenon, gadolinium-DTPA solutions were prepared containing Gd and DTPA in the molar ratios 0.9:1, 1.0:1 and 1.1:1. Their effect on 67 Ga biodistribution at 24 h was investigated using mature female Balb/c mice after i.v. 67 Ga-citrate, injected 4 h after i.v. GD-DTPA. The model was verified by identical studies using inactive GA(III) and FE(III) at 0. 1 mmol/kg. The effects of GD(III) and DTPA ligand at this dose were also determined . Following administration of GD-DTPA up to 0.5 mmol/kg, no significant changes in 67 Ga biodistribution were observed. Minor changes occurred after 0. 1 mmol/kg Gd(III), notably increased renal (49%) and splenic (92%) uptake. With free DTPA, slightly higher blood (33%) and bone (22%) levels were found, but other tissues were not affected. These differences are unable to account for the marked scan changes reported above. However, inactive GA(III) and FE(III) caused a reduction of 67 Ga in all tissues except bone. It is concluded that GD-DTPA or its constituents do not significantly alter the biodistribution of 67 Ga-citrate in mice. The reported scan changes may be the result of extensive chemotherapy

  19. Photoinduced electron transfer between Fe(III) and adenosine triphosphate-BODIPY conjugates: Application to alkaline-phosphatase-linked immunoassay.

    Science.gov (United States)

    Lin, Jia-Hui; Yang, Ya-Chun; Shih, Ya-Chen; Hung, Szu-Ying; Lu, Chi-Yu; Tseng, Wei-Lung

    2016-03-15

    Fluorescent boron dipyrromethene (BODIPY) analogs are often used as sensors for detecting various species because of their relatively high extinction coefficients, outstanding fluorescence quantum yields, photostability, and pH-independent fluorescence. However, there is little-to-no information in the literature that describes the use of BODIPY analogs for detecting alkaline phosphatase (ALP) activity and inhibition. This study discovered that the fluorescence of BODIPY-conjugated adenosine triphosphate (BODIPY-ATP) was quenched by Fe(III) ions through photoinduced electron transfer. The ALP-catalyzed hydrolysis of BODIPY-ATP resulted in the formation of BODIPY-adenosine and phosphate ions. The fluorescence of the generated BODIPY-adenosine was insensitive to the change in the concentration of Fe(III) ions. Thus, the Fe(III)-induced fluorescence quenching of BODIPY-ATP can be paired with its ALP-mediated dephosphorylation to design a turn-on fluorescence probe for ALP sensing. A method detection limit at a signal-to-noise ratio of 3 for ALP was estimated to be 0.02 units/L (~6 pM; 1 ng/mL). This probe was used for the screening of ALP inhibitors, including Na3VO4, imidazole, and arginine. Because ALP is widely used in enzyme-linked immunosorbent assays, the probe was coupled to an ALP-linked immunosorbent assay for the sensitive and selective detection of immunoglobulin G (IgG). The lowest detectable concentration for IgG in this system was 5 ng/mL. Compared with the use of 3,6-fluorescein diphosphate as a signal reporter in an ALP-linked immunosorbent assay, the proposed system provided comparable sensitivity, large linear range, and high stability over temperature and pH changes. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. THE UTILIZATION OF Fe(III WASTE OF ETCHING INDUSTRY AS QUALITY ENHANCHEMENT MATERIAL IN CERAMIC ROOFTILE SYNTHESIS

    Directory of Open Access Journals (Sweden)

    Eva Vaulina Yulistia Delsy

    2015-11-01

    Full Text Available Waste is produced from various industrial activities. FeCl3 used in this study as an addition to the material quality in synthesis of ceramic rooftile from Kalijaran village clay, Purbalingga. Etching industrial waste FeCl3 contacted with clay. Waste being varied waste as diluted and undiluted while clay grain size varied as 60, 80, 100, 140, and 230 mesh. Both clay and waste are contacted at 30-100 minutes. The results showed that the optimum of time and grain size variation is clay with 80 mesh grain size within 70 minutes. While physical properties of the rooftile contained Fe meet all ISO standards and are known to tile, the best quality is to use clay that has been in contact with the waste that is created 1000 times dilution. The stripping test of Fe (III by rain water and sea water showed that the average rate of Fe-striped of the tile body that is made with soaked with diluted waste are 0.068 ppm/day and 0.055 ppm/day while for tile bodies soaked with waste is not diluted are 0.0722 ppm/day and 0.0560 ppm/day.

  1. Transformation of pristine and citrate-functionalized CeO2 nanoparticles in a laboratory-scale activated sludge reactor.

    Science.gov (United States)

    Barton, Lauren E; Auffan, Melanie; Bertrand, Marie; Barakat, Mohamed; Santaella, Catherine; Masion, Armand; Borschneck, Daniel; Olivi, Luca; Roche, Nicolas; Wiesner, Mark R; Bottero, Jean-Yves

    2014-07-01

    Engineered nanomaterials (ENMs) are used to enhance the properties of many manufactured products and technologies. Increased use of ENMs will inevitably lead to their release into the environment. An important route of exposure is through the waste stream, where ENMs will enter wastewater treatment plants (WWTPs), undergo transformations, and be discharged with treated effluent or biosolids. To better understand the fate of a common ENM in WWTPs, experiments with laboratory-scale activated sludge reactors and pristine and citrate-functionalized CeO2 nanoparticles (NPs) were conducted. Greater than 90% of the CeO2 introduced was observed to associate with biosolids. This association was accompanied by reduction of the Ce(IV) NPs to Ce(III). After 5 weeks in the reactor, 44 ± 4% reduction was observed for the pristine NPs and 31 ± 3% for the citrate-functionalized NPs, illustrating surface functionality dependence. Thermodynamic arguments suggest that the likely Ce(III) phase generated would be Ce2S3. This study indicates that the majority of CeO2 NPs (>90% by mass) entering WWTPs will be associated with the solid phase, and a significant portion will be present as Ce(III). At maximum, 10% of the CeO2 will remain in the effluent and be discharged as a Ce(IV) phase, governed by cerianite (CeO2).

  2. Expanding the Therapeutic Potential of the Iron Chelator Deferasirox in the Development of Aqueous Stable Ti(IV) Anticancer Complexes.

    Science.gov (United States)

    Loza-Rosas, Sergio A; Vázquez-Salgado, Alexandra M; Rivero, Kennett I; Negrón, Lenny J; Delgado, Yamixa; Benjamín-Rivera, Josué A; Vázquez-Maldonado, Angel L; Parks, Timothy B; Munet-Colón, Charlene; Tinoco, Arthur D

    2017-07-17

    The recent X-ray structure of titanium(IV)-bound human serum transferrin (STf) exhibiting citrate as a synergistic anion reveals a difference in Ti(IV) coordination versus iron(III), the metal endogenously delivered by the protein to cells. This finding enriches our bioinspired drug design strategy for Ti(IV)-based anticancer therapeutics, which applies a family of Fe(III) chelators termed chemical transferrin mimetic (cTfm) ligands to inhibit Fe bioavailability in cancer cells. Deferasirox, a drug used for iron overload disease, is a cTfm ligand that models STf coordination to Fe(III), favoring Fe(III) binding versus Ti(IV). This metal affinity preference drives deferasirox to facilitate the release of cytotoxic Ti(IV) intracellularly in exchange for Fe(III). An aqueous speciation study performed by potentiometric titration from pH 4 to 8 with micromolar levels of Ti(IV) deferasirox at a 1:2 ratio reveals exclusively Ti(deferasirox) 2 in solution. The predominant complex at pH 7.4, [Ti(deferasirox) 2 ] 2- , exhibits the one of the highest aqueous stabilities observed for a potent cytotoxic Ti(IV) species, demonstrating little dissociation even after 1 month in cell culture media. UV-vis and 1 H NMR studies show that the stability is unaffected by the presence of biomolecular Ti(IV) binders such as citrate, STf, and albumin, which have been shown to induce dissociation or regulate cellular uptake and can alter the activity of other antiproliferative Ti(IV) complexes. Kinetic studies on [Ti(deferasirox) 2 ] 2- transmetalation with Fe(III) show that a labile Fe(III) source is required to induce this process. The initial step of this process occurs on the time scale of minutes, and equilibrium for the complete transmetalation is reached on a time scale of hours to a day. This work reveals a mechanism to deliver Ti(IV) compounds into cells and trigger Ti(IV) release by a labile Fe(III) species. Cellular studies including other cTfm ligands confirm the Fe(III) depletion

  3. The CrIIL reduction of [2Fe-2S] ferredoxins and site of attachment of CrIII using 1H NMR and site-directed mutagenesis.

    Science.gov (United States)

    Im, S C; Worrall, J A; Liu, G; Aliverti, A; Zanetti, G; Luchinat, C; Bertini, I; Sykes, A G

    2000-04-17

    The recently reported NMR solution structure of FeIIIFeIII parsley FdI has made possible 2D NOESY NMR studies to determine the point of attachment of CrIIIL in FeIIIFeIII...CrIIIL. The latter Cr-modified product was obtained by reduction of FeIIIFeIII parsley and spinach FdI forms with [Cr(15-aneN4) (H2O)2]2+ (15-aneN4 = 1,4,8,12-tetraazacyclopentadecane), referred to here as CrIIL, followed by air oxidation and chromatographic purification. From a comparison of NMR cross-peak intensities of native and Cr-modified proteins, two surface sites designated A and B, giving large paramagnetic CrIIIL broadening of a number of amino acid peaks, have been identified. The effects at site A (residues 19-22, 27, and 30) are greater than those at site B (residues 92-94 and 96), which is on the opposite side of the protein. From metal (ICP-AES) and electrospray ionization mass spectrometry (EIMS) analyses on the Cr-modified protein, attachment of a single CrIIIL only is confirmed for both parsley and spinach FdI and FdII proteins. Electrostatic interaction of the 3+ CrIIIL center covalently attached to one protein molecule (charge approximately -18) with a second (like) molecule provides an explanation for the involvement of two regions. Thus for 3-4 mM FeIIIFeIII...CrIIIL solutions used in NMR studies (CrIIIL attached at A), broadening effects due to electrostatic interactions at B on a second molecule are observed. Experiments with the Cys18Ala spinach FdI variant have confirmed that the previously suggested Cys-18 at site A is not the site of CrIIIL attachment. Line broadening at Val-22 of A gives the largest effect, and CrIIIL attachment at one or more adjacent (conserved) acidic residues in this region is indicated. The ability of CrIIL to bind in some (parsley and spinach) but not all cases (Anabaena variabilis) suggests that intramolecular H-bonding of acidic residues at A is relevant. The parsley and spinach FeIIFeIII...CrIIIL products undergo a second stage of reduction

  4. Factors affecting the line-shape of the EPR signal of high-spin Fe(III) in soybean lipoxygenase-1

    NARCIS (Netherlands)

    Slappendel, S.; Aasa, R.; Malmström, B.G.; Verhagen, J.; Veldink, G.A.; Vliegenthart, J.F.G.

    1982-01-01

    The yellow form of soybean lipoxygenase-1 (linoleate:oxygen oxidoreductase, EC 1.13.11.12), obtained upon addition of one molar equivalent of acid (13--HPOD) to the native enzyme, shows a complex EPR signal around g 6 which results from contributions of different high-spin Fe(III) species with

  5. Research by Moessbauer and infrared spectroscopy of films of polyacrylonitrile doped with FeCl2 and FeCl3

    International Nuclear Information System (INIS)

    Santos, Vadilson M. dos; Silva Filho, Eloi A. da; Nunes Filho, Evaristo

    2009-01-01

    The heating effect on films of polyacrylonitrile and doping of the ions Fe(II) and Fe (III) may reveal important aspects of the use of this polymer in the search for new materials. This paper was done the doping of the films of PAN with ions Fe(II) and Fe (III), with thermo heating is range of 60 a 90 deg C e de 90 a 170 deg C through the alkaline and acid hydrolysis of the CN groups used spectroscopy of FTIR and Moessbauer techniques to evaluate the structural changes results of doping process this polymer. The results showed that the FTIR spectral have a strong interaction of the ions Fe(II) and Fe (III) with PAN and confirmed by Moessbauer data. (author)

  6. Size- and composition-dependent toxicity of synthetic and soil-derived Fe oxide colloids for the nematode Caenorhabditis elegans.

    Science.gov (United States)

    Höss, Sebastian; Fritzsche, Andreas; Meyer, Carolin; Bosch, Julian; Meckenstock, Rainer U; Totsche, Kai Uwe

    2015-01-06

    Colloidal iron oxides (FeOx) are increasingly released to the environment due to their use in environmental remediation and biomedical applications, potentially harming living organisms. Size and composition could affect the bioavailability and toxicity of such colloids. Therefore, we investigated the toxicity of selected FeOx with variable aggregate size and variably composed FeOx-associated organic matter (OM) toward the nematode Caenorhabditis elegans. Ferrihydrite colloids containing citrate were taken up by C. elegans with the food and accumulated inside their body. The toxicity of ferrihydrite, goethite, and akaganeite was dependent on aggregate size and specific surface area, with EC50 values for reproduction ranging from 4 to 29 mg Fe L(-1). Experiments with mutant strains lacking mitochondrial superoxide dismutase (sod-2) showed oxidative stress for two FeOx and Fe(3+)-ions, however, revealed that it was not the predominant mechanism of toxicity. The OM composition determined the toxicity of mixed OM-FeOx phases on C. elegans. FeOx associated with humic acids or citrate were less toxic than OM-free FeOx. In contrast, soil-derived ferrihydrite, containing proteins and polysaccharides from mobile OM, was even more toxic than OM-free Fh of similar aggregate size. Consequently, the careful choice of the type of FeOx and the type of associated OM may help in reducing the ecological risks if actively applied to the subsurface.

  7. Desulfuromonas svalbardensis sp. nov. and Desulfuromusa ferrireducens sp. nov., psychrophilic, Fe(III)-reducing bacteria isolated from Arctic sediments, Svalbard

    DEFF Research Database (Denmark)

    Vandieken, Verona; Mussmann, Marc; Niemann, Helge

    2006-01-01

    Two psychrophilic, Gram-negative, rod-shaped, motile bacteria (strains 112T and 102T) that conserved energy from dissimilatory Fe(III) reduction concomitant with acetate oxidation were isolated from permanently cold Arctic marine sediments. Both strains grew at temperatures down to -2 degrees C...

  8. Desulfuromonas svalbardensis sp nov and Desulfuromusa ferrireducens sp nov., psychrophilic, Fe(III)-reducing bacteria isolated from Arctic sediments, Svalbard

    DEFF Research Database (Denmark)

    Vandieken, V.; Mussmann, M.; Niemann, Hans Henrik

    2006-01-01

    Two psychrophilic, Gram-negative, rod-shaped, motile bacteria (strains 112(T) and 102(T)) that conserved energy from dissimilatory Fe(III) reduction concomitant with acetate oxidation were isolated from permanently cold Arctic marine sediments. Both strains grew at temperatures down to -2 degrees C...

  9. Probing phosphate ion via the europium(III)-modulated fluorescence of gold nanoclusters

    International Nuclear Information System (INIS)

    Ding, Shou-Nian; Li, Chun-Mei; Gao, Bu-Hong; Kargbo, Osman; Zhou, Chan; Chen, Xi; Wan, Neng

    2014-01-01

    Fluorescent gold nanoclusters (Au-NCs) were synthesized by a one-pot method using 11-mercaptoundecanoic acid as a reducing and capping reagent. It is found that the red fluorescence of the Au-NCs is quenched by the introduction of Eu(III) at pH 7.0, but that fluorescence is restored on addition of phosphate. The Au-NCs were investigated by transmission electron microscopy and fluorescence photographs. The effect of pH on fluorescence was studied in the range from pH 6 to 10 and is found to be strong. Based on these findings, we have developed an assay for phosphate. Ions such as citrate, Fe(CN) 6 3− , SO 4 2− , S 2 O 8 2− , Cl − , HS − , Br − , AcO − , NO 2 − , SCN − , ClO 4 − , HCO 3 − , NO 3 − , Cd 2+ , Ba 2+ , Zn 2+ , Mg 2+ , and glutamate do not interfere, but ascorbate and Fe 3+ can quench Au-NCs fluorescence. The fluorescent nanocluster probe responds to phosphate in the range from 0.18 to 250 μM, and the detection limit is 180 nM. The probe also responds to pyrophosphate and ATP. (author)

  10. Formation, aggregation and reactivity of amorphous ferric oxyhydroxides on dissociation of Fe(III)-organic complexes in dilute aqueous suspensions

    Science.gov (United States)

    Bligh, Mark W.; Waite, T. David

    2010-10-01

    While chemical reactions that take place at the surface of amorphous ferric oxides (AFO) are known to be important in aquatic systems, incorporation of these reactions into kinetic models is hindered by a lack of ability to reliably quantify the reactivity of the surface and the changes in reactivity that occur over time. Long term decreases in the reactivity of iron oxides may be considered to result from changes in the molecular structure of the solid, however, over shorter time scales where substantial aggregation may occur, the mechanisms of reactivity loss are less clear. Precipitation of AFO may be described as a combination of homogeneous and heterogeneous reactions, however, despite its potentially significant role, the latter reaction is usually neglected in kinetic models of aquatic processes. Here, we investigate the role of AFO in scavenging dissolved inorganic ferric (Fe(III)) species (Fe') via the heterogeneous precipitation reaction during the net dissociation of organically complexed Fe(III) in seawater. Using sulfosalicylic acid (SSA) as a model ligand, AFO was shown to play a significant role in inducing the net dissociation of the Fe-SSA complexes with equations describing both the heterogeneous precipitation reaction and the aging of AFO being required to adequately describe the experimental data. An aggregation based mechanism provided a good description of AFO aging over the short time scale of the experiments. The behaviour of AFO described here has implications for the bioavailability of iron in natural systems as a result of reactions involving AFO which are recognised to occur over time scales of minutes, including adsorption of Fe' and AFO dissolution, precipitation and ageing.

  11. Comparison of the efficiency of clomiphene citrate and letrozole in combination with metformin in moderately obese clomiphene citrate-resistant polycystic ovarian syndrome patients.

    Science.gov (United States)

    Bjelica, Artur; Trninić-Pjević, Aleksandra; Mladenović-Segedi, Ljiljana; Cetković, Nenad; Petrović, Djordje

    2016-01-01

    Polycystic ovary syndrome is the most common endocrinopathy in women of reproductive-age. Therapy for those who want to get pregnant involves ovulation induction using clomiphene citrate, metformin, letrozole and gonadotropins. The aim of the study was to compare the efficacy of combinations of clomiphene citrate-metformin and letrozole-metformin in obese patients who are resistant to clomiphene citrate alone. The investigation was conducted as a retrospective study involving 60 moderately obese patients with polycystic ovary syndrome. Thirty-one of them received the clomiphene citrate-metformin, and 29 letrozole-metformin therapy. Stimulation was carried out for the procedures of intrauterine insemination (IUI). The age of patients, duration of infertility, and body mass index in both groups were similar. There was statistically significant difference in the thickness of the endometrium in favor of the group having the letrozole-metformin therapy (8.9 ± 1.7 mm) compared with the group receiving the clomiphene citrate-metformin treatment (6.3 ± 1.3 mm). The number of follicles was not statistically significantly different. Pregnancy rate in the first cycle of IUI in the clomiphene citrate group was 6.4%, and 17.2% in the letrozole group, which also was not statistically different. After the third IUI cycle, the pregnancy rate was significantly higher in the letrozole group (20.6%), while in the clomiphene citrate group it was (9.6%). This retrospective study demonstrated the advantages of the use of letrozole over clomiphene citrate in combination with metformin in moderately obese patients with polycystic ovary syndrome who are resistant to stimulation with clomiphene citrate alone.

  12. Physiology, Fe(II oxidation, and Fe mineral formation by a marine planktonic cyanobacterium grown under ferruginous conditions

    Directory of Open Access Journals (Sweden)

    Elizabeth D. Swanner

    2015-10-01

    Full Text Available Evidence for Fe(II oxidation and deposition of Fe(III-bearing minerals from anoxic or redox-stratified Precambrian oceans has received support from decades of sedimentological and geochemical investigation of Banded Iron Formations (BIF. While the exact mechanisms of Fe(II oxidation remains equivocal, reaction with O2 in the marine water column, produced by cyanobacteria or early oxygenic phototrophs, was likely. In order to understand the role of cyanobacteria in the deposition of Fe(III minerals to BIF, we must first know how planktonic marine cyanobacteria respond to ferruginous (anoxic and Fe(II-rich waters in terms of growth, Fe uptake and homeostasis, and Fe mineral formation. We therefore grew the common marine cyanobacterium Synechococcus PCC 7002 in closed bottles that began anoxic, and contained Fe(II concentrations that span the range of possible concentrations in Precambrian seawater. These results, along with cell suspension experiments, indicate that Fe(II is likely oxidized by this strain via chemical oxidation with oxygen produced during photosynthesis, and not via any direct enzymatic or photosynthetic pathway. Imaging of the cell-mineral aggregates with scanning electron microscopy (SEM and confocal laser scanning microscopy (CLSM are consistent with extracellular precipitation of Fe(III (oxyhydroxide minerals, but that >10% of Fe(III sorbs to cell surfaces rather than precipitating. Proteomic experiments support the role of reactive oxygen species (ROS in Fe(II toxicity to Synechococcus PCC 7002. The proteome expressed under low Fe conditions included multiple siderophore biosynthesis and siderophore and Fe transporter proteins, but most siderophores are not expressed during growth with Fe(II. These results provide a mechanistic and quantitative framework for evaluating the geochemical consequences of perhaps life’s greatest metabolic innovation, i.e. the evolution and activity of oxygenic photosynthesis, in ferruginous

  13. XAS signatures of Am(III) adsorbed onto magnetite and maghemite

    DEFF Research Database (Denmark)

    Finck, N.; Radulescu, L.; Schild, D.

    2016-01-01

    Trivalent americium was adsorbed on magnetite and maghemite under similar chemical conditions and the local environment probed by EXAFS spectroscopy. In both samples, partially hydrated Am(III) binds the surface but slightly different surface complexes were identified. On Fe3O4, Am(III) forms...... monomeric tridentate surface complexes similar to that reported for Pu(III) at the (111) surface. In contrast, the lower number of detected Fe atoms may suggest that Am(III) forms monomeric bidentate surface complexes on γ-Fe2O3. Alternatively, the lower Fe coordination number can also be due...

  14. Enclomiphene Citrate for the Treatment of Secondary Male Hypogonadism

    Science.gov (United States)

    Rodriguez, Katherine M.; Pastuszak, Alexander W.; Lipshultz, Larry I.

    2016-01-01

    Introduction Hypogonadism is a growing concern in an aging male population. Historically treated using exogenous testosterone, concerns about possible adverse effects of testosterone have led physicians to seek alternative treatment approaches. Areas Covered Enclomiphene citrate is the trans isomer of clomiphene citrate, a non-steroidal estrogen receptor antagonist that is FDA-approved for the treatment of ovarian dysfunction in women. Clomiphene citrate has also been used off-label for many years to treat secondary male hypogonadism, particularly in the setting of male infertility. Here we review the literature examining the efficacy and safety of enclomiphene citrate in the setting of androgen deficiency. Expert Opinion Initial results support the conclusion that enclomiphene citrate increases serum testosterone levels by raising luteinizing hormone (LH) and follicle stimulating hormone (FSH) levels, without negatively impacting semen parameters. The ability to treat testosterone deficiency in men while maintaining fertility supports a role for enclomiphene citrate in the treatment of men in whom testosterone therapy is not a suitable option. PMID:27337642

  15. Iron(III) protoporphyrin IX-single-wall carbon nanotubes modified electrodes for hydrogen peroxide and nitrite detection

    International Nuclear Information System (INIS)

    Turdean, Graziella L.; Popescu, Ionel Catalin; Curulli, Antonella; Palleschi, Giuseppe

    2006-01-01

    Iron(III) protoporphyrin IX (Fe(III)P), adsorbed either on single-walled carbon nanotubes (SWCNT) or on hydroxyl-functionalized SWCNT (SWCNT-OH), was incorporated within a Nafion matrix immobilized on the surface of a graphite electrode. From cyclic voltammetric measurements, performed under different experimental conditions (pH and potential scan rate), it was established that the Fe(III)P/Fe(II)P redox couple involves 1e - /1H + . The heterogeneous electron transfer process occurred faster when Fe(III)P was adsorbed on SWCNT-OH (∼11 s -1 ) than on SWCNT (∼4.9 s -1 ). Both the SWCNT-Fe(III)P- and SWCNT-OH-Fe(III)P-modified graphite electrodes exhibit electrocatalytic activity for H 2 O 2 and nitrite reduction. The modified electrodes sensitivities were found varying in the following sequences: S SWCNT-OH-Fe(III)P = 2.45 mA/M ∼ S SWCNT-Fe(III)P = 2.95 mA/M > S Fe(III)P = 1.34 mA/M for H 2 O 2 , and S SWCNT-Fe(III)P = 3.54 mA/M > S Fe(III)P 1.44 mA/M > S SWCNT-OH-Fe(III)P = 0.81 mA/M for NO 2 -

  16. pH-Responsive Fe(III)-Gallic Acid Nanoparticles for In Vivo Photoacoustic-Imaging-Guided Photothermal Therapy.

    Science.gov (United States)

    Zeng, Jianfeng; Cheng, Ming; Wang, Yong; Wen, Ling; Chen, Ling; Li, Zhen; Wu, Yongyou; Gao, Mingyuan; Chai, Zhifang

    2016-04-06

    pH-responsive biocompatible Fe(III)-gallic acid nanoparticles with strong near-infrared absorbance are very stable in mild acidic conditions, but easily decomposed in neutral conditions, which enables the nanoparticles to be stable in a tumor and easily metabolized in other organs, thus providing a safe nanoplatform for in vivo photoacoustic imaging/photothermal therapy theranostic applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Magnetic properties of Fe-doped organic-inorganic nanohybrids

    Science.gov (United States)

    Silva, N. J. O.; Amaral, V. S.; Carlos, L. D.; de Zea Bermudez, V.

    2003-05-01

    We present a magnetic study of Fe-doped diureasils (siloxane-based networks to which poly(ethylene oxide)-based chains are grafted by urea cross linkages doped with Fe(II) or Fe(III) ions. Structural studies show that the Fe(II) ions interact mainly with the organic chain, whereas the incorporation of Fe(III) leads to the formation of iron-based nanoclusters, with radius increasing from 20 to 40 Å. Fe(II)-doped samples behave as simple paramagnets, with μeff=5.32μB. Fe(III)-doped hybrids present antiferromagnetic interactions, with TN increasing with Fe(III) concentration up to 13.6 K for 6% doping. Thermal irreversibility was observed below ˜40 K and is stronger for higher concentrations. The coercive fields (HC) are of the order of 1000 Oe at 5 K. Hysteresis cycles are shifted to negative fields, revealing the presence of exchange anisotropy interactions with exchange fields (HE) of the order of 100 Oe. Both fields decrease rapidly with increasing temperature. We analyze this behavior in terms of the contribution of surface spin disorder to exchange anisotropy.

  18. Antitumor effect and toxicity of free rhodium (II) citrate and rhodium (II) citrate-loaded maghemite nanoparticles in mice bearing breast cancer.

    Science.gov (United States)

    Carneiro, Marcella Lemos Brettas; Peixoto, Raphael C A; Joanitti, Graziela A; Oliveira, Ricardo G S; Telles, Luis A M; Miranda-Vilela, Ana L; Bocca, Anamélia L; Vianna, Leonora M S; da Silva, Izabel C R; de Souza, Aparecido R; Lacava, Zulmira G M; Báo, Sônia N

    2013-02-16

    Magnetic fluids containing superparamagnetic iron oxide nanoparticles represent an attractive platform as nanocarriers in chemotherapy. Recently, we developed a formulation of maghemite nanoparticles coated with rhodium (II) citrate, which resulted in in vitro cytotoxicity enhanced up to 4.6 times when compared to free rhodium (II) citrate formulation on breast carcinoma cells. In this work, we evaluate the antitumor activity and toxicity induced by these formulations in Balb/c mice bearing orthotopic 4T1 breast carcinoma. Mice were evaluated with regard to the treatments' toxicity through analyses of hemogram, serum levels of alanine aminotransferase, iron, and creatinine; DNA fragmentation and cell cycle of bone marrow cells; and liver, kidney and lung histology. In addition, the antitumor activity of rhodium (II) citrate and maghemite nanoparticles coated with rhodium (II) citrate was verified by tumor volume reduction, histology and immunohistochemistry. Regarding the treatments' toxicity, no experimental groups had alterations in levels of serum ALT or creatinine, and this suggestion was corroborated by the histopathologic examination of liver and kidney of mice. Moreover, DNA fragmentation frequency of bone marrow cells was lower than 15% in all experimental groups. On the other hand, the complexes rhodium (II) citrate-functionalized maghemite and free rhodium (II) citrate led to a marked growth inhibition of tumor and decrease in CD31 and Ki-67 staining. In summary, we demonstrated that both rhodium (II) citrate and maghemite nanoparticles coated with rhodium (II) citrate formulations exhibited antitumor effects against 4T1 metastatic breast cancer cell line following intratumoral administration. This antitumor effect was followed by inhibition of both cell proliferation and microvascularization and by tumor tissue injury characterized as necrosis and fibrosis. Remarkably, this is the first published report demonstrating the therapeutic efficacy of maghemite

  19. Charge transport in micas: The kinetics of FeII/III electron transfer in the octahedral sheet

    International Nuclear Information System (INIS)

    Rosso, Kevin M.; Ilton, Eugene S.

    2003-01-01

    The two principal FeII/III electron exchange reactions underlying charge transport in the octahedral sheet of ideal end-member annite were modeled using a combination of ab initio calculations and Marcus electron transfer theory. A small polaron model was applied which yielded electron hopping activation energies that agree well with the limited available experimental data. A small ab initio cluster model successfully reproduced several important structural, energetic, and magnetic characteristics of the M1 and M2 Fe sites in the annite octahedral sheet. The cluster enabled calculation of the internal reorganization energy and electronic coupling matrix elements for the M2-M2 and M1-M2 electron transfer reactions. The M2-M2 electron transfer is symmetric with a predicted forward/reverse electron hopping rate of 106 s-1. The M1-M2 electron transfers are asymmetric due to the higher ionization potential by 0.46 eV of FeII in the M1 site. The electronic coupling matrix elements for these reactions are predicted to be small and of similar magnitude, suggesting the possibility that the coupling is essentially direction independent amongst hopping directions in the octahedral sheet. M1 Fe sites are predicted to be efficient electron traps and charge transport should occur by nearest-neighbor electron hops along the M2 Fe sublattice

  20. Role of an organic carbon-rich soil and Fe(III) reduction in reducing the toxicity and environmental mobility of chromium(VI) at a COPR disposal site.

    Science.gov (United States)

    Ding, Weixuan; Stewart, Douglas I; Humphreys, Paul N; Rout, Simon P; Burke, Ian T

    2016-01-15

    Cr(VI) is an important contaminant found at sites where chromium ore processing residue (COPR) is deposited. No low cost treatment exists for Cr(VI) leaching from such sites. This study investigated the mechanism of interaction of alkaline Cr(VI)-containing leachate with an Fe(II)-containing organic matter rich soil beneath the waste. The soil currently contains 0.8% Cr, shown to be present as Cr(III)(OH)3 in EXAFS analysis. Lab tests confirmed that the reaction of Cr(VI) in site leachate with Fe(II) present in the soil was stoichiometrically correct for a reductive mechanism of Cr accumulation. However, the amount of Fe(II) present in the soil was insufficient to maintain long term Cr(VI) reduction at historic infiltration rates. The soil contains a population of bacteria dominated by a Mangroviflexus-like species, that is closely related to known fermentative bacteria, and a community capable of sustaining Fe(III) reduction in alkaline culture. It is therefore likely that in situ fermentative metabolism supported by organic matter in the soil produces more labile organic substrates (lactate was detected) that support microbial Fe(III) reduction. It is therefore suggested that addition of solid phase organic matter to soils adjacent to COPR may reduce the long term spread of Cr(VI) in the environment. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

  1. Concurrent nitrate and Fe(III) reduction during anaerobic biodegradation of phenols in a sandstone aquifer

    DEFF Research Database (Denmark)

    Broholm, Mette; Crouzet, C.; Arvin, Erik

    2000-01-01

    The biodegradation of phenols (similar to 5, 60, 600 mg 1(-1)) under anaerobic conditions (nitrate enriched and unamended) was studied in laboratory microcosms with sandstone material and groundwater from within an anaerobic ammonium plume in an aquifer, The aqueous phase was sampled and analyzed...... for phenols and selected redox sensitive parameters on a regular basis. An experiment with sandstone material from specific depth intervals from a vertical profile across the ammonium plume was also conducted. The miniature microcosms used in this experiment were sacrificed for sampling for phenols...... and selected redox sensitive parameters at the end of the experiment. The sandstone material was characterized with respect to oxidation and reduction potential and Fe(II) and Fe(III) speciation prior to use for all microcosms and at the end of the experiments for selected microcosms. The redox conditions...

  2. Resonance Raman detection of iron-ligand vibrations in cyano(pyridine)(octaethylporphinato)iron(III): Effects of pyridine basicity on the Fe-CN bond strength

    International Nuclear Information System (INIS)

    Uno, Tadayuki; Hatano, Keiichiro; Nishimura, Yoshifumi; Arata, Yoji

    1988-01-01

    The influence of axial ligand basicity on the bonding of iron(III) in cyano adducts of octaethylporphyrin has been studied by resonance Raman spectroscopy. In a six-coordinate ferric low-spin complex, cyano(pyridine)(octaethylporphinato)iron(III), Fe(OEP)(CN)(py), Raman lines at 449 and 191 cm -1 were assigned to the ν(Fe-CN) and ν(Fe-py) stretching modes, respectively. When pyridine was displaced with its derivatives, py-X, where X = 4-cyano, 3-acetyl, 3-methyl, 4-methyl, 3,4-dimethyl, and 4-dimethylamino, the ν(Fe-CN) stretching frequency was found to decrease in the complex with a high pyridine basicity. It was concluded that the stronger the trans pyridine basicity, the weaker the iron-carbon (cyanide) bond. A clear frequency shift was observed in the ν 4 model, though most of the porphyrin vibrations were insensitive to the ligand substitution. The frequency of the ν 4 mode, which is the C a -N(pyrrole) breathing vibration of the porphyrin skeleton, was found to increase with an increase in pyridine basicity. This is contrary to what was found in ferrous low-spin hemes as CO complexes. The ν 4 shift in the CN complexes was explained in terms of forward π donation; donation of electrons from the porphyrin π orbital to the d π vacancy of the low-spin iron(III) weakened the C a -N(pyrrole) bonds and hence decreased the ν 4 frequency. 32 references, 8 figures

  3. Visible light photodegradation of phenanthrene catalyzed by Fe(III)-smectite: role of soil organic matter.

    Science.gov (United States)

    Jia, Hanzhong; Li, Li; Fan, Xiaoyun; Liu, Mingdeng; Deng, Wenye; Wang, Chuanyi

    2013-07-15

    In the present study, phenanthrene is employed as a model to explore the roles played by three soil organic matter (SOM) fractions, i.e., dissolved organic matter (DOM), humic acid (HA), and fulvic acid (FA), in its photodegradation with assistance of Fe(III)-smectite under visible-light. Slight decrease in phenanthrene photodegradation rate was observed in the presence of DOM, which is explained in terms of oxidative-radical competition between DOM and target phenanthrene molecules due to the high electron-donor capacity of phenolic moieties in DOM. On the other hand, a critic content is observed with FA (0.70mg/g) and HA (0.65mg/g). Before reaching the critic content, the removal of phenanthrene is accelerated; while after that, the photodegradation rate is suppressed. The acceleration of phenanthrene degradation can be attributed to the photosensitization of FA and HA. Due to the strong interaction between phenanthrene and the phenyl rings, however, the retention of phenanthrene on SOM-Fe(III)-smectite in the presence of high content of HA or FA is enhanced, thus slowing down its photodegradation. Those observations provide valuable insights into the transformation and fate of PAHs in the natural soil environment and open a window for using clay-humic substances complexes for remediation of contaminated soil. Copyright © 2013 Elsevier B.V. All rights reserved.

  4. Accumulation of Fe oxyhydroxides in the Peruvian oxygen deficient zone implies non-oxygen dependent Fe oxidation

    Science.gov (United States)

    Heller, Maija I.; Lam, Phoebe J.; Moffett, James W.; Till, Claire P.; Lee, Jong-Mi; Toner, Brandy M.; Marcus, Matthew A.

    2017-08-01

    Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here we have measured the redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). We present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen.

  5. Synthesis and characterization of the Rhodium (II) citrate complex

    International Nuclear Information System (INIS)

    Najjar, R.; Santos, F.S. dos; Seidel, W.

    1987-01-01

    The preparation and characterization of the rhodium (II) citrate is described. Rhodium citrate was prepared by reacting citric acid trihydrated (3,4 g, 16 mmols) with anhydrous rhodium acetate (0,44 g, 1 mmol). Th electronic instruments, thermogravimetric curve and spectrum of rhodium (II) citrate are analysed. (M.J.C.) [pt

  6. The Role of Coulomb Interactions for Spin Crossover Behaviors and Crystal Structural Transformation in Novel Anionic Fe(III Complexes from a π-Extended ONO Ligand

    Directory of Open Access Journals (Sweden)

    Suguru Murata

    2016-05-01

    Full Text Available To investigate the π-extension effect on an unusual negative-charged spin crossover (SCO FeIII complex with a weak N2O4 first coordination sphere, we designed and synthesized a series of anionic FeIII complexes from a π-extended naphthalene derivative ligand. Acetonitrile-solvate tetramethylammonium (TMA salt 1 exhibited an SCO conversion, while acetone-solvate TMA salt 2 was in a high-spin state. The crystal structural analysis for 2 revealed that two-leg ladder-like cation-anion arrays derived from π-stacking interactions between π-ligands of the FeIII complex anion and Coulomb interactions were found and the solvated acetone molecules were in one-dimensional channels between the cation-anion arrays. A desolvation-induced single-crystal-to-single-crystal transformation to desolvate compound 2’ may be driven by Coulomb energy gain. Furthermore, the structural comparison between quasi-polymorphic compounds 1 and 2 revealed that the synergy between Coulomb and π-stacking interactions induces a significant distortion of coordination structure of 2.

  7. Comparison of the efficiency of clomiphene citrate and letrozole in combination with metformin in moderately obese clomiphene citrate - resistant polycystic ovarian syndrome patients

    Directory of Open Access Journals (Sweden)

    Bjelica Artur

    2016-01-01

    Full Text Available Introduction. Polycystic ovary syndrome is the most common endocrinopathy in women of reproductiveage. Therapy for those who want to get pregnant involves ovulation induction using clomiphene citrate, metformin, letrozole and gonadotropins. Objective. The aim of the study was to compare the efficacy of combinations of clomiphene citrate-metformin and letrozole-metformin in obese patients who are resistant to clomiphene citrate alone. Methods. The investigation was conducted as a retrospective study involving 60 moderately obese patients with polycystic ovary syndrome. Thirty-one of them received the clomiphene citrate-metformin, and 29 letrozole-metformin therapy. Stimulation was carried out for the procedures of intrauterine insemination (IUI. Results. The age of patients, duration of infertility, and body mass index in both groups were similar. There was statistically significant difference in the thickness of the endometrium in favor of the group having the letrozole-metformin therapy (8.9 ± 1.7 mm compared with the group receiving the clomiphene citrate-metformin treatment (6.3 ± 1.3 mm. The number of follicles was not statistically significantly different. Pregnancy rate in the first cycle of IUI in the clomiphene citrate group was 6.4%, and 17.2% in the letrozole group, which also was not statistically different. After the third IUI cycle, the pregnancy rate was significantly higher in the letrozole group (20.6%, while in the clomiphene citrate group it was (9.6%. Conclusion. This retrospective study demonstrated the advantages of the use of letrozole over clomiphene citrate in combination with metformin in moderately obese patients with polycystic ovary syndrome who are resistant to stimulation with clomiphene citrate alone.

  8. Synthesis, Characterization and Thermal Decomposition Studies of Cr(III, Mn(II and Fe(III Complexes of N, N '-Bis[1,3-benzodioxol-5-ylmethylene]butane-1,4-diamine

    Directory of Open Access Journals (Sweden)

    Prasad M. Alex

    2009-01-01

    Full Text Available A bidentate Schiff base ligand namely, N,N'-bis-1,3-benzodioxol-5-ylmethylene]butane-1,4-diamine was synthesised by condensing piperonal (3,4-dioxymethylenebenzaldehyde with butane-1,4-diamine. Cr(III, Mn(II, Fe(III complexes of this chelating ligand were synthesised using acetates, chlorides, bromides, nitrates and perchlorates of these metals. The ligand and the complexes were characterised by elemental analysis, 1H NMR, UV-Vis and IR spectra, conductance and magnetic susceptibility measurements and thermogravimetric analysis. The thermograms of three complexes were analysed and the kinetic parameters for the different stages of decompositions were determined.

  9. Clomiphene citrate-induced visual hallucinations: a case report

    OpenAIRE

    Venkatesh, Ramesh; Gujral, Gaganjeet Singh; Gurav, Prachi; Tibrewal, Shailja; Mathur, Umang

    2017-01-01

    Background Polycystic ovary syndrome is a common cause of chronic anovulation and infertility in otherwise healthy fertile couples. Clomiphene citrate is used as a first-line ovulation induction therapy in patients with polycystic ovary syndrome. Clomiphene citrate can cause both systemic and ocular side effects. We report a rare side effect of illusory palinopsias in a patient with polycystic ovary syndrome treated with ovulation induction therapy with clomiphene citrate, and emphasize the n...

  10. Preparation of lead titanate zirconate from metal citrates

    International Nuclear Information System (INIS)

    Bastos, C.M.R.

    1994-01-01

    Lead titanate zirconate (PZT) preparation from its metal constituent citrates have been investigated. Metal citrates were obtained by forced precipitation using a dehydration alcohol mixture. Salt solutions of lead nitrate and octahydrated zirconyl chloride, and titanium tetrachloride were treated separately with citric acid and ammonium hydroxide. Zirconium, titanium and lead oxides resulted from thermal decomposition of corresponding citrates at 500 0 C, 450 0 C and 250 0 C, respectively. Lead titanate (PT) and lead zirconate (P Z) were obtained by calcining at 450 0 C and 500 0 C, respectively, after adequate heating of citrates mechanically mixed in ethyl ether. PZT samples were obtained with different starting stoichiometry. Rhombohedral PZT-1 53/47 sample was prepared from co precipitating zirconyl ammonium and ammonium lead citrates in presence of ethanolic titanium oxide dispersion, and calcinating at 800 0 C. Rhombohedral PZT-q 52/48 sample was obtained from heating at 500 0 C for 2 hours a mixture of metal citrates coprecipitated by dehydration mixture of acetone-ethanol-formic acid (2:1:0,06). Tetragonal PZT-m stoichiometry 53/47 sample were obtained by calcining at after 600 0 C for 2 hours after heating a mechanically mixed metal citrates. PT phase arose at 400 0 C. PZT-m powders obtained in a range of 400 0 C-800 0 C were isostatically pressed, and sintered at 1100 0 C and 1200 0 C in saturated Pb O atmosphere. Rhombohedral sintered PZT was obtained with 7,78 g.cm -3 at 1200 0 C. (author). 123 refs, 53 figs, 32 tabs

  11. Anodic Stripping Voltammetric Detection of Arsenic(III) at Platinum-Iron(III) Nanoparticle Modified Carbon Nanotube on Glassy Carbon Electrode

    International Nuclear Information System (INIS)

    Shin, Seung Hyun; Hong, Hun Gi

    2010-01-01

    The electrochemical detection of As(III) was investigated on a platinum-iron(III) nanoparticles modified multiwalled carbon nanotube on glassy carbon electrode(nanoPt-Fe(III)/MWCNT/GCE) in 0.1 M H 2 SO 4 . The nanoPt-Fe(III)/ MWCNT/GCE was prepared via continuous potential cycling in the range from .0.8 to 0.7 V (vs. Ag/AgCl), in 0.1 M KCl solution containing 0.9 mM K 2 PtCl 6 and 0.6 mM FeCl 3 . The Pt nanoparticles and iron oxide were co-electrodeposited into the MWCNT-Nafion composite film on GCE. The resulting electrode was examined by cyclic voltammetry (CV), scanning electron microscopy (SEM), and anodic stripping voltammetry (ASV). For the detection of As(III), the nanoPt-Fe(III)/MWCNT/GCE showed low detection limit of 10 nM (0.75 ppb) and high sensitivity of 4.76 μAμM -1 , while the World Health Organization's guideline value of arsenic for drinking water is 10 ppb. It is worth to note that the electrode presents no interference from copper ion, which is the most serious interfering species in arsenic detection

  12. Hemodiafiltration using pre-dilutional on-line citrate dialysate: A new technique for regional citrate anticoagulation: A feasibility study

    Directory of Open Access Journals (Sweden)

    Radhouane Bousselmi

    2015-01-01

    Full Text Available A prospective, observational, feasibility study was carried out on four patients with end-stage renal failure undergoing bicarbonate hemodialysis to study the feasibility of an on-line hemodiafiltration technique using a citrate dialysate with pre-dilutional infusion of citrate as a technique for regional citrate anticoagulation. All patients had contraindication to systemic heparin anticoagulation. The dialysis technique consisted of an on-line hemodiafiltration with a citrate dialysate without calcium using a Fresenius 4008S dialysis machine and Fresenius Polysulfone F60 dialyzers. The infusion solution was procured directly from the dialysate and was infused into the arterial line. To avoid the risk of hypocalcemia, calcium gluconate was infused to the venous return line. The study was carried out in two stages. During the first stage, the citrate infusion rate was 80 mL/min and the calcium infusion rate was 9 mmol/h. At the second stage, the rates were 100 mL/min and 11 mmol/h, respectively. The primary endpoint of this study was the incidence of thrombosis in the extracorporeal blood circuit and/or the dialyzer. A total of 78 sessions were conducted. All the sessions were well tolerated clinically and there were no major incidents in any of the four patients. At the first stage of the study, there were five incidences of small clots in the venous blood chamber, an incidence of extracorporeal blood circuit thrombosis of 12.5%. At the second stage of the study, no cases of extracorporeal blood circuit or dialyzer thrombosis were noted. Hemodiafiltration with on-line citrate dialysate infusion to the arterial line is safe and allows an effective regional anticoagulation of the extracorporeal blood circuit without the need for systemic anticoagulation.

  13. Microbial Mn(IV) and Fe(III) reduction in northern Barents Sea sediments under different conditions of ice cover and organic carbon deposition

    DEFF Research Database (Denmark)

    Nickel, Maren; Vandieken, Verona; Brüchert, Volker

    2008-01-01

    station, with seasonally extended ice cover, low organic carbon content and sedimentation rate combined with relatively high concentrations of Mn and Fe(III) oxides favored dissimilatory Fe and Mn reduction (98% of anaerobic carbon oxidation) over sulfate reduction in the top 12 cm of the sediment....... In contrast, in a sediment that had not been ice covered for at least 12 months and with more organic carbon and a higher sedimentation rate, sulfate reduction was the most important anaerobic electron-accepting process (>80% of anaerobic carbon oxidation). In the upper 3 cm, microbial Fe and sulfate...

  14. As(III) oxidation by MnO2 during groundwater treatment.

    Science.gov (United States)

    Gude, J C J; Rietveld, L C; van Halem, D

    2017-03-15

    The top layer of natural rapid sand filtration was found to effectively oxidise arsenite (As(III)) in groundwater treatment. However, the oxidation pathway has not yet been identified. The aim of this study was to investigate whether naturally formed manganese oxide (MnO 2 ), present on filter grains, could abiotically be responsible for As(III) oxidation in the top of a rapid sand filter. For this purpose As(III) oxidation with two MnO 2 containing powders was investigated in aerobic water containing manganese(II) (Mn(II)), iron(II) (Fe(II)) and/or iron(III) (Fe(III)). The first MnO 2 powder was a very pure - commercially available - natural MnO 2 powder. The second originated from a filter sand coating, produced over 22 years in a rapid filter during aeration and filtration. Jar test experiments showed that both powders oxidised As(III). However, when applying the MnO 2 in aerated, raw groundwater, As(III) removal was not enhanced compared to aeration alone. It was found that the presence of Fe(II)) and Mn(II) inhibited As(III) oxidation, as Fe(II) and Mn(II) adsorption and oxidation were preferred over As(III) on the MnO 2 surface (at pH 7). Therefore it is concluded that just because MnO 2 is present in a filter bed, it does not necessarily mean that MnO 2 will be available to oxidise As(III). However, unlike Fe(II), the addition of Fe(III) did not hinder As(III) oxidation on the MnO 2 surface; resulting in subsequent effective As(V) removal by the flocculating hydrous ferric oxides. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. Citrate and succinate uptake by potato mitochondria

    International Nuclear Information System (INIS)

    Jung, D.W.; Laties, G.G.

    1979-01-01

    Potato mitochondria, in the absence of respiration, have a very low capacity for uptake by exchange with endogenous anions, taking up only 2.4 nanomoles citrate and 2.0 nanomoles succinate per milligram protein. Maximum citrate uptake of over 17 nanomoles per milligram protein occurs in the presence of inorganic phosphate, a dicarboxylic acid, and an external energy source (NADH), conditions where net anion accumulation proceeds, mediated by the interlinking of the inorganic phosphate, dicarboxylate, and tricarboxylate carriers. Maximum succinate uptake in the absence of respiratory inhibitors requires only added inorganic phosphate. Compounds which inhibit respiration (antimycin), the exchange carriers (mersalyl and benzylmalonate), or the establishment of the membrane proton motive force (uncouplers) reduce substrate accumulation. A potent inhibitor of the citrate carrier in animal mitochondria, 1,2,3-benzenetricarboxylic acid, does not inhibit citrate uptake in potato mitochondria. Citrate uptake is reduced by concurrent ADP phosphorylation and this reduction is sensitive to oligomycin. The initiation of state 3 after a 3-minute substrate state results in a reduction of the steady-state of citrate uptake by approximately 50%. Accumulation of succinate initially is inhibited by increasing sucrose concentration in the reaction medium from 50 to 400 millimolar. Limited substrate uptake is one of the factors responsible for the often observed depressed initial state 3 respiration rates in many mitochondrial preparations. Since nonlimiting levels of substrate in the matrix cannot be attained by energy-independent exchange, a dependence on respiration for adequate uptake results. Substrate limitation therefore occurs in the matrix for the period of time needed for energy-dependent accumulation of nonlimiting levels

  16. Novel mode of microbial energy metabolism: organic carbon oxidation coupled to dissimilatory reduction of iron or manganese.

    Science.gov (United States)

    Lovley, D R; Phillips, E J

    1988-06-01

    A dissimilatory Fe(III)- and Mn(IV)-reducing microorganism was isolated from freshwater sediments of the Potomac River, Maryland. The isolate, designated GS-15, grew in defined anaerobic medium with acetate as the sole electron donor and Fe(III), Mn(IV), or nitrate as the sole electron acceptor. GS-15 oxidized acetate to carbon dioxide with the concomitant reduction of amorphic Fe(III) oxide to magnetite (Fe(3)O(4)). When Fe(III) citrate replaced amorphic Fe(III) oxide as the electron acceptor, GS-15 grew faster and reduced all of the added Fe(III) to Fe(II). GS-15 reduced a natural amorphic Fe(III) oxide but did not significantly reduce highly crystalline Fe(III) forms. Fe(III) was reduced optimally at pH 6.7 to 7 and at 30 to 35 degrees C. Ethanol, butyrate, and propionate could also serve as electron donors for Fe(III) reduction. A variety of other organic compounds and hydrogen could not. MnO(2) was completely reduced to Mn(II), which precipitated as rhodochrosite (MnCO(3)). Nitrate was reduced to ammonia. Oxygen could not serve as an electron acceptor, and it inhibited growth with the other electron acceptors. This is the first demonstration that microorganisms can completely oxidize organic compounds with Fe(III) or Mn(IV) as the sole electron acceptor and that oxidation of organic matter coupled to dissimilatory Fe(III) or Mn(IV) reduction can yield energy for microbial growth. GS-15 provides a model for how enzymatically catalyzed reactions can be quantitatively significant mechanisms for the reduction of iron and manganese in anaerobic environments.

  17. Effect of Iron Fe (II and Fe (III in a Binary System Evaluated Bioluminescent Method

    Directory of Open Access Journals (Sweden)

    Elena Sorokina

    2013-01-01

    Full Text Available The effect of iron ions Fe2+ and Fe3+ on the bioluminescent recombinant strain of Escherichia coli in a single-component and binary system. Found that for the bacteria E. coli Fe3+ ions are more toxic than Fe2+. Under the combined effect of iron toxicity increases, the percentage of luminescence quenching increases, but the value is much less than the sum of the indicator for the Fe2+ and Fe3+. The biological effect of insertion of iron is not proportional to their content in the mixture.

  18. Extraction behaviour of Am(III) and Eu(III) from nitric acid medium in TEHDGA-HDEHP impregnated resins

    Energy Technology Data Exchange (ETDEWEB)

    Saipriya, G.; Kumar, T. [Bhabha Atomic Research Centre Facilities, Kalpakkam (India). Kalpakkam Reprocessing Plant; Kumaresan, R.; Nayak, P.K.; Venkatesan, K.A.; Antony, M.P. [Indira Gandhi Center for Atomic Research, Kalpakkam (India). Fuel Chemistry Div.

    2016-07-01

    The extraction behaviour of Am(III) and Eu(III) from nitric acid medium was studied in the solvent impregnated resins containing extractants such as tetra-bis(2-ethylhexyl)diglycolamide (TEHDGA) or bis-(2-ethylhexyl)phosphoric acid (HDEHP) or mixture of TEHDGA+HDEHP. The rate of extraction of Am(III) and Eu(III) from 1 M nitric acid and the effect of various parameters, such as the concentration of nitric acid in aqueous phase and concentration of TEHDGA and HDEHP in resin phase, on the distribution coefficient of Am(III) and Eu(III) was studied. The distribution coefficient of Am(III) and Eu(III) in HDEHP-impregnated resin decreased and that in TEHDGA-impregnated resin increased, with increase in the concentration of nitric acid. However, in (TEHDGA+HDEHP) - impregnated resin, synergic extraction was observed at lower nitric acid concentration and antagonism at higher nitric acid concentration. The mechanism of Am(III) and Eu(III) extraction in the combined resin was investigated by slope analysis method. The extraction of various metal ions present in the fast reactor simulated high-level liquid waste was studied. The separation factor of Am(III) over Eu(III) was studied using citrate-buffered diethylenetriaminepentaacetic acid (DTPA) solution.

  19. Mechanisms of Fe biofortification and mitigation of Cd accumulation in rice (Oryza sativa L.) grown hydroponically with Fe chelate fertilization.

    Science.gov (United States)

    Chen, Zhe; Tang, Ye-Tao; Zhou, Can; Xie, Shu-Ting; Xiao, Shi; Baker, Alan J M; Qiu, Rong-Liang

    2017-05-01

    Cadmium contaminated rice from China has become a global food safety issue. Some research has suggested that chelate addition to substrates can affect metal speciation and plant metal content. We investigated the mitigation of Cd accumulation in hydroponically-grown rice supplied with EDTANa 2 Fe(II) or EDDHAFe(III). A japonica rice variety (Nipponbare) was grown in modified Kimura B solution containing three concentrations (0, 10, 100 μΜ) of the iron chelates EDTANa 2 Fe(II) or EDDHAFe(III) and 1 μΜ Cd. Metal speciation in solution was simulated by Geochem-EZ; growth and photosynthetic efficiency of rice were evaluated, and accumulation of Cd and Fe in plant parts was determined. Net Cd fluxes in the meristematic zone, growth zone, and maturation zone of roots were monitored by a non-invasive micro-test technology. Expression of Fe- and Cd-related genes in Fe-sufficient or Fe-deficient roots and leaves were studied by QRT-PCR. Compared to Fe deficiency, a sufficient or excess supply of Fe chelates significantly enhanced rice growth by elevating photosynthetic efficiency. Both Fe chelates increased the Fe content and decreased the Cd content of rice organs, except for the Cd content of roots treated with excess EDDHAFe(III). Compared to EDDHAFe(III), EDTANa 2 Fe(II) exhibited better mitigation of Cd accumulation in rice by generating the EDTANa 2 Cd complex in solution, decreasing net Cd influx and increasing net Cd efflux in root micro-zones. Application of EDTANa 2 Fe(II) and EDDHAFe(III) also reduced Cd accumulation in rice by inhibiting expression of genes involved in transport of Fe and Cd in the xylem and phloem. The 'win-win' situation of Fe biofortification and Cd mitigation in rice was achieved by application of Fe chelates. Root-to-stem xylem transport of Cd and redistribution of Cd in leaves by phloem transport can be regulated in rice through the use of Fe chelates that influence Fe availability and Fe-related gene expression. Fe fertilization

  20. Fe++/Fe+++ concentration relationship and mechanical properties of phosphate glasses useful for wastes immobilization

    International Nuclear Information System (INIS)

    Garcia, D.A.; Prado, Miguel O.

    2007-01-01

    Under different melting conditions, glasses with different Fe(II)/Fe(III) concentration relationship were prepared within each type of glass 43Fe 2 O 3 -57P 2 O 5 and 33,33Fe 2 O 3 - 66,67P 2 O 5 . Using Moessbauer spectroscopy Fe(II)/Fe(III) concentration values were determined. Vickers and Knoop indentations were used for determining their hardness, toughness, Young modulus and brittleness. The same measurements were carried on some silicate and aluminosilicate glasses. Also Weibull statistics was done to determine the characteristics (Weibull modulus and and fracture probability) of glass fracture. We found that silicate glasses (SG) are harder than phosphate glasses (PG). Toughness values for PG, are in the same range than for SG, although for the same density exhibit larger values or smaller brittleness than silicate glasses. For one of the glasses it was found that the mechanical load P 0 needed for a fracture probability of 63% increases with the Fe(II) content. (author)

  1. Preparation and biodistribution of {sup 59}Fe-radiolabelled iron oxide nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Pospisilova, Martina, E-mail: martinapospisilova@gmail.com; Zapotocky, Vojtech; Nesporova, Kristina [Contipro a.s (Czech Republic); Laznicek, Milan; Laznickova, Alice [Charles University, Faculty of Pharmacy in Hradec Králové (Czech Republic); Zidek, Ondrej; Cepa, Martin; Vagnerova, Hana; Velebny, Vladimir [Contipro a.s (Czech Republic)

    2017-02-15

    We report on the {sup 59}Fe radiolabelling of iron oxide nanoparticle cores through post-synthetic isotope exchange ({sup 59}Fe-IONP{sub ex}) and precursor labelling ({sup 59}Fe-IONP{sub pre}). Scanning electron microscopy and dynamic light scattering measurements showed no impact of radiolabelling on nanoparticle size or morphology. While incorporation efficiencies of these methods are comparable—83 and 90% for precursor labelling and post-synthetic isotope exchange, respectively—{sup 59}Fe-IONP{sub pre} exhibited much higher radiochemical stability in citrated human plasma. Quantitative ex vivo biodistribution study of {sup 59}Fe-IONP{sub pre} coated with triethylene glycol was performed in Wistar rats. Following the intravenous administration, high {sup 59}Fe concentration was observed in the lung and the organs of the reticuloendothelial system such as the liver, the spleen and the femur.

  2. A test of the citrate method of PMI estimation from skeletal remains.

    Science.gov (United States)

    Wilson, Sarah J; Christensen, Angi M

    2017-01-01

    Citrate content in bone has been shown to be associated with the postmortem interval (PMI), with citrate decreasing after death as a function of time. Here we test this method using porcine ribs for the period of 1-165days after death, and also assess citrate content and variation from samples placed into two different postmortem environments (terrestrial and aquatic). Higher citrate variation, lower citrate recovery, and a weaker association with time were found in this study as compared to others. Citrate content, however, was found to decrease with increasing PMI, and the method was found to be easy and inexpensive to apply. No significant differences were found in citrate loss between terrestrial and aquatic environments. Although more research is needed, citrate content appears to be a promising new approach in estimating PMI from skeletal remains. Published by Elsevier B.V.

  3. Influence of organics and silica on Fe(II) oxidation rates and cell-mineral aggregate formation by the green-sulfur Fe(II)-oxidizing bacterium Chlorobium ferrooxidans KoFox - Implications for Fe(II) oxidation in ancient oceans

    Science.gov (United States)

    Gauger, Tina; Byrne, James M.; Konhauser, Kurt O.; Obst, Martin; Crowe, Sean; Kappler, Andreas

    2016-06-01

    Most studies on microbial phototrophic Fe(II) oxidation (photoferrotrophy) have focused on purple bacteria, but recent evidence points to the importance of green-sulfur bacteria (GSB). Their recovery from modern ferruginous environments suggests that these photoferrotrophs can offer insights into how their ancient counterparts grew in Archean oceans at the time of banded iron formation (BIF) deposition. It is unknown, however, how Fe(II) oxidation rates, cell-mineral aggregate formation, and Fe-mineralogy vary under environmental conditions reminiscent of the geological past. To address this, we studied the Fe(II)-oxidizer Chlorobium ferrooxidans KoFox, a GSB living in co-culture with the heterotrophic Geospirillum strain KoFum. We investigated the mineralogy of Fe(III) metabolic products at low/high light intensity, and in the presence of dissolved silica and/or fumarate. Silica and fumarate influenced the crystallinity and particle size of the produced Fe(III) minerals. The presence of silica also enhanced Fe(II) oxidation rates, especially at high light intensities, potentially by lowering Fe(II)-toxicity to the cells. Electron microscopic imaging showed no encrustation of either KoFox or KoFum cells with Fe(III)-minerals, though weak associations were observed suggesting co-sedimentation of Fe(III) with at least some biomass via these aggregates, which could support diagenetic Fe(III)-reduction. Given that GSB are presumably one of the most ancient photosynthetic organisms, and pre-date cyanobacteria, our findings, on the one hand, strengthen arguments for photoferrotrophic activity as a likely mechanism for BIF deposition on a predominantly anoxic early Earth, but, on the other hand, also suggest that preservation of remnants of Fe(II)-oxidizing GSB as microfossils in the rock record is unlikely.

  4. An isoelectronic NO dioxygenase reaction using a nonheme iron(III)-peroxo complex and nitrosonium ion.

    Science.gov (United States)

    Yokoyama, Atsutoshi; Han, Jung Eun; Karlin, Kenneth D; Nam, Wonwoo

    2014-02-18

    Reaction of a nonheme iron(III)-peroxo complex, [Fe(III)(14-TMC)(O2)](+), with NO(+), a transformation which is essentially isoelectronic with that for nitric oxide dioxygenases [Fe(III)(O2˙(-)) + NO], affords an iron(IV)-oxo complex, [Fe(IV)(14-TMC)(O)](2+), and nitrogen dioxide (NO2), followed by conversion to an iron(III)-nitrato complex, [Fe(III)(14-TMC)(NO3)(F)](+).

  5. Synthesis, investigation and spectroscopic characterization of piroxicam ternary complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with glycine and DL-phenylalanine

    Science.gov (United States)

    Mohamed, Gehad G.; El-Gamel, Nadia E. A.

    2004-11-01

    The ternary piroxicam (Pir; 4-hydroxy-2-methyl- N-(2-pyridyl)-2H-1,2-benzothiazine-3-carboxamide 1,1-dioxide) complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with various amino acids (AA) such as glycine (Gly) or DL-phenylalanine (PhA) were prepared and characterized by elemental analyses, molar conductance, IR, UV-Vis, magnetic moment, diffuse reflectance and X-ray powder diffraction. The UV-Vis spectra of Pir and the effect of metal chelation on the different interligand transitions are discussed in detailed manner. IR and UV-Vis spectra confirm that Pir behaves as a neutral bidentate ligand coordinated to the metal ions via the pyridine- N and carbonyl group of the amide moiety. Gly molecule acted as a uninegatively monodentate ligand and coordinate to the metal ions through its carboxylic group, in addition PhA acted as a uninegatively bidentate ligand and coordinate to the metal ions through its carboxylic and amino groups. All the chelates have octahedral geometrical structures while Cu(II)- and Zn(II)-ternary chelates with PhA have square planar geometrical structures. The molar conductance data reveal that most of these chelates are non electrolytes, while Fe(III)-Pir-Gly, Co(II)-, Ni(II)-, Cu(II)- and Zn(II)-Pir-PhA cheletes were 1:1 electrolytes. X-ray powder diffraction is used as a new tool to estimate the crystallinity of chelates as well as to elucidate their geometrical structures.

  6. Influence of Ni(II) and Fe(III) complexes of 1,2 dihydroxy 9,10 anthraquinone on the modification in calf thymus DNA upon gamma irradiation

    International Nuclear Information System (INIS)

    Das, Saurabh; Mandal, Parikshit C.

    2009-01-01

    Ionizing radiation when allowed to fall upon cells or DNA, the radicals produced modify the base-pair region of the double strands. Radiation-induced double-strand modifications in calf thymus DNA were detected using Ni(II) and Fe(III) complexes of 1,2 dihydroxy 9,10 anthraquinone (DHA). 60 Co was used as the source for γ-radiation and ethidium bromide (EB) as the fluorescent dye for detecting double-strand modifications caused in DNA. Results show that the Fe(III)-DHA complex is more efficient in modifying the base-pair region in double-stranded DNA in comparison to DHA or the Ni(II)-DHA complex

  7. An isoelectronic NO dioxygenase reaction using a nonheme iron(III)-peroxo complex and nitrosonium ion†

    Science.gov (United States)

    Yokoyama, Atsutoshi; Han, Jung Eun; Karlin, Kenneth D.; Nam, Wonwoo

    2014-01-01

    Reaction of a nonheme iron(III)-peroxo complex, [FeIII(14-TMC)(O2)]+, with NO+, a transformation which is essentially isoelectronic with that for nitric oxide dioxygenases [Fe(III)(O2•−) + NO], affords an iron(IV)-oxo complex, [FeIV(14-TMC)(O)]2+, and nitrogen dioxide (NO2), followed by conversion to an iron(III)-nitrato complex, [FeIII(14-TMC)(NO3)(F)]+. PMID:24394960

  8. An isoelectronic NO dioxygenase reaction using a nonheme iron(III)-peroxo complex and nitrosonium ion†

    OpenAIRE

    Yokoyama, Atsutoshi; Han, Jung Eun; Karlin, Kenneth D.; Nam, Wonwoo

    2014-01-01

    Reaction of a nonheme iron(III)-peroxo complex, [FeIII(14-TMC)(O2)]+, with NO+, a transformation which is essentially isoelectronic with that for nitric oxide dioxygenases [Fe(III)(O2•−) + NO], affords an iron(IV)-oxo complex, [FeIV(14-TMC)(O)]2+, and nitrogen dioxide (NO2), followed by conversion to an iron(III)-nitrato complex, [FeIII(14-TMC)(NO3)(F)]+.

  9. FERRIC CITRATE: AN IRON-BASED ORAL PHOSPHATE BINDER

    Directory of Open Access Journals (Sweden)

    T. Christopher Bond

    2012-06-01

    Based on actual physician behavior in response to ferritin and TSAT increases and ferric citrate clinical trial results, and assuming equivalent pricing to other PBs, there would be cost savings with ferric citrate use through reduced ESA and iron use.

  10. Preparation of electrocatalysts by reduction of precursors with sodium citrate

    OpenAIRE

    Briskeby, Stein Trygve; Tsypkin, Mikhail; Tunold, Reidar; Sunde, Svein

    2014-01-01

    In this work synthesis of Pt/C catalysts by reduction of H2PtCl6 with sodium citrate has been investigated. The strong pH-dependence of citrate as a reducing and stabilizing agent has been explored, and an optimum pH range for production of well dispersed catalysts is proposed. To achieve stabilizing and reducing conditions, the presence of both citrate anions and protonated citrates are required. This is achieved in an intermediate pH range between pKa2 and pKa3 (4.76 and 6.4) of citric acid...

  11. Controls on Fe reduction and mineral formation by a subsurface bacterium

    Science.gov (United States)

    Glasauer, Susan; Weidler, Peter G.; Langley, Sean; Beveridge, Terry J.

    2003-04-01

    The reductive dissolution of FeIII (hydr)oxides by dissimilatory iron-reducing bacteria (DIRB) could have a large impact on sediment genesis and Fe transport. If DIRB are able to reduce FeIII in minerals of high structural order to carry out anaerobic respiration, their range could encompass virtually every O 2-free environment containing FeIII and adequate conditions for cell growth. Previous studies have established that Shewanella putrefaciens CN32, a known DIRB, will reduce crystalline Fe oxides when initially grown at high densities in a nutrient-rich broth, conditions that poorly model the environments where CN32 is found. By contrast, we grew CN32 by batch culture solely in a minimal growth medium. The stringent conditions imposed by the growth method better represent the conditions that cells are likely to encounter in their natural habitat. Furthermore, the expression of reductases necessary to carry out dissimilatory Fe reduction depends on the method of growth. It was found that under anaerobic conditions CN32 reduced hydrous ferric oxide (HFO), a poorly crystalline FeIII mineral, and did not reduce suspensions containing 4 mM FeIII in the form of poorly ordered nanometer-sized goethite (α-FeOOH), well-ordered micron-sized goethite, or nanometer-sized hematite (α-Fe 2O 3) crystallites. Transmission electron microscopy (TEM) showed that all minerals but the micron-sized goethite attached extensively to the bacteria and appeared to penetrate the outer cellular membrane. In the treatment with HFO, new FeII and FeIII minerals formed during reduction of HFO-Fe in culture medium containing 4.0 mmol/L P i (soluble inorganic P), as observed by TEM with energy-dispersive X-ray spectroscopy, selected area electron diffraction, and X-ray diffraction. The minerals included magnetite (Fe 3O 4), goethite, green rust, and vivianite [Fe 3(PO 4) 2 · 8H 2O]. Vivianite appeared to be the stable end product and the mean coherence length was influenced by the rate of FeIII

  12. The third phase of the OECD/NEA TDB project: TDB III

    International Nuclear Information System (INIS)

    Mompean, F.J.; Illemassene, M.; Perrone, J.

    2005-01-01

    In 2003 with a foreseen duration of four years. The main objective of this new phase is to extend the existing critically reviewed database for elements of relevance in radioactive waste management, paying attention to the needs of the various national programmes. Following the decision by the Project Management Board (integrated by representatives of 16 organisations with responsibilities in radioactive waste management in 12 OECD member countries) the elements contemplated in this new phase are Th, Sn and Fe, with a higher priority being allocated to inorganic species and compounds. In addition to the corresponding review teams for these elements, an additional expert team has been constituted to prepare guidelines for the evaluation of thermodynamic data for solid solutions. As was the case in TDB Phase II, the basic project review methodology remains unaltered in TDB III. The Figure illustrates the relationship between the various TDB bodies, with an International Organisation, the OECD NEA, acting as Project Coordinator and linking the independent scientific teams and the project governing bodies. This organizational paradigm has proven successful with the recent completion of the five Phase II Reviews (Update, Ni, Se, Zr and Organic Ligands). The review and expert team activities were started in 2004 (except for Fe, being started in 2005) following an initiation stage. This preliminary stage was designed in order to tailor the team compositions to the existing literature for each element. The first reviews stemming from TDB III are scheduled to appear in published form in 2007. The successful completion of these objectives will add three further reports to the current series of nine volumes (dealing with the chemical thermodynamics of U, Np, Pu, Am, Tc, Ni, Se, Zr and compounds and complexes of these elements with oxalate, citrate, EDTA and isa). (authors)

  13. Negative impact of oxygen molecular activation on Cr(VI) removal with core–shell Fe@Fe2O3 nanowires

    International Nuclear Information System (INIS)

    Mu, Yi; Wu, Hao; Ai, Zhihui

    2015-01-01

    Highlights: • The presence of oxygen inhibited Cr(VI) removal efficiency with nZVI by near 3 times. • Cr(VI) removal with nZVI was related to adsorption, reduction, co-precipitation, and adsorption reactions. • Molecular oxygen activation competed donor electrons from Fe 0 core and surface bound Fe(II) of nZVI. • Thicker Cr(III)/Fe(III)/Cr(VI) oxyhydroxides shell of nZVI leaded to the electron transfer inhibition. - Abstract: In this study, we demonstrate that the presence of oxygen molecule can inhibit Cr(VI) removal with core–shell Fe@Fe 2 O 3 nanowires at neutral pH of 6.1. 100% of Cr(VI) removal was achieved by the Fe@Fe 2 O 3 nanowires within 60 min in the anoxic condition, in contrast, only 81.2% of Cr(VI) was sequestrated in the oxic condition. Removal kinetics analysis indicated that the presence of oxygen could inhibit the Cr(VI) removal efficiency by near 3 times. XRD, SEM, and XPS analysis revealed that either the anoxic or oxic Cr(VI) removal was involved with adsorption, reduction, co-precipitation, and re-adsorption processes. More Cr(VI) was bound in a reduced state of Cr(III) in the anoxic process, while a thicker Cr(III)/Fe(III)/Cr(VI) oxyhydroxides shell, leading to inhibiting the electron transfer, was found under the oxic process. The negative impact of oxygen molecule was attributed to the oxygen molecular activation which competed with Cr(VI) adsorbed for the consumption of donor electrons from Fe 0 core and ferrous ions bound on the iron oxides surface under the oxic condition. This study sheds light on the understanding of the fate and transport of Cr(VI) in oxic and anoxic environment, as well provides helpful guide for optimizing Cr(VI) removal conditions in real applications

  14. Crystal structure of octakis(4-methoxypyridinium bis(4-methoxypyridine-κNtetrakis(thiocyanato-κNferrate(III bis[(4-methoxypyridine-κNpentakis(thiocyanato-κNferrate(III] hexakis(thiocyanato-κNferrate(III with iron in three different octahedral coordination environments

    Directory of Open Access Journals (Sweden)

    Aleksej Jochim

    2018-03-01

    Full Text Available The crystal structure of the title salt, (C6H8NO8[Fe(NCS4(C6H7NO2][Fe(NCS5(C6H7NO]2[Fe(NCS6], comprises three negatively charged octahedral FeIII complexes with different coordination environments in which the FeIII atoms are coordinated by a different number of thiocyanate anions and 4-methoxypyridine ligands. Charge balance is achieved by 4-methoxypyridinium cations. The asymmetric unit consists of three FeIII cations, one of which is located on a centre of inversion, one on a twofold rotation axis and one in a general position, and ten thiocyanate anions, two 4-methoxypyridine ligands and 4-methoxypyridinium cations (one of which is disordered over two sets of sites. Beside to Coulombic interactions between organic cations and the ferrate(III anions, weak N—H...S hydrogen-bonding interactions involving the pyridinium N—H groups of the cations and the thiocyanate S atoms of the complex anions are mainly responsible for the cohesion of the crystal structure.

  15. Arsenic removal with iron(II) and iron(III) in waters with high silicate and phosphate concentrations.

    Science.gov (United States)

    Roberts, Linda C; Hug, Stephan J; Ruettimann, Thomas; Billah, Morsaline; Khan, Abdul Wahab; Rahman, Mohammad Tariqur

    2004-01-01

    Arsenic removal by passive treatment, in which naturally present Fe(II) is oxidized by aeration and the forming iron(III) (hydr)oxides precipitate with adsorbed arsenic, is the simplest conceivable water treatment option. However, competing anions and low iron concentrations often require additional iron. Application of Fe(II) instead of the usually applied Fe(III) is shown to be advantageous, as oxidation of Fe(II) by dissolved oxygen causes partial oxidation of As(III) and iron(III) (hydr)oxides formed from Fe(II) have higher sorption capacities. In simulated groundwater (8.2 mM HCO3(-), 2.5 mM Ca2+, 1.6 mM Mg2+, 30 mg/L Si, 3 mg/L P, 500 ppb As(III), or As(V), pH 7.0 +/- 0.1), addition of Fe(II) clearly leads to better As removal than Fe(III). Multiple additions of Fe(II) further improved the removal of As(II). A competitive coprecipitation model that considers As(III) oxidation explains the observed results and allows the estimation of arsenic removal under different conditions. Lowering 500 microg/L As(III) to below 50 microg/L As(tot) in filtered water required > 80 mg/L Fe(III), 50-55 mg/L Fe(II) in one single addition, and 20-25 mg/L in multiple additions. With As(V), 10-12 mg/L Fe(II) and 15-18 mg/L Fe(III) was required. In the absence of Si and P, removal efficiencies for Fe(II) and Fe(III) were similar: 30-40 mg/L was required for As(II), and 2.0-2.5 mg/L was required for As(V). In a field study with 22 tubewells in Bangladesh, passive treatment efficiently removed phosphate, but iron contents were generally too low for efficient arsenic removal.

  16. Determination of stability constants of iron(III and chromium(III-nitrilotriacetate-methyl cysteine mixed complexes by electrophoretic technique

    Directory of Open Access Journals (Sweden)

    Brij Bhushan Tewari

    2004-06-01

    Full Text Available The stability constants of Fe(III and Cr(III with methyl cysteine and nitrilotriacetate (NTA were determined by paper electrophoretic technique. Beside binary ternary complexes have also been studied, in which nitrilotriacetate and methyl cysteine acts as primary and secondary ligand, respectively. The stability constants of mixed ligand complexes metal (M-nitrilotriacetate-methyl cysteine have been found to be 5.72 plus or minus 0.09 and 5.54 plus or minus 0.11 (log K values for Fe(III and Cr(III complexes, respectively, at 35 oC and ionic strength 0.1 M.

  17. Synthesis, physicochemical characterization, DFT calculation and biological activities of Fe(III) and Co(II)-omeprazole complexes. Potential application in the Helicobacter pylori eradication

    Science.gov (United States)

    Russo, Marcos G.; Vega Hissi, Esteban G.; Rizzi, Alberto C.; Brondino, Carlos D.; Salinas Ibañez, Ángel G.; Vega, Alba E.; Silva, Humberto J.; Mercader, Roberto; Narda, Griselda E.

    2014-03-01

    The reaction between the antiulcer agent omeprazole (OMZ) with Fe(III) and Co(II) ions was studied, observing a high ability to form metal complexes. The isolated microcrystalline solid complexes were characterized by elemental analysis, X-ray powder diffraction (XRPD), Scanning Electron Microscopy (SEM), magnetic measurements, thermal study, FTIR, UV-Visible, Mössbauer, electronic paramagnetic resonance (EPR), and DFT calculations. The metal-ligand ratio for both complexes was 1:2 determined by elemental and thermal analysis. FTIR spectroscopy showed that OMZ acts as a neutral bidentate ligand through the pyridinic nitrogen of the benzimidazole ring and the oxygen atom of the sulfoxide group, forming a five-membered ring chelate. Electronic, Mössbauer, and EPR spectra together with magnetic measurements indicate a distorted octahedral geometry around the metal ions, where the coordination sphere is completed by two water molecules. SEM and XRPD were used to characterize the morphology and the crystal nature of the complexes. The most favorable conformation for the Fe(III)-OMZ and Co(II)-OMZ complexes was obtained by DFT calculations by using B3LYP/6-31G(d)&LanL2DZ//B3LYP/3-21G(d)&LanL2DZ basis set. Studies of solubility along with the antibacterial activity against Helicobacter pylori for OMZ and its Co(II) and Fe(III) complexes are also reported. Free OMZ and both metal complexes showed antibacterial activity against H. pylori. Co(II)-OMZ presented a minimal inhibitory concentration ˜32 times lower than that of OMZ and ˜65 lower than Fe(III)-OMZ, revealing its promising potential use for the treatment of gastric pathologies associated with the Gram negative bacteria. The morphological changes observed in the cell membrane of the bacteria after the incubation with the metal-complexes were also analyzed by SEM microscopy. The antimicrobial activity of the complexes was proved by the viability test.

  18. Bacteria attenuation by iron electrocoagulation governed by interactions between bacterial phosphate groups and Fe(III) precipitates.

    Science.gov (United States)

    Delaire, Caroline; van Genuchten, Case M; Amrose, Susan E; Gadgil, Ashok J

    2016-10-15

    Iron electrocoagulation (Fe-EC) is a low-cost process in which Fe(II) generated from an Fe(0) anode reacts with dissolved O2 to form (1) Fe(III) precipitates with an affinity for bacterial cell walls and (2) bactericidal reactive oxidants. Previous work suggests that Fe-EC is a promising treatment option for groundwater containing arsenic and bacterial contamination. However, the mechanisms of bacteria attenuation and the impact of major groundwater ions are not well understood. In this work, using the model indicator Escherichia coli (E. coli), we show that physical removal via enmeshment in EC precipitate flocs is the primary process of bacteria attenuation in the presence of HCO3(-), which significantly inhibits inactivation, possibly due to a reduction in the lifetime of reactive oxidants. We demonstrate that the adhesion of EC precipitates to cell walls, which results in bacteria encapsulation in flocs, is driven primarily by interactions between EC precipitates and phosphate functional groups on bacteria surfaces. In single solute electrolytes, both P (0.4 mM) and Ca/Mg (1-13 mM) inhibited the adhesion of EC precipitates to bacterial cell walls, whereas Si (0.4 mM) and ionic strength (2-200 mM) did not impact E. coli attenuation. Interestingly, P (0.4 mM) did not affect E. coli attenuation in electrolytes containing Ca/Mg, consistent with bivalent cation bridging between bacterial phosphate groups and inorganic P sorbed to EC precipitates. Finally, we found that EC precipitate adhesion is largely independent of cell wall composition, consistent with comparable densities of phosphate functional groups on Gram-positive and Gram-negative cells. Our results are critical to predict the performance of Fe-EC to eliminate bacterial contaminants from waters with diverse chemical compositions. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Seasonal changes in Fe species and soluble Fe concentration in the atmosphere in the Northwest Pacific region based on the analysis of aerosols collected in Tsukuba, Japan

    Directory of Open Access Journals (Sweden)

    Y. Takahashi

    2013-08-01

    Full Text Available Atmospheric iron (Fe can be a significant source of nutrition for phytoplankton inhabiting remote oceans, which in turn has a large influence on the Earth's climate. The bioavailability of Fe in aerosols depends mainly on the fraction of soluble Fe (= [FeSol]/[FeTotal], where [FeSol] and [FeTotal] are the atmospheric concentrations of soluble and total Fe, respectively. However, the numerous factors affecting the soluble Fe fraction have not been fully understood. In this study, the Fe species, chemical composition, and soluble Fe concentrations in aerosols collected in Tsukuba, Japan were investigated over a year (nine samples from December 2002 to October 2003 to identify the factors affecting the amount of soluble Fe supplied into the ocean. The soluble Fe concentration in aerosols is correlated with those of sulfate and oxalate originated from anthropogenic sources, suggesting that soluble Fe is mainly derived from anthropogenic sources. Moreover, the soluble Fe concentration is also correlated with the enrichment factors of vanadium and nickel emitted by fossil fuel combustion. These results suggest that the degree of Fe dissolution is influenced by the magnitude of anthropogenic activity, such as fossil fuel combustion. X-ray absorption fine structure (XAFS spectroscopy was performed in order to identify the Fe species in aerosols. Fitting of XAFS spectra coupled with micro X-ray fluorescence analysis (μ-XRF showed the main Fe species in aerosols in Tsukuba to be illite, ferrihydrite, hornblende, and Fe(III sulfate. Moreover, the soluble Fe fraction in each sample measured by leaching experiments is closely correlated with the Fe(III sulfate fraction determined by the XAFS spectrum fitting, suggesting that Fe(III sulfate is the main soluble Fe in the ocean. Another possible factor that can control the amount of soluble Fe supplied into the ocean is the total Fe(III concentration in the atmosphere, which was high in spring due to the high

  20. Extraction behaviour of Am(III) and Eu(III) from nitric acid medium in CMPO-HDEHP impregnated resins

    Energy Technology Data Exchange (ETDEWEB)

    Saipriya, K.; Kumar, T. [Bhabha Atomic Research Centre Facilities (India). Kalpakkam Reproscessing Plants; Kumaresan, R.; Nayak, P.K.; Venkatesan, K.A.; Antony, M.P. [Indira Gandhi Center for Atomic Research, Kalpakkam (India). Fuel Chemistry Div.

    2016-05-01

    Chromatographic resin containing extractants such as octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) or bis-(2-ethylhexyl)phosphoric acid (HDEHP) or mixture of extractants (CMPO + HDEHP) in an acrylic polymer matrix was prepared and studied for the extraction of Am(III) and Eu(III) over a range of nitric acid concentration. The effect of various parameters such as concentration of nitric acid in aqueous phase and the concentration of CMPO and HDEHP in the resin phase was studied. The distribution coefficient of Am(III) and Eu(III) in the impregnated resin increased with increased in the concentration of nitric acid for CMPO-impregnated resin, whereas a reverse trend was observed in HDEHP impregnated resin. In case of resin containing both the extractants, synergism was observed at low nitric acid concentration and antagonism at high nitric acid concentration. The mechanism of extraction was probed by slope analysis method at 0.01 and 2 M nitric acid concentrations. Citrate-buffered DTPA was used for the selective separation of Am(III), and a separation factor of 3-4 was obtained at pH 3.

  1. Influence of Y and La substitution on particle size, structural and magnetic properties of nanosized nickel ferrite prepared by using citrate precursor method

    Energy Technology Data Exchange (ETDEWEB)

    Anh, Luong Ngoc [International Training Institute for Materials Science (ITIMS), Hanoi University of Science and Technology, 1 Dai Co Viet Road, Hanoi (Viet Nam); Loan, To Thanh, E-mail: totloan@itims.edu.vn [International Training Institute for Materials Science (ITIMS), Hanoi University of Science and Technology, 1 Dai Co Viet Road, Hanoi (Viet Nam); Duong, Nguyen Phuc [International Training Institute for Materials Science (ITIMS), Hanoi University of Science and Technology, 1 Dai Co Viet Road, Hanoi (Viet Nam); Vietnam-Japan International Institute for Science of Technology (VJIIST), Hanoi University of Science and Technology, 1 Dai Co Viet Road, Hanoi (Viet Nam); Soontaranon, Siriwat [Synchrotron Light Research Institute, 111 University Avenue, Suranaree, Muang, Nakhon Ratchasima 30000 (Thailand); Viet Nga, Tran Thi; Hien, Than Duc [International Training Institute for Materials Science (ITIMS), Hanoi University of Science and Technology, 1 Dai Co Viet Road, Hanoi (Viet Nam)

    2015-10-25

    The compounds with the formulas NiFe{sub 2}O{sub 4}, NiFe{sub 1.9}Y{sub 0.1}O{sub 4} and NiFe{sub 1.9}La{sub 0.1}O{sub 4} were prepared by citrate precursor method and followed by heat treatment in air at 600 °C for 5 h. Crystal structure, valence state, chemical bonding and composition of the samples were studied rigorously by XRD, SXRD, XANES, FTIR and ICP–AES. Rietveld refinement of XRD and SXRD patterns reveals that the samples crystallize in single spinel phase with almost inverted structure in which the substituted ions Y{sup 3+} and La{sup 3+} locate in the octahedral sites and about ten percents of nickel atoms were found at the tetrahedral sites. Morphology and particle size were studied by SEM and TEM. The results show that the samples are composed of clustered nanoparticles with mean particle size decreases approximately from 20 nm in NiFe{sub 2}O{sub 4} sample to 10 nm in the substituted ones. The magnetic measurements were carried out by means of a VSM. Spontaneous magnetization, magnetic coercivity, Curie temperature, superparamagnetic transition temperature, interparticle interaction energy and effective anisotropy were determined and explained on the basis of the surface and finite–size effects and cation distribution. - Highlights: • Y{sup 3+} and La{sup 3+} substituted NiFe{sub 2}O{sub 4} nanoparticles are synthesized by citrate precursor method involving less energy. • XRD, SXRD and FTIR spectra reveal the crystallographic site occupancy of Y{sup 3+} and La{sup 3+}. • Compositions and valence states of cations are verified by ICP-AES and XANES. • Y{sup 3+} and La{sup 3+} substitution decreases the mean particle size to about 10 nm. • Influence of rare earth substitution and finite size in magnetic properties are investigated.

  2. Visible light photodegradation of phenanthrene catalyzed by Fe(III)-smectite: Role of soil organic matter

    Energy Technology Data Exchange (ETDEWEB)

    Jia, Hanzhong, E-mail: jiahz0143@yahoo.com.cn [Laboratory of Eco-Materials and Sustainable Technology (LEMST), Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi, Xinjiang 830011 (China); Li, Li [Laboratory of Eco-Materials and Sustainable Technology (LEMST), Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi, Xinjiang 830011 (China); The Graduate School of Chinese Academy of Science, Beijing 100049 (China); Fan, Xiaoyun [Laboratory of Eco-Materials and Sustainable Technology (LEMST), Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi, Xinjiang 830011 (China); Liu, Mingdeng [Laboratory of Eco-Materials and Sustainable Technology (LEMST), Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi, Xinjiang 830011 (China); The Graduate School of Chinese Academy of Science, Beijing 100049 (China); Deng, Wenye [Laboratory of Eco-Materials and Sustainable Technology (LEMST), Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi, Xinjiang 830011 (China); Wang, Chuanyi, E-mail: cywang@ms.xjb.ac.cn [Laboratory of Eco-Materials and Sustainable Technology (LEMST), Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi, Xinjiang 830011 (China)

    2013-07-15

    Highlights: • Soil organic matter (SOM) has significant influence on the transformation of PAHs. • Photodegradation rate is strongly dependent on the SOM fractions and their content. • Photolysis is determined by the interaction between phenanthrene, clay and SOM. -- Abstract: In the present study, phenanthrene is employed as a model to explore the roles played by three soil organic matter (SOM) fractions, i.e., dissolved organic matter (DOM), humic acid (HA), and fulvic acid (FA), in its photodegradation with assistance of Fe(III)-smectite under visible-light. Slight decrease in phenanthrene photodegradation rate was observed in the presence of DOM, which is explained in terms of oxidative-radical competition between DOM and target phenanthrene molecules due to the high electron–donor capacity of phenolic moieties in DOM. On the other hand, a critic content is observed with FA (0.70 mg/g) and HA (0.65 mg/g). Before reaching the critic content, the removal of phenanthrene is accelerated; while after that, the photodegradation rate is suppressed. The acceleration of phenanthrene degradation can be attributed to the photosensitization of FA and HA. Due to the strong interaction between phenanthrene and the phenyl rings, however, the retention of phenanthrene on SOM–Fe(III)-smectite in the presence of high content of HA or FA is enhanced, thus slowing down its photodegradation. Those observations provide valuable insights into the transformation and fate of PAHs in the natural soil environment and open a window for using clay–humic substances complexes for remediation of contaminated soil.

  3. Study of the oxidation-reduction kinetics involved in the Np(V) + Fe(II) in equilibrium Np(IV) + Fe(III) system in nitric acid solutions

    International Nuclear Information System (INIS)

    Jao, Y.

    1975-08-01

    Ferrous nitrate-hydrazine is one of the more attractive alternate reactants to the currently used reagent, ferrous sulfamate, for partitioning plutonium from neptunium and uranium. An understanding of the kinetics of the reduction of Np(VI) to Np(IV) by ferrous nitrate-hydrazine is needed before a satisfactory evaluation of the feasibility of this reductant in actinide element separations can be made. The purpose of this work was to study the kinetics and mechanisms of the reduction of Np(V) by Fe(II) and the oxidation of Np(IV) by Fe(III) in 1-2 M nitric acid solutions. The acid concentration range was chosen to include that typically used in the separation of plutonium from neptunium and uranium by solvent extraction with tributylphosphate. The forward and reverse rate constants, hydrogen ion dependence, temperature dependence, ionic strength effects and nitrate ion influence were determined. The proposed reaction mechanisms involve protonation of the NpO 2 + ions and hydroxyoxygenation of Np 4 + ions. (LK)

  4. Moessbauer study of FePO4 cathode for lithium- and sodium-ion batteries

    International Nuclear Information System (INIS)

    Tetsuaki Nishida; Masahiro Tokunaga; Toshiharu Nishizumi; Takafumi Yamamoto; Tomoyuki Shiratsuchi; Shigeto Okada; Jun-ichi Yamaki

    2005-01-01

    LiFePO 4 of olivine type has attracted much interest as a rare-metal free cathode for lithium-ion battery. The present authors' group has found a low-cost preparation method for new cathode material FePO 4 (P 321 ) from an aqueous solution of metallic iron and P 2 O 5 . A cathode pellet was prepared by mixing FePO 4 , acetylene black (AB) and polytetrafluoroethylene (PTFE) binder at a mass ratio of 70:25:5. Electrochemical cathode performance was investigated under a constant current density of 0.1 mA/cm 2 with a coin-type cell with an anode of metallic Li and Na for Li- and Na-ion batteries, respectively. Moessbauer spectra were measured by a constant accele- ration method with a Moessbauer source of 57 Co(Pd) and an α-Fe foil as a reference of the isomer shift. Moessbauer spectra of the original cathode pellet top left and right) composed of amorphous FePO 4 indicate that all the Fe III atoms have a tetrahedral symmetry. After discharging the Li-(second left) and Na-batteries (second right), all the Fe III were reduced to octahedral Fe II . The reduction of Fe III to Fe II indicates penetration of Li + and Na + into the FePO 4 cathode which accompanies an electron capture; Li + (or Na + ) + Fe III PO 4 + e - = LiFe II PO 4 (or NaFe II PO 4 ) After charging the Li-cell (bottom left), all the Fen atoms were oxidized to tetrahedral Fe III , while 69 % of Fe II was oxidized to Fe III in the Na-ion cell (bottom right) due to a lower cell voltage: 4.0 V. Oxidation of Fe II to Fe III reflects a release of Li + or Na + ions from the FePO 4 cathode to the electrolyte, i.e., an inverse reaction of eq.

  5. Preliminary study on the photoproduction of hydroxyl radicals in aqueous solution with Aldrich humic acid, algae and Fe(III) under high-pressure mercury lamp irradiation.

    Science.gov (United States)

    Liu, Xianli; Xu, Dong; Wu, Feng; Liao, Zhenhuan; Liu, Jiantong; Deng, Nansheng

    2004-03-01

    Under a high-pressure mercury lamp (HPML) and using an exposure time of 4 h, the photoproduction of hydroxyl radicals (*OH) could be induced in an aqueous solution containing humic acid (HA). Hydroxyl radicals were determined by high-performance liquid chromatography using benzene as a probe. The results showed that *OH photoproduction increased from 1.80 to 2.74 microM by increasing the HA concentration from 10 to 40 mg L(-1) at an exposure time of 4 h (pH 6.5). Hydroxyl radical photoproduction in aqueous solutions of HA containing algae was greater than that in the aqueous solutions of HA without algae. The photoproduction of *OH in the HA solution with Fe(III) was greater than that of the solution without Fe(III) at pH ranging from 4.0 to 8.0. The photoproduction of *OH in HA solution with algae with or without Fe(III) under a 250 W HPML was greater than that under a 125 W HPML. The photoproduction of *OH in irradiated samples was influenced by the pH. The results showed that HPML exposure for 4 h in the 4-8 pH range led to the highest *OH photoproduction at pH 4.0.

  6. Synthesis of Zn–Fe layered double hydroxides via an oxidation process and structural analysis of products

    Energy Technology Data Exchange (ETDEWEB)

    Morimoto, Kazuya, E-mail: kazuya.morimoto@aist.go.jp [Institute for Geo-Resources and Environment, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8567 (Japan); Tamura, Kenji [Environmental Remediation Materials Unit, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan); Anraku, Sohtaro [Graduate School of Engineering, Hokkaido University, Kita 13 Nishi 8, Kita-ku, Sapporo 060-8628 (Japan); Sato, Tsutomu [Faculty of Engineering, Hokkaido University, Kita 13 Nishi 8, Kita-ku, Sapporo 060-8628 (Japan); Suzuki, Masaya [Institute for Geo-Resources and Environment, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8567 (Japan); Yamada, Hirohisa [Environmental Remediation Materials Unit, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan)

    2015-08-15

    The synthesis of Zn–Fe(III) layered double hydroxides was attempted, employing different pathways using either Fe(II) or Fe(III) species together with Zn as the initial reagents. The product derived from the synthesis employing Fe(II) was found to transition to a Zn–Fe(III) layered double hydroxides phase following oxidation process. In contrast, the product obtained with Fe(III) did not contain a layered double hydroxides phase, but rather consisted of simonkolleite and hydrous ferric oxide. It was determined that the valency of the Fe reagent used in the initial synthesis affected the generation of the layered double hydroxides phase. Fe(II) species have ionic radii and electronegativities similar to those of Zn, and therefore are more likely to form trioctahedral hydroxide layers with Zn species. - Graphical abstract: The synthesis of Zn–Fe(III) layered double hydroxides was attempted, employing different pathways using either Fe(II) or Fe(III) species together with Zn as the initial reagents. - Highlights: • Iron valency affected the generation of Zn–Fe layered double hydroxides. • Zn–Fe layered double hydroxides were successfully synthesized using Fe(II). • Fe(II) species were likely to form trioctahedral hydroxide layers with Zn species.

  7. Valence-delocalization of the mixed-valence oxo-centered trinuclear iron propionates [FeIII2FeIIO(C2H5CO2)6(py)3[npy; n = 0, 1.5

    International Nuclear Information System (INIS)

    Nakamoto, Tadahiro; Katada, Motomi; Kawata, Satoshi; Kitagawa, Susumu; Sano, Hirotoshi; Konno, Michiko

    1994-01-01

    Mixed-valence trinuclear iron propionates [Fe III 2 Fe II O(C 2 H 5 CO 2 ) 6 (py) 3 [npy, where n = 0, 1.5, were synthesized and the structure of the pyridine-solvated complex was determined by single-crystal X-ray diffraction. Moessbauer spectra of the solvated propionate complex showed a temperature-dependent mixed-valence state related to phase transitions, reaching an almost delocalized valence state at room temperature. On the other hand, the non-solvated propionate showed a remarkable change of the spectral shape related to a phase transition, remaining in a localized valence state at higher temperatures up to room temperature. (orig.)

  8. Whole-body retention studies of /sup 167/Tm--citrate. Estimation of radiation dose to humans from /sup 167/Tm--citrate

    Energy Technology Data Exchange (ETDEWEB)

    Hiraki, T; Ando, A [Kanazawa Univ. (Japan). School of Paramedicine; Mori, H; Ando, I; Sakamoto, K

    1978-02-01

    For the purpose of calculating absorbed dose to humans from /sup 167/Tm-citrate, the whole-body retention studies using 5 rats were carried out. Up to 40 days following intravenous injection of /sup 167/Tm-citrate, the whole-body counts were monitored with an animal counter. The whole-body retention curve was obtained with three exponential components. Namely, the 26% of the injected /sup 167/Tm-citrate had a biological half-time of 3.4 hours, 12.5% had a biological half-time of 99 hours and 61.5% had a biological half-time of 106 days. These results indicate, that three components consist of the rapid clearance from the kidneys, the retention in the liver and other soft tissues with relatively long half-time and the retention in the bones with long half-time. Based on these biological data and the MIRD Committee method, the average dose estimates to the bone and whole-body from intravenous administration of 1 mCi /sup 167/Tm-citrate were 7.08 rads and 1.28 rads, respectively.

  9. Effect of chronic administration of sildenafil citrate (Viagra) on the histology of the retina and optic nerve of adult male rat.

    Science.gov (United States)

    Eltony, Sohair A; Abdelhameed, Sally Y

    2017-04-01

    Abnormal vision has been reported by 3% of patients treated with sildenafil citrate (Viagra). Although many men use Viagra for an extended period for treatment of erectile dysfunction, the implications of the long term-daily use of it on the retina and optic nerve are unclear. To investigate the effect of chronic daily use of sildenafil citrate in a dose equivalent to men preferred therapeutic dose on the histology of the retina and optic nerve of adult male rat. Eighteen adult male Wistar rats were equally divided into three groups. Group I: control. Group II: treated with sildenafil citrate orally (10mg/kg/day) for 8 weeks. Group III (withdrawal): treated as group II and then left for 4 weeks without treatment. Specimens from the retina and optic nerve were processed for light and electron microscopy. In sildenafil citrate treated group, the retina and optic nerve revealed vacuolations and congested blood capillaries with apoptotic endothelial and pericytic cells, and thickened basal lamina. Caspase-3 (apoptotic marker) and CD31 (endothelial marker) expression increased. Glial cells revealed morphological changes: Müller cells lost their processes, activated microglia, astrocytic clasmatodendrosis, degenerated oligodendrocytes surrounded by disintegrated myelin sheathes of the optic nerve fibers. The retina and optic nerve of the withdrawal group revealed less vacuolations and congestion, and partial recovery of the glial cells. Chronic treatment with sildenafil citrate (Viagra) caused toxic effect on the structure of the retina and optic nerve of the rat. Partial recovery was observed after drug withdrawal. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Is it safe to prescribe clomiphene citrate without ultrasound monitoring facilities?

    LENUS (Irish Health Repository)

    Coughlan, C

    2010-05-01

    The majority of triplet and higher order multiple pregnancies now result from ovulation induction\\/superovulation rather than in vitro fertilisation. However, clomiphene citrate is still widely prescribed by gynaecologists and general practitioners who do not have access to ultrasound monitoring. The objective of our study was to determine the prevalence of multifollicular development with different doses of clomiphene citrate. A retrospective review of transvaginal ultrasound monitoring of 425 cycles in 182 women receiving clomiphene citrate from January 2002 to December 2003, was studied. Three or more follicles of >or= 14 mm were identified in 58 cycles (14%). Patients received 50 mg of clomiphene citrate in 52 of these 58 cycles and 25 mg in the remaining six. One patient was noted to have developed five follicles and 10 patients developed four follicles. One patient developed six follicles, despite receiving only 25 mg clomiphene citrate daily. It was concluded that a significant number of women (14%) developed three or more follicles, despite receiving low doses of clomiphene citrate.

  11. Pathogenic mutations of the human mitochondrial citrate carrier SLC25A1 lead to impaired citrate export required for lipid, dolichol, ubiquinone and sterol synthesis.

    Science.gov (United States)

    Majd, Homa; King, Martin S; Smith, Anthony C; Kunji, Edmund R S

    2018-01-01

    Missense mutations of the human mitochondrial citrate carrier, encoded by the SLC25A1 gene, lead to an autosomal recessive neurometabolic disorder characterised by neonatal-onset encephalopathy with severe muscular weakness, intractable seizures, respiratory distress, and lack of psychomotor development, often resulting in early death. Here, we have measured the effect of all twelve known pathogenic mutations on the transport activity. The results show that nine mutations abolish transport of citrate completely, whereas the other three reduce the transport rate by >70%, indicating that impaired citrate transport is the most likely primary cause of the disease. Some mutations may be detrimental to the structure of the carrier, whereas others may impair key functional elements, such as the substrate binding site and the salt bridge network on the matrix side of the carrier. To understand the consequences of impaired citrate transport on metabolism, the substrate specificity was also determined, showing that the human citrate carrier predominantly transports citrate, isocitrate, cis-aconitate, phosphoenolpyruvate and malate. Although D-2- and L-2 hydroxyglutaric aciduria is a metabolic hallmark of the disease, it is unlikely that the citrate carrier plays a significant role in the removal of hydroxyglutarate from the cytosol for oxidation to oxoglutarate in the mitochondrial matrix. In contrast, computer simulations of central metabolism predict that the export of citrate from the mitochondrion cannot be fully compensated by other pathways, restricting the cytosolic production of acetyl-CoA that is required for the synthesis of lipids, sterols, dolichols and ubiquinone, which in turn explains the severe disease phenotypes. Copyright © 2017. Published by Elsevier B.V.

  12. Effect of Fe substitution on multiferroic hexagonal YMnO3

    International Nuclear Information System (INIS)

    Zaghrioui, M.; Greneche, J.M.; Autret-Lambert, C.; Gervais, M.

    2011-01-01

    Polycrystalline YMn 1-x Fe x O 3 (x=0.02-0.20) powders were synthesized by means of modified citrate method. Powder X-ray diffraction gives evidence that all the samples are single phase and exhibit hexagonal structure with P6 3 cm space group as observed for YMnO 3 . The solubility limit of Fe was determined as about 6 wt.%. Cell parameter values were found to increase with Fe content, since Fe 3+ and Mn 3+ have the same ionic radii. This can be attributed to the increase of the tilting of MnO 5 bipyramid and the buckling of Y atoms. In addition, 57 Fe Moessbauer spectrometry provides evidence of two Fe 3+ sites attributed to two different nearest atomic neighbours. Magnetic properties reveal a paramagnetic-to-antiferromagnetic transition, a possible increase of the magnetic anisotropy, and a competition between ferromagnetic and antiferromagnetic interactions. - Research highlights: → The increase of the tilting of MnO 5 bipyramid and the buckling of Y atoms leads to the increase of cell parameter in YMn 1-x Fe x O 3 . → 57 Fe Moessbauer spectrometry provides evidence of two Fe 3+ sites.

  13. Mössbauer spectroscopy of reduced forms of a Fe-tetraphenylporphyrine complex

    Directory of Open Access Journals (Sweden)

    Kaczmarzyk Tomasz

    2015-03-01

    Full Text Available Molecular and electronic structure changes during successive reduction of a Fe-tetraphenylporphyrin chloride [Fe(III(TPP:Cl] complex are reported on the basis of Mössbauer spectroscopy and DFT calculations. It is established that the attachment of additional electrons to a neutral Fe(III(TPP:Cl molecule leads to significant shortening of Fe-N distances at the first stage of the reduction Fe(III(TPP:Cl → Fe(II(TPP and lengthening of these bonds at the second stage Fe(II(TPP → Fe(I(TPP. Changes of other bond lengths of the porphyrin ring also appear but in less degree. Interaction of Fe(II and Fe(I(TPP with tetrahydrofuran (THF solvent is considered. Electron configuration of Fe(II(TPP corresponds to intermediate-spin (S = 1 state and in the case of Fe(I(TPP low-spin state (S = ½ is observed. Electron density distribution in Fe(II- and Fe(I(TPP complexes, in association with Mössbauer data, is analyzed. Good correlation between experimental and theoretical results was obtained.

  14. Citrate-Induced Nanocubes: A Re-Examination of the Role of Citrate as a Shape-Directing Capping Agent for Ag-Based Nanostructures.

    Science.gov (United States)

    Hajfathalian, Maryam; Gilroy, Kyle D; Hughes, Robert A; Neretina, Svetlana

    2016-07-01

    Seed-mediated syntheses utilizing facet-selective surface passivation provide the necessary chemical controls to direct noble metal nanostructure formation to a predetermined geometry. The foremost protocol for the synthesis of (111)-faceted Ag octahedra involves the reduction of metal ions onto pre-existing seeds in the presence of citrate and ascorbic acid. It is generally accepted that the capping of (111) facets with citrate dictates the shape while ascorbic acid acts solely as the reducing agent. Herein, a citrate-based synthesis is demonstrated in which the presence or absence of ascorbic acid is the shape-determining factor. Reactions are carried out in which Ag(+) ions are reduced onto substrate-immobilized Ag, Au, Pd, and Pt seeds. Syntheses lacking ascorbic acid, in which citrate acts as both the capping and the reducing agent, result in a robust nanocube growth mode able to withstand wide variations in the concentration of reactants, reaction rates, seed material, seed orientation and faceting, pH, and substrate material. If, however, ascorbic acid is included in these syntheses, then the growth mode reverts to one that advances the octahedral geometry. The implication of these results is that citrate, or one of its oxidation products, selectively caps (100) facets, but where this capability is compromised by ascorbic acid. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Improving Hybrid III injury assessment in steering wheel rim to chest impacts using responses from finite element Hybrid III and human body model.

    Science.gov (United States)

    Holmqvist, Kristian; Davidsson, Johan; Mendoza-Vazquez, Manuel; Rundberget, Peter; Svensson, Mats Y; Thorn, Stefan; Törnvall, Fredrik

    2014-01-01

    The main aim of this study was to improve the quality of injury risk assessments in steering wheel rim to chest impacts when using the Hybrid III crash test dummy in frontal heavy goods vehicle (HGV) collision tests. Correction factors for chest injury criteria were calculated as the model chest injury parameter ratios between finite element (FE) Hybrid III, evaluated in relevant load cases, and the Total Human Model for Safety (THUMS). This is proposed to be used to compensate Hybrid III measurements in crash tests where steering wheel rim to chest impacts occur. The study was conducted in an FE environment using an FE-Hybrid III model and the THUMS. Two impactor shapes were used, a circular hub and a long, thin horizontal bar. Chest impacts at velocities ranging from 3.0 to 6.0 m/s were simulated at 3 impact height levels. A ratio between FE-Hybrid III and THUMS chest injury parameters, maximum chest compression C max, and maximum viscous criterion VC max, were calculated for the different chest impact conditions to form a set of correction factors. The definition of the correction factor is based on the assumption that the response from a circular hub impact to the middle of the chest is well characterized and that injury risk measures are independent of impact height. The current limits for these chest injury criteria were used as a basis to develop correction factors that compensate for the limitations in biofidelity of the Hybrid III in steering wheel rim to chest impacts. The hub and bar impactors produced considerably higher C max and VC max responses in the THUMS compared to the FE-Hybrid III. The correction factor for the responses of the FE-Hybrid III showed that the criteria responses for the bar impactor were consistently overestimated. Ratios based on Hybrid III and THUMS responses provided correction factors for the Hybrid III responses ranging from 0.84 to 0.93. These factors can be used to estimate C max and VC max values when the Hybrid III is

  16. Effect of citrate on Aspergillus niger phytase adsorption and catalytic activity in soil

    Science.gov (United States)

    Mezeli, Malika; Menezes-Blackburn, Daniel; Zhang, Hao; Giles, Courtney; George, Timothy; Shand, Charlie; Lumsdon, David; Cooper, Patricia; Wendler, Renate; Brown, Lawrie; Stutter, Marc; Blackwell, Martin; Darch, Tegan; Wearing, Catherine; Haygarth, Philip

    2015-04-01

    .5 when compared to the free enzymes or in soil solution. The effect of ionic strength on enzyme activity was studied by increasing NaCl concentration on the activity buffer. A significant loss of activity was seen at ionic strengths over 0.6 M but enzymes in soil solution showed increased loss of activity on initial increase in ionic strength. No significant effect of citrate on phytase catalytic efficiency was observed towards free, adsorbed and precipitated (Al, Fe, Ca) phytate, except for the free phytase towards adsorbed phytase which showed a ~160% increase in P release with the addition of citric acid. This data suggest that citrate addition has no impact on the adsorption or catalytic activity of phytase in soil solution or that immobilised on soil particles, suggesting that its impact is associated with the availability of the substrate rather than effects on the enzyme per se. The ionic strength of soil solution does, however, have an impact on phytase activity suggesting that both wetting/drying cycles and fertilisation will have discrete impacts on the activity of phytases once released to soil and thus their ability to make organic P available for uptake by plants and microbes.

  17. Purification of Anthocyanins with o-Dihydroxy Arrangement by Sorption in Cationic Resins Charged with Fe(III

    Directory of Open Access Journals (Sweden)

    Araceli Castañeda-Ovando

    2014-01-01

    Full Text Available In the present work, a new purification method of anthocyanins with o-dihydroxy arrangement is proposed. This method is based on a ligand-exchange mechanism, using a cationic exchange resin loaded with metallic ions in order to increase the affinity of the resin to the anthocyanin(s with o-dihydroxy arrangement. This method was used to purify the main anthocyanin (cyanidin-3-glucoside; Cy-3-glc from the anthocyanic methanolic extract of blue corn. The best sorption result was using Fe(III in its ion form. The purification procedure begins with the formation of a metal-anthocyanin complex (Cy-3-glc-Fe which was optimal at pH 5, followed by a NaOH 0.1 M elution process in order to eliminate anthocyanins without o-dihydroxy arrangement, sugars, and organic acids. Finally, the pure anthocyanin is obtained by adding HCl 0.1 M which breaks the metal-anthocyanin complex.

  18. Citrate Anticoagulation during Continuous Renal Replacement Therapy.

    Science.gov (United States)

    Ricci, Davide; Panicali, Laura; Facchini, Maria Grazia; Mancini, Elena

    2017-01-01

    During extracorporeal dialysis, some anticoagulation strategy is necessary to prevent the coagulation of blood. Heparin has historically been used as an anticoagulant because of its efficacy combined with low cost. However, a variable incidence of hemorrhagic complications (5-30%) has been documented in patients undergoing continuous renal replacement therapy (CRRT) with heparin as an anticoagulant. Citrate has anticoagulation properties secondary to its ability to chelate calcium, which is necessary for the coagulation cascade. Citrate may thus be used in a regional anticoagulation (RCA), limited to the extracorporeal circuit of CRRT, to avoid systemic anticoagulation. Recent meta-analysis confirmed the advantage of RCA over heparin in terms of incidence of bleeding during CRRT. Moreover, an increase in filter lifespan is documented, with a secondary advantage in reaching the prescribed dialysis dose. In our experience, we could confirm this positive effect. In fact, with a progressive increase in the proportion of CRRT with citrate as RCA, we obtained a reduction in the number of filters used for every 72 h of treatment (from 2.4 in 2011 to 1.3 in 2015), and most importantly, a reduction in the difference between the prescribed and delivered dialysis doses (from 22 to 7%). Citrate has an intense effect on the acid-base balance as well, if fully metabolized through the Krebs cycle, due to the production of bicarbonate. Even more severely ill patients, such as those with liver dysfunction, may be treated with RCA without severe complications, because modern machines for CRRT are equipped with simple systems that are able to manage the citrate infusion and control the calcium levels, with minimal risks of metabolic derangements. © 2017 S. Karger AG, Basel.

  19. Preparation and Eh-pH diagrams of Fe(II)-Fe(III) green rust compounds; hyperfine interaction characteristics and stoichiometry of hydroxy-chloride, -sulphate and -carbonate

    International Nuclear Information System (INIS)

    Genin, J.-M.R.; Refait, Ph.; Simon, L.; Drissi, S.H.

    1998-01-01

    Fe(II)-Fe(III) hydroxy-chloride, -sulphate and -carbonate were prepared by oxidation of a ferrous hydroxide precipitate in anion-containing aqueous solutions. The compounds are characterized by monitoring the redox potential E h and the pH of stochiometric suspension vs time with the appropriate concentration ratios. X-ray diffraction allows us to characterize the crystal structure by distinguishing 'green rust one' (GR1) from 'green rust two' (GR2). Since green rusts (GRs) are of a pyroaurite-sjoegrenite-like structure, i.e., consisting of intercalated foreign anions and water molecules in the interlayers between the brucite-like layers of Fe(OH) 2 , their chemical formulae can be determined from the Moessbauer spectra. Three quadrupole doublets are observed: D 1 and D 2 correspond to a ferrous state with isomershift IS of about 1.27 mm s -1 and quadrupole splittings QS of about 2.85 and 2.60 mm s -1 , respectively, whereas D 3 corresponds to a ferric state with IS and QS of about 0.4 mm s -1 . The hyperfine parameters of these doublets are similar from one green rust to another but their intensity ratios vary considerably. Finally, E h and pH equilibrium diagrams of the Fe species in the presence of chloride, sulphate and carbonate anions contained within the water solution are drawn and the thermodynamic conditions of existence and degrees of oxidation of green rusts are discussed

  20. Preparation, characterization and visible-light-driven photocatalytic activity of a novel Fe(III) porphyrin-sensitized TiO{sub 2} nanotube photocatalyst

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Meng [National Engineering Lab of Textile Fiber Materials & Processing Technology, Zhejiang Sci-Tech University, Hangzhou 310018 (China); Wan, Junmin, E-mail: wwjm2001@126.com [National Engineering Lab of Textile Fiber Materials & Processing Technology, Zhejiang Sci-Tech University, Hangzhou 310018 (China); State Key Laboratory of advanced Textiles Materials and Manufacture Technology, MOE, Zhejiang Sci-Tech University, Hangzhou 310018 (China); Hu, Zhiwen; Peng, Zhiqin; Wang, Bing [National Engineering Lab of Textile Fiber Materials & Processing Technology, Zhejiang Sci-Tech University, Hangzhou 310018 (China); Wang, Huigang [State Key Laboratory of advanced Textiles Materials and Manufacture Technology, MOE, Zhejiang Sci-Tech University, Hangzhou 310018 (China)

    2017-01-01

    Highlights: • FeTCPP-TNT photocatalysts are synthesized. • FeTCPP and tube-like structure are helpful to induce interfacial charge transfer at surface junction. • FeTCPP and tube-like structure are favorable for enhancing photocatalytic activity. • The photocatalytic mechanism of FeTCPP-TNT is proposed. • The photocatalyst are proven to be effective and chemically-stable catalysts. - Abstract: Iron(III) meso-tetra(4-carboxyphenyl) porphyrin (FeTCPP) loaded on the surface of TiO{sub 2} nanotubes (TNTs) has been successfully prepared through improved hydrothermal and heating reflux process. The new photocatalyst has been characterized and analyzed by TEM/EDS, BET, XRD, FT-IR, DRS, PL, XPS and EPR. The photocatalytic activity of FeTCPP/TNT nanocomposite was evaluated by the photodegradation of MB under visible light irradiation. The degradation results showed a purification of more than 90% MB in simulating wastewater, and confirmed that the prepared FeTCPP/TNT nanocomposite has acquired superior photocatalytic activitiy. The 6 times cycled results suggested the great stability of the photocatalyst. These results confirmed the FeTCPP played an important role in capturing photons and expanding the absorption wavelength to the visible light region, and the FeTCPP/TNT photocatalyst is also beneficial for the electron transfer and long-distance transmission, and could efficiently increase the separation of the electron-hole pairs, and accelerate the decomposition of organic pollutants. In addition, nano-sized structures can increase adsorption capability.

  1. Detoxification of Pesticide-Containing Wastewater with FeIII, Activated Carbon and Fenton Reagent and Its Control Using Three Standardized Bacterial Inhibition Tests

    Directory of Open Access Journals (Sweden)

    Eduard Rott

    2017-12-01

    Full Text Available Discharge of toxic industrial wastewaters into biological wastewater treatment plants may result in inhibition of activated sludge bacteria (ASB. In order to find an appropriate method of detoxification, the wastewater of a pesticide-processing plant in Vietnam was treated with three different methods (FeIII, powdered activated carbon (PAC, Fenton (FeII/H2O2 analyzing the detoxification effect with the nitrification inhibition test (NIT, respiration inhibition test (RIT and luminescent bacteria test (LBT. The heterotrophic ASB were much more resistant to the wastewater than the autotrophic nitrificants. The NIT turned out to be more suitable than the RIT since the NIT was less time-consuming and more reliable. In addition, the marine Aliivibrio fischeri were more sensitive than the nitrificants indicating that a lack of inhibition in the very practical and time-efficient LBT correlates with a lack of nitrification inhibition. With 95%, the Fenton method showed the highest efficiency regarding the chemical oxygen demand (COD removal. Although similar COD removal (60–65% was found for both the FeIII and the PAC method, the inhibitory effect of the wastewater was reduced much more strongly with PAC. Both the NIT and the LBT showed that the PAC and Fenton methods led to a similar reduction in the inhibitory effect.

  2. Nanocrystalline Axially Bridged Iron Phthalocyanine Polymeric Conductor: (μ-Thiocyanato(phthalocyaninatoiron(III

    Directory of Open Access Journals (Sweden)

    Eiza Shimizu

    2016-01-01

    Full Text Available Skewered Iron(III phthalocyanine conducting polymer can be constructed with the utilization of axial thiocyanato ligands ((μ-thiocyanato(phthalocyaninatoiron(III; (FeIII(Pc(SCNn thereby creating additional avenues for electron transport through a linear SCN bridge, apart from the intermolecular π-π orbital overlap between the Pc molecules. In this paper, we report on the conversion of bulk FeIII(Pc(SCNn polymeric organic conductor into crystalline nanostructures through horizontal vapor phase growth process. The needle-like nanostructures are deemed to provide more ordered and, thus, more π-π interactive interskewer FeIII(Pc(SCNn polymer orientation, resulting in a twofold increase of its electrical conductivity per materials density unit.

  3. Crystal structure of a sodium, zinc and iron(III-based non-stoichiometric phosphate with an alluaudite-like structure: Na1.67Zn1.67Fe1.33(PO43

    Directory of Open Access Journals (Sweden)

    Jamal Khmiyas

    2015-06-01

    Full Text Available The new title compound, disodium dizinc iron(III tris(phosphate, Na1.67Zn1.67Fe1.33(PO43, which belongs to the alluaudite family, has been synthesized by solid-state reactions. In this structure, all atoms are in general positions except for four, which are located on special positions of the C2/c space group. This structure is characterized by cation substitutional disorder at two sites, one situated on the special position 4e (2 and the other on the general position 8f. The 4e site is partially occupied by Na+ [0.332 (3], whereas the 8f site is entirely filled by a mixture of Fe and Zn. The full-occupancy sodium and zinc atoms are located at the Wyckoff positions on the inversion center 4a (-1 and on the twofold rotation axis 4e, respectively. Refinement of the occupancy ratios, bond-valence analysis and the electrical neutrality requirement of the structure lead to the given composition for the title compound. The three-dimensional framework of this structure consists of kinked chains of edge-sharing octahedra stacked parallel to [10-1]. The chains are formed by a succession of trimers based on [ZnO6] octahedra and the mixed-cation FeIII/ZnII [(Fe/ZnO6] octahedra [FeIII:ZnIII ratio 0.668 (3/0.332 (3]. Continuous chains are held together by PO4 phosphate groups, forming polyhedral sheets perpendicular to [010]. The stacked sheets delimit two types of tunnels parallel to the c axis in which the sodium cations are located. Each Na+ cation is coordinated by eight O atoms. The disorder of Na in the tunnel might presage ionic mobility for this material.

  4. Risks and benefits of citrate anticoagulation for continuous renal replacement therapy.

    Science.gov (United States)

    Shum, H P; Yan, W W; Chan, T M

    2015-04-01

    Heparin, despite its significant side-effects, is the most commonly used anticoagulant for continuous renal replacement therapy in critical care setting. In recent years, citrate has gained much popularity by improving continuous renal replacement therapy circuit survival and decreasing blood transfusion requirements. However, its complex metabolic consequences warrant modification in the design of the citrate-based continuous renal replacement therapy protocol. With thorough understanding of the therapeutic mechanism of citrate, a simple and practicable protocol can be devised. Citrate-based continuous renal replacement therapy can be safely and widely used in the clinical setting with appropriate clinical staff training.

  5. Alkali replacement raises urinary citrate excretion in patients with topiramate-induced hypocitraturia.

    Science.gov (United States)

    Jhagroo, R Allan; Wertheim, Margaret L; Penniston, Kristina L

    2016-01-01

    The aims of this study were to assess (1) the magnitude and temporality of decreased urinary citrate excretion in patients just starting topiramate and (2) the effect of alkali replacement on topiramate-induced hypocitraturia. Study 1 was a prospective, non-intervention study in which patients starting topiramate for headache remediation provided pre- and post-topiramate 24 h urine collections for measurement of urine citrate. Study 2 was a clinical comparative effectiveness study in which patients reporting to our stone clinic for kidney stones and who were treated with topiramate were prescribed alkali therapy. Pre- and post-alkali 24 h urinary citrate excretion was compared. Data for 12 and 22 patients (studies 1 and 2 respectively) were evaluated. After starting topiramate, urinary citrate excretion dropped significantly by 30 days (P = 0.016) and 62% of patients had hypocitraturia (citrate alkali, urine citrate increased in stone-forming patients on topiramate (198 ± 120 to 408 ± 274 mg day(-1) ; P = 0.042 for difference). 85% of patients were hypocitraturic on topiramate alone vs. 40% after adding alkali. The increase in urinary citrate was greater in patients provided ≥ 90 mEq potassium citrate. Our study is the first to provide clinical evidence that alkali therapy can raise urinary citrate excretion in patients who form kidney stones while being treated with topiramate. Clinicians should consider alkali therapy for reducing the kidney stone risk of patients benefitting from topiramate treatment for migraine headaches or other conditions. © 2015 The British Pharmacological Society.

  6. Sildenafil citrate (Viagra) enhances vasodilatation in fetal growth restriction.

    Science.gov (United States)

    Wareing, Mark; Myers, Jenny E; O'Hara, Maureen; Baker, Philip N

    2005-05-01

    Fetal growth restriction (FGR) affects up to 8% of all pregnancies and has massive short-term (increased fetal morbidity and mortality) and long-term (increased incidence of cardiovascular disease in adulthood) health implications. Doppler waveform analysis of pregnancies complicated by FGR suggests compromised uteroplacental circulation and placental hypoperfusion. Our aim was to determine whether myometrial small artery function was aberrant in FGR and to assess whether sildenafil citrate could improve vasodilatation in FGR pregnancies. Small arteries dissected from myometrial biopsies obtained at cesarean section from normal pregnant women (n = 27) or women whose pregnancies were complicated by FGR (n = 12) were mounted on wire myographs. Vessels were constricted (with arginine vasopressin or U46619) and relaxed (with bradykinin) before and after incubation with a phosphodiesterase-5 inhibitor, sildenafil citrate. We demonstrated increased myometrial small artery vasoconstriction and decreased endothelium-dependent vasodilatation in vessels from women whose pregnancies were complicated by FGR. Sildenafil citrate significantly reduced vasoconstriction and significantly improved relaxation of FGR small arteries. We conclude that sildenafil citrate improves endothelial function of myometrial vessels from women whose pregnancies are complicated by intrauterine growth restriction. Sildenafil citrate may offer a potential therapeutic strategy to improve uteroplacental blood flow in FGR pregnancies.

  7. Study of Np speciation in citrate medium

    Energy Technology Data Exchange (ETDEWEB)

    Bonin, L.; Den Auwer, C.; Ansoborlo, E.; Moisy, P. [CEA Valrho - DEN/DRCP/SCPS, Bagnols sur Ceze (France); Cote, G. [ENSP - LECA, UMR 7575, Paris (France)

    2007-07-01

    In the framework of the French Environmental Nuclear Toxicology program, additional experiments related to the decorporation of actinides are planned. Decorporation is the removal or release from target organs (bones, liver, kidney..), tissues or cells of radioactive material previously incorporated in them, using chelating agents or other administrated pharmaceutical agents. The contradictory data on the neptunium complexation behaviour within blood and its transfer to target organs, as well as the inefficiency of therapeutic treatments, led us to study the complexation of this element with biological constituents. Within this purpose, the in vitro behaviour of Np(IV) and Np(V) in simple media simulating biological fluids was studied. This study was more specifically focused on the behaviour of neptunium with citrate ion, which is an essential component in a number of metalloenzyme active sites. In order to determine the speciation of this system, spectrophotometry was more particularly used. Concerning the complexation phenomenon, the existence of several complexes of Np(V) with various acido-basic forms of the citrate anion was observed; regarding Np(IV), complexes with Cit{sup 3-} have been observed. From the quantitative study of these equilibria, the values of the absolute constants for the complexation of Np(IV) and Np(V) with citrate were determined. Concerning the stability of neptunium towards oxydo-reduction, it was confirmed that Np(VI) was very quickly reduced to Np(V) by the citrate anions, whereas Np(IV) was stable. In the case of Np(V), it was observed that, depending on the pH and the citrate concentration, Np(V) was unstable and was reduced to Np(IV). The E-pH diagrams, constructed using the stability constants determined in this study, showed that this instability was due to the Np(V) disproportionation. (orig.)

  8. Comparative Study of Catalytic Oxidation of Ethanol to Acetaldehyde Using Fe(III Dispersed on Sb2O5 Grafted on SiO2 and on Untreated SiO2 Surfaces

    Directory of Open Access Journals (Sweden)

    Benvenutti Edilson V.

    1998-01-01

    Full Text Available Fe(III was supported on Sb(V oxide grafted on the silica gel surface and directly on the silica gel surface using ion-exchange and impregnation processes producing Fe/Sb/SiO2 and Fe/SiO2, respectively. The catalytic conversion of ethanol to acetaldehyde was much more efficient using Fe/Sb/SiO2 than Fe/SiO2 as catalyst. This higher efficiency of the former catalyst takes into account two aspects: a the new phase FeSbO4 formed when Fe/Sb/SiO2 is heat treated and, b it is higher dispersion on the matrix.

  9. Influence of Halogen Substituents on the Catalytic Oxidation of 2,4,6-Halogenated Phenols by Fe(III-Tetrakis(p-hydroxyphenyl porphyrins and Potassium Monopersulfate

    Directory of Open Access Journals (Sweden)

    Seiya Nagao

    2011-12-01

    Full Text Available The influence of halogen substituents on the catalytic oxidation of 2,4,6-trihalogenated phenols (TrXPs by iron(III-porphyrin/KHSO5 catalytic systems was investigated. Iron(III-5,10,15,20-tetrakis(p-hydroxyphenylporphyrin (FeTHP and its supported variants were employed, where the supported catalysts were synthesized by introducing FeTHP into hydroquinone-derived humic acids via formaldehyde poly-condensation. F (TrFP, Cl (TrCP, Br (TrBP and I (TrIP were examined as halogen substituents for TrXPs. Although the supported catalysts significantly enhanced the degradation and dehalogenation of TrFP and TrCP, the oxidation of TrBP and TrIP was not enhanced, compared to the FeTHP catalytic system. These results indicate that the degree of oxidation of TrXPs is strongly dependent on the types of halogen substituent. The order of dehalogenation levels for halogen substituents in TrXPs was F > Cl > Br > I, consistent with their order of electronegativity. The electronegativity of a halogen substituent affects the nucleophilicity of the carbon to which it is attached. The levels of oxidation products in the reaction mixtures were analyzed by GC/MS after extraction with n-hexane. The most abundant dimer product from TrFP via 2,6-difluoroquinone is consistent with a scenario where TrXP, with a more electronegative halogen substituent, is readily oxidized, while less electronegative halogen substituents are oxidized less readily by iron(III-porphyrin/KHSO5 catalytic systems.

  10. 2 : 2 Fe(III): ligand and "adamantane core" 4 : 2 Fe(III): ligand (hydr)oxo complexes of an acyclic ditopic ligand

    DEFF Research Database (Denmark)

    Ghiladi, Morten; Larsen, Frank B.; McKenzie, Christine J.

    2005-01-01

    A bis-hydroxo-bridged diiron(III) complex and a bis-mu-oxo-bis-mu-hydroxo-bridged tetrairon( III) complex are isolated from the reaction of 2,6-bis((N, N'-bis-(2-picolyl) amino) methyl)-4-tert-butylphenol (Hbpbp) with iron perchlorate in acidic and neutral solutions respectively. The X-ray struct......A bis-hydroxo-bridged diiron(III) complex and a bis-mu-oxo-bis-mu-hydroxo-bridged tetrairon( III) complex are isolated from the reaction of 2,6-bis((N, N'-bis-(2-picolyl) amino) methyl)-4-tert-butylphenol (Hbpbp) with iron perchlorate in acidic and neutral solutions respectively. The X...

  11. Mechanism of thermal decomposition of K{sub 2}FeO{sub 4} and BaFeO{sub 4}: A review

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Virender K., E-mail: vsharma@sph.tamhsc.edu [Texas A& M University, Department of Environmental and Occupational Health, School of Public Health (United States); Machala, Libor [Palacky University, Regional Centre of Advanced Technologies and Materials, Departments of Experimental Physics and Physical Chemistry, Faculty of Science (Czech Republic)

    2016-12-15

    This paper presents thermal decomposition of potassium ferrate(VI) (K{sub 2}FeO{sub 4}) and barium ferrate(VI) (BaFeO{sub 4}) in air and nitrogen atmosphere. Mössbauer spectroscopy and nuclear forward scattering (NFS) synchrotron radiation approaches are reviewed to advance understanding of electron-transfer processes involved in reduction of ferrate(VI) to Fe(III) phases. Direct evidences of Fe {sup V} and Fe {sup IV} as intermediate iron species using the applied techniques are given. Thermal decomposition of K{sub 2}FeO{sub 4} involved Fe {sup V}, Fe {sup IV}, and K{sub 3}FeO{sub 3} as intermediate species while BaFeO{sub 3} (i.e. Fe {sup IV}) was the only intermediate species during the decomposition of BaFeO{sub 4}. Nature of ferrite species, formed as final Fe(III) species, of thermal decomposition of K{sub 2}FeO{sub 4} and BaFeO{sub 4} under different conditions are evaluated. Steps of the mechanisms of thermal decomposition of ferrate(VI), which reasonably explained experimental observations of applied approaches in conjunction with thermal and surface techniques, are summarized.

  12. Preservation of water samples for arsenic(III/V) determinations: An evaluation of the literature and new analytical results

    Science.gov (United States)

    McCleskey, R. Blaine; Nordstrom, D. Kirk; Maest, A.S.

    2004-01-01

    Published literature on preservation procedures for stabilizing aqueous inorganic As(III/V) redox species contains discrepancies. This study critically evaluates published reports on As redox preservation and explains discrepancies in the literature. Synthetic laboratory preservation experiments and time stability experiments were conducted for natural water samples from several field sites. Any field collection procedure that filters out microorganisms, adds a reagent that prevents dissolved Fe and Mn oxidation and precipitation, and isolates the sample from solar radiation will preserve the As(III/V) ratio. Reagents that prevent Fe and Mn oxidation and precipitation include HCl, H 2SO4, and EDTA, although extremely high concentrations of EDTA are necessary for some water samples high in Fe. Photo-catalyzed Fe(III) reduction causes As(III) oxidation; however, storing the sample in the dark prevents photochemical reactions. Furthermore, the presence of Fe(II) or SO 4 inhibits the oxidation of As(III) by Fe(III) because of complexation reactions and competing reactions with free radicals. Consequently, fast abiotic As(III) oxidation reactions observed in the laboratory are not observed in natural water samples for one or more of the following reasons: (1) the As redox species have already stabilized, (2) most natural waters contain very low dissolved Fe(III) concentrations, (3) the As(III) oxidation caused by Fe(III) photoreduction is inhibited by Fe(II) or SO4.

  13. Preservation of water samples for arsenic(III/V) determinations: an evaluation of the literature and new analytical results

    International Nuclear Information System (INIS)

    McCleskey, R.Blaine; Nordstrom, D.Kirk; Maest, Ann S.

    2004-01-01

    Published literature on preservation procedures for stabilizing aqueous inorganic As(III/V) redox species contains discrepancies. This study critically evaluates published reports on As redox preservation and explains discrepancies in the literature. Synthetic laboratory preservation experiments and time stability experiments were conducted for natural water samples from several field sites. Any field collection procedure that filters out microorganisms, adds a reagent that prevents dissolved Fe and Mn oxidation and precipitation, and isolates the sample from solar radiation will preserve the As(III/V) ratio. Reagents that prevent Fe and Mn oxidation and precipitation include HCl, H 2 SO 4 , and EDTA, although extremely high concentrations of EDTA are necessary for some water samples high in Fe. Photo-catalyzed Fe(III) reduction causes As(III) oxidation; however, storing the sample in the dark prevents photochemical reactions. Furthermore, the presence of Fe(II) or SO 4 inhibits the oxidation of As(III) by Fe(III) because of complexation reactions and competing reactions with free radicals. Consequently, fast abiotic As(III) oxidation reactions observed in the laboratory are not observed in natural water samples for one or more of the following reasons: (1) the As redox species have already stabilized, (2) most natural waters contain very low dissolved Fe(III) concentrations, (3) the As(III) oxidation caused by Fe(III) photoreduction is inhibited by Fe(II) or SO 4

  14. Crystal structures and magnetic properties of iron (III)-based phosphates: Na4NiFe(PO4)3 and Na2Ni2Fe(PO4)3

    International Nuclear Information System (INIS)

    Essehli, Rachid; Bali, Brahim El; Benmokhtar, Said; Bouziane, Khalid; Manoun, Bouchaib; Abdalslam, Mouner Ahmed; Ehrenberg, Helmut

    2011-01-01

    Graphical abstract: A perspective view of the Na 2 Ni 2 Fe(PO 4 ) 3 structure along the [0 0 1] direction. Both compounds seem to exibit antiferromagnetic interactions between magnetic entities at low temperature. Display Omitted Research highlights: → Nasicon and Alluaudite compounds, Iron(III)-based phosphates, Crystal structures of Na 4 NiFe(PO 4 ) 3 and Na 2 Ni 2 Fe(PO 4 ) 3 . → Magnetism behaviours of Na 4 NiFe(PO 4 ) 3 and Na 2 Ni 2 Fe(PO 4 ) 3 . → Antiferromagnetism interactions. → Mossbauer spectroscopy. - Abstract: Crystal structures from two new phosphates Na 4 NiFe(PO 4 ) 3 (I) and Na 2 Ni 2 Fe(PO 4 ) 3 (II) have been determined by single crystal X-ray diffraction analysis. Compound (I) crystallizes in a rhombohedral system (S. G: R-3c, Z = 6, a = 8.7350(9) A, c = 21.643(4) A, R 1 = 0.041, wR 2 =0.120). Compound (II) crystallizes in a monoclinic system (S. G: C2/c, Z = 4, a = 11.729(7) A, b = 12.433(5) A, c = 6.431(2) A, β = 113.66(4) o , R 1 = 0.043, wR 2 =0.111). The three-dimensional structure of (I) is closely related to the Nasicon structural type, consisting of corner sharing [(Ni/Fe)O 6 ] octahedra and [PO 4 ] tetrahedra forming [NiFe(PO 4 ) 3 ] 4+ units which align in chains along the c-axis. The Na + cations fill up trigonal antiprismatic sites within these chains. The crystal structure of (II) belongs to the alluaudite type. Its open framework results from [Ni 2 O 10 ] units of edge-sharing [NiO 6 ] octahedra, which alternate with [FeO 6 ] octahedra that form infinite chains. Coordination of these chains yields two distinct tunnels in which site Na + . The magnetization data of compound (I) reveal antiferromagnetic (AFM) interactions by the onset of deviations from a Curie-Weiss behaviour at low temperature as confirmed by Moessbauer measurements performed at 4.2 K. The corresponding temperature dependence of the reciprocal susceptibility χ -1 follows a typical Curie-Weiss behaviour for T > 105 K. A canted AFM state is proposed for

  15. Factors to Enable Crystallization of Environmentally Stable Bioscorodite from Dilute As(III-Contaminated Waters

    Directory of Open Access Journals (Sweden)

    Masahito Tanaka

    2018-01-01

    Full Text Available Applicability of the bioscorodite method (use of the thermo-acidophilic Fe(II-oxidizing archaeon Acidianus brierleyi for arsenic (As oxidation and immobilization at 70 °C was tested for synthetic copper refinery wastewaters of a wide range of dilute initial As(III concentrations ([As(III]ini = 3.3–20 mM with varying initial [Fe(II]/[As(III] molar ratios ([Fe(II]ini/[As(III]ini = 0.8–6.0. Crystallization of scorodite (FeAsO4·2H2O tends to become increasingly challenging at more dilute As(III solutions. Optimization of conditions such as initial pH, seed feeding and initial [Fe(II]/[As(III] molar ratio was found critical in improving final As removal and product stability: Whilst setting the initial pH at 1.2 resulted in an immediate single-stage precipitation of crystalline bioscorodite, the initial pH 1.5 led to a two-stage As precipitation (generation of brown amorphous precursors followed by whitish crystalline bioscorodite particles with a greater final As removal. The formation process of bioscorodite precipitates differed significantly depending on the type of seed crystals fed (bio- versus chemical- scorodite seeds. Feeding the former was found effective not only in accelerating the reaction, but also in forming more recalcitrant bioscorodite products (0.59 mg/L; Toxicity Characteristic Leaching Procedure (TCLP test. Under such favorable conditions, 94–99% of As was successfully removed as crystalline bioscorodite at all dilute As(III concentrations tested by setting [Fe(II]ini/[As(III]ini at 1.4–2.0. Providing an excess Fe(II (closer to [Fe(II]ini/[As(III]ini = 2.0 was found beneficial to improve the final As removal (up to 98–99% especially from more dilute As(III solutions.

  16. Electrode reactions of iron oxide-hydroxide colloids.

    Science.gov (United States)

    Mahmoudi, Leila; Kissner, Reinhard

    2014-11-07

    Small-sized FeO(OH) colloids stabilised by sugars, commercially available for the clinical treatment of iron deficiency, show two waves during cathodic polarographic sweeps, or two current maxima with stationary electrodes, in neutral to slightly alkaline aqueous medium. Similar signals are observed with Fe(III) in alkaline media, pH > 12, containing citrate in excess. Voltammetric and polarographic responses reveal a strong influence of fast adsorption processes on gold and mercury. Visible spontaneous accumulation was also observed on platinum. The voltammetric signal at more positive potential is caused by Fe(III)→Fe(II) reduction, while the one at more negative potential has previously been assigned to Fe(II)→Fe(0) reduction. However, the involvement of adsorption phenomena leads us to the conclusion that the second cathodic current is caused again by Fe(III)→Fe(II), of species deeper inside the particles than those causing the first wave. This is further supported by X-ray photoelectron spectra obtained after FeO(OH) particle adsorption and reduction on a gold electrode surface. The same analysis suggests that sucrose stabilising the colloid is still bound to the adsorbed material, despite dilution and rinsing.

  17. Comparison of pregnancy rates in PCOS patients undergoing clomiphene citrate and IUI treatment with different leading follicular sizes.

    Science.gov (United States)

    Seckin, Berna; Pekcan, Meryem Kuru; Bostancı, Esra Isci; Inal, Hasan Ali; Cicek, Mahmut Nedim

    2016-04-01

    The objective of the study was to compare the pregnancy rates in PCOS patients undergoing clomiphene citrate (CC) and intrauterine insemination (IUI) treatment with different leading follicular sizes. A total of 358 infertile women with PCOS who underwent 563 clomiphene citrate and IUI treatment cycles were included in this prospective study. Treatment cycles were divided into three groups according to leading follicular size on the day of hCG administration: Group I: follicular size 17-18 mm (n = 177), Group II: 19-22 mm (n = 321), and Group III : >22 mm (n = 65). Pregnancy rates were evaluated. Treatment outcomes of the groups were further analyzed related to endometrial thickness measurement on the day of hCG. For this purpose, cycles were placed into three subgroups as follows: endometrial thickness 9 mm. There was no statistically significant difference in clinical pregnancy rate per cycle between the groups (8.5, 10, and 9.2 % for Group I, II, and III, respectively, p = 0.86). In further analyses related to endometrial thickness, no significant difference was also found in pregnancy rate among the groups. This results suggest that pregnancy rate is not related to leading follicle size on the day of hCG administration in PCOS patients treated with CC and IUI. In addition, pregnancy rate in women with different follicular sizes is not influenced by the endometrial thickness.

  18. Cs[FeSe{sub 2}], Cs{sub 3}[FeSe{sub 2}]{sub 2}, and Cs{sub 7}[Fe{sub 4}Se{sub 8}]. Missing links of known chalcogenido ferrate series

    Energy Technology Data Exchange (ETDEWEB)

    Stueble, Pirmin; Roehr, Caroline [Institut fuer Anorganische und Analytische Chemie, Universitaet Freiburg (Germany)

    2017-11-17

    The three cesium selenido ferrate title compounds with an Se:Fe ratio of 2:1 were synthesized from stoichiometric samples reacting elemental Cs either (A) with Fe and Se in a double-crucible setup (Cs[FeSe{sub 2}], Cs{sub 3}[FeSe{sub 2}]{sub 2}) or (B) with previously prepared FeSe{sub 2} (Cs{sub 3}[FeSe{sub 2}]{sub 2}, Cs{sub 7}[Fe{sub 4}S{sub 8}]) (T{sub max} = 800-1000 C). The pure Fe{sup III} ferrate Cs[FeSe{sub 2}] crystallizes in the Tl[FeSe{sub 2}] type [monoclinic, space group C2/m, a = 1392.95(10), b = 564.43(3), c = 737.44(6) pm, β = 119.163(5) , Z = 4, R{sub 1} = 0.0550]. It is thus not isotypic to all other alkali ferrates(III) A[FeS{sub 2}] and A[FeSe{sub 2}] containing chains of edge-sharing tetrahedra, but crystallizes in a t2 subgroup of the Immm structure of Cs[FeS{sub 2}]. The mixed-valent chain compound Cs{sub 3}[FeSe{sub 2}]{sub 2} is isotypic to its sulfido analogue [orthorhombic, space group Pnma, a = 777.88(6), b = 1151.02(6), c = 1341.61(7) pm, Z = 4, R{sub 1} = 0.0470]. In contrast to the isopunctal Na{sub 3}[FeSe{sub 2}]{sub 2} type K/Rb compounds the chains are only slightly corrugated. The monoclinic, likewise mixed-valent Fe{sup II/III} selenido ferrate Cs{sub 7}[Fe{sub 4}Se{sub 8}] [monoclinic, space group C2/c, a = 1953.79(10), b = 879.71(5), c = 1717.03(10) pm, β = 117.890(2) , Z = 4, R{sub 1} = 0.0816] is isostructural both to the cesium sulfido and tellurido compound. The structure contains oligomeric moieties of four edge sharing [FeSe{sub 4}] tetrahedra forming slightly distorted tetrahedral clusters [Fe{sub 4}Se{sub 8}]{sup 7-}, which are surrounded by a cube of 26 Cs cations. Based on a structure map, the crystal chemistry of the three title compounds is discussed together with all chain/cluster ferrates of the general series A{sub 1+x}[Fe{sup III}{sub 1-x}Fe{sup II}{sub x}Q{sub 2}] (x = 0-1; A = Na, K, Rb, Cs; Q = S, Se, Te). (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. Effect of magnetic field annealing on the magneto-elastic properties of nanocrystalline NiFe{sub 2}O{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Sowmya, N. Shara [Defence Metallurgical Research Laboratory, Kanchanbagh, Hyderabad 500 058 (India); National Institute of Technology, Warangal 506004 (India); Srinivas, A., E-mail: adirajs@gmail.com [Defence Metallurgical Research Laboratory, Kanchanbagh, Hyderabad 500 058 (India); Saravanan, P. [Defence Metallurgical Research Laboratory, Kanchanbagh, Hyderabad 500 058 (India); Reddy, K. Venu Gopal [National Institute of Technology, Warangal 506004 (India); Reddy, Monaji Vinitha; Das, Dibakar [School of Engineering Science and Technology, University of Hyderabad, Hyderabad 500 046 (India); Kamat, S.V. [Defence Metallurgical Research Laboratory, Kanchanbagh, Hyderabad 500 058 (India)

    2017-08-15

    Highlights: • NiFe{sub 2}O{sub 4} was processed by citrate-gel method followed by magnetic-field annealing. • Field-annealing resulted in induced magneto-crystalline anisotropy. • M{sub s} of 41 emu/g and λ{sub s} of −40 ppm at 2 kOe was achieved after field-annealing. • Maximum strain sensitivity ‘q’ of −3.3 ppm/Oe was obtained at 5 Oe. • Schematic was proposed and explained using atomic-pair ordering theory. - Abstract: The effect of magnetic-field annealing on the strain sensitivity (q) and saturation magnetostriction (λ{sub s}) of NiFe{sub 2}O{sub 4} nanoparticles synthesized by citrate-gel method was investigated. The use of field-annealing resulted in improved magnetoelastic properties at the expense of coercivity. A maximum λ{sub s} of −40 ppm at 2 kOe, associated with q value of −3.3 ppm/Oe at 5 Oe was achieved in the field-annealed NiFe{sub 2}O{sub 4}.

  20. Effectiveness of ranitidine bismuth citrate and proton pump inhibitor ...

    African Journals Online (AJOL)

    Effectiveness of ranitidine bismuth citrate and proton pump inhibitor based triple therapies of Helicobacter pylori in Turkey. ... Results: When we look at the eradication rates of the treatment groups, only two groups (ranitidine bismuth citrate and rabeprazole groups) had eradication rates greater than 80%, both at intention to ...

  1. Citrate increases glass transition temperature of vitrified sucrose preparations

    NARCIS (Netherlands)

    Kets, E.P.W.; Lipelaar, P.J.; Hoekstra, F.A.; Vromans, H.

    2004-01-01

    The aim of this study was to investigate the effect of sodium citrate on the properties of dried amorphous sucrose glasses. Addition of sodium citrate to a sucrose solution followed by freeze-drying or convective drying resulted in a glass transition temperature (T-g) that was higher than the

  2. CoFeRh alloys

    International Nuclear Information System (INIS)

    Tabakovic, Ibro; Qiu Jiaoming; Riemer, Steve; Sun Ming; Vas'ko, Vlad; Kief, Mark

    2008-01-01

    The electrochemical behavior of Rh(III) species in CoFe solution containing RhCl 3 , NH 4 Cl, H 3 BO 3 , CoSO 4 , FeSO 4 , saccharin, and NaLS (Na lauryl sulfate) has been investigated. The electrochemistry of Rh(III) species is influenced by each of the compounds present in CoFe plating solution, but especially by addition of saccharin and H 3 BO 3 to the RhCl 3 -NH 4 Cl solution. The nucleation and growth of Rh on GC (glassy carbon), Ru, and Cu electrodes from NH 4 Cl solution was studied using the potentiostatic current-transient methods. The results support a predominantly progressive nucleation of Rh on all three-electrode surfaces. The nucleation kinetic parameters ANo (steady state nucleation rate) and Ns (saturation nuclear number density) were found to vary with potential and are electrode-dependent in order: GC > Ru∼Cu. The electrodeposited Rh films obtained from NH 4 Cl solution and nonmagnetic CoFeRh film obtained from CoFe solution were characterized in terms of the following properties: morphology, surface roughness, crystal structure and chemical composition. The origin of light elements found in Rh and CoFeRh films (O, Cl, S, C, N) was discussed

  3. Indolenine meso-substituted dibenzotetraaza[14]annulene and its coordination chemistry toward the transition metal ions Mn(III), Fe(III), Co(II), Ni(II), Cu(II), and Pd(II).

    Science.gov (United States)

    Khaledi, Hamid; Olmstead, Marilyn M; Ali, Hapipah Mohd; Thomas, Noel F

    2013-02-18

    A new dibenzotetraaza[14]annulene bearing two 3,3-dimethylindolenine fragments at the meso positions (LH(2)), has been synthesized through a nontemplate method. X-ray crystallography shows that the whole molecule is planar. The basicity of the indolenine ring permits the macrocycle to be protonated external to the core and form LH(4)(2+)·2Cl(-). Yet another structural modification having strong C-H···π interactions was found in the chloroform solvate of LH(2). The latter two modifications are accompanied by a degree of nonplanar distortion. The antiaromatic core of the macrocycle can accommodate a number of metal ions, Mn(III), Fe(III), Co(II), Ni(II) and Cu(II), to form complexes of [Mn(L)Br], [Mn(L)Cl], [Fe(LH(2))Cl(2)](+)·Cl(-), [Co(L)], [Ni(L)], and [Cu(L)]. In addition, the reaction of LH(2) with the larger Pd(II) ion leads to the formation of [Pd(2)(LH(2))(2)(OAc)(4)] wherein the macrocycle acts as a semiflexible ditopic ligand to coordinate pairs of metal ions via its indolenine N atoms into dinuclear metallocycles. The compounds LH(2), [Co(L)], and [Ni(L)] are isostructural and feature close π-stacking as well as linear chain arrangements in the case of the metal complexes. Variable temperature magnetic susceptibility measurements showed thermally induced paramagnetism in [Ni(L)].

  4. Robust and Selective Switching of an FeIII Spin-Crossover Compound on Cu2N/Cu(100) with Memristance Behavior.

    Science.gov (United States)

    Jasper-Toennies, Torben; Gruber, Manuel; Karan, Sujoy; Jacob, Hanne; Tuczek, Felix; Berndt, Richard

    2017-11-08

    The switching between two spin states makes spin-crossover molecules on surfaces very attractive for potential applications in molecular spintronics. Using scanning tunneling microscopy, the successful deposition of [Fe(pap) 2 ] + (pap = N-2-pyridylmethylidene-2-hydroxyphenylaminato) molecules on Cu 2 N/Cu(100) surface is evidenced. The deposited Fe III spin-crossover compound is controllably switched between three different states, each of them exhibiting a characteristic tunneling conductance. The conductance is therefore employed to readily read the state of the molecules. A comparison of the experimental data with the results of density functional theory calculations reveals that all Fe(pap) 2 molecules are initially in their high-spin state. The two other states are compatible with the low-spin state of the molecule but differ with respect to their coupling to the substrate. As a proof of concept, the reversible and selective nature of the switching is used to build a two-molecule memory.

  5. Determination of amino acid and protein peroxides by the xylenol orange-Fe(III) complex

    International Nuclear Information System (INIS)

    Collins, J.; Craig, G.; Gebicki, J.

    1996-01-01

    Oxidative stress imposed on living organisms is believed to lead to the depletion of their antioxidant defences, followed by chemical changes in the cell constituents. These may ultimately develop into pathological conditions such as cancer or cardiovascular disease. An assay of peroxides which could be applied to tissues or simple tissue extracts would prove extremely useful in the studies of the phenomenon of oxidative stress. With this purpose, the authors have tested the ability of two peroxide assay techniques to measure the formation of amino acid and protein peroxides in aqueous solutions irradiated with gamma rays, using a modification of the method based on the oxidation of Fe(II)) by peroxides and complexing of the Fe(III) produced by xylenol orange. The molar extinction coefficients of the peroxides tested were determined by comparison with the well-tested iodometric assay. This work was extended to the detection of all organic peroxides in human blood plasma or serum subjected to oxidative stress, where the iodometric assay proved difficult to apply and unreliable because of the binding of iodine to the blood components. Preliminary results suggest that exposure of serum to gamma radiation leads to immediate peroxidation of the proteins, with a delay before generation of lipid peroxides

  6. Effect of dissimilatory Fe(III) reducers on bio-reduction and nickel-cobalt recovery from Sukinda chromite-overburden.

    Science.gov (United States)

    Esther, Jacintha; Panda, Sandeep; Behera, Sunil K; Sukla, Lala B; Pradhan, Nilotpala; Mishra, Barada K

    2013-10-01

    The effect of an adapted dissimilatory iron reducing bacterial consortium (DIRB) towards bio-reduction of Sukinda chromite overburden (COB) with enhanced recovery of nickel and cobalt is being reported for the first time. The remarkable ability of DIRB to utilize Fe(III) as terminal electron acceptor reducing it to Fe(II) proved beneficial for treatment of COB as compared to previous reports for nickel leaching. XRD studies showed goethite as the major iron-bearing phase in COB. Under facultative anaerobic conditions, goethite was reduced to hematite and magnetite with the exposure of nickel oxide. FESEM studies showed DIRB to be associated with COB through biofilm formation with secondary mineral precipitates of magnetite deposited as tiny globular clusters on the extra polymeric substances. The morphological and mineralogical changes in COB, post DIRB application, yielded a maximum of 68.5% nickel and 80.98% cobalt in 10 days using 8M H2SO4. Copyright © 2013 Elsevier Ltd. All rights reserved.

  7. Identification of Genes Involved in Biofilm Formation and Respiration via Mini-Himar Transposon Mutagenesis of Geobacter sulfurreducens▿ †

    Science.gov (United States)

    Rollefson, Janet B.; Levar, Caleb E.; Bond, Daniel R.

    2009-01-01

    Electron transfer from cells to metals and electrodes by the Fe(III)-reducing anaerobe Geobacter sulfurreducens requires proper expression of redox proteins and attachment mechanisms to interface bacteria with surfaces and neighboring cells. We hypothesized that transposon mutagenesis would complement targeted knockout studies in Geobacter spp. and identify novel genes involved in this process. Escherichia coli mating strains and plasmids were used to develop a conjugation protocol and deliver mini-Himar transposons, creating a library of over 8,000 mutants that was anaerobically arrayed and screened for a range of phenotypes, including auxotrophy for amino acids, inability to reduce Fe(III) citrate, and attachment to surfaces. Following protocol validation, mutants with strong phenotypes were further characterized in a three-electrode system to simultaneously quantify attachment, biofilm development, and respiratory parameters, revealing mutants defective in Fe(III) reduction but unaffected in electron transfer to electrodes (such as an insertion in GSU1330, a putative metal export protein) or defective in electrode reduction but demonstrating wild-type biofilm formation (due to an insertion upstream of the NHL domain protein GSU2505). An insertion in a putative ATP-dependent transporter (GSU1501) eliminated electrode colonization but not Fe(III) citrate reduction. A more complex phenotype was demonstrated by a mutant containing an insertion in a transglutaminase domain protein (GSU3361), which suddenly ceased to respire when biofilms reached approximately 50% of the wild-type levels. As most insertions were not in cytochromes but rather in transporters, two-component signaling proteins, and proteins of unknown function, this collection illustrates how biofilm formation and electron transfer are separate but complementary phenotypes, controlled by multiple loci not commonly studied in Geobacter spp. PMID:19395486

  8. Preparation of chitosan-stabilized Fe{sup 0} nanoparticles for removal of hexavalent chromium in water

    Energy Technology Data Exchange (ETDEWEB)

    Geng, Bing [Key Laboratory of Pollution Processes and Environmental Criteria, Ministry of Education, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Jin, Zhaohui, E-mail: jinzh@nankai.edu.cn [Key Laboratory of Pollution Processes and Environmental Criteria, Ministry of Education, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Li, Tielong; Qi, Xinhua [Key Laboratory of Pollution Processes and Environmental Criteria, Ministry of Education, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China)

    2009-09-01

    Chitosan-stabilized Fe{sup 0} nanoparticles (CTO-Fe{sup 0}) and Fe{sup 0} nanoparticles synthesized in ethanol-water mixed system (EW-Fe{sup 0}) were tested for reduction of Cr(VI) in water. Fourier transform infrared (FTIR) study suggested that nitrogen and oxygen atoms are the binding sites for chitosan on iron which was accountable for the stability of Fe{sup 0} nanoparticles. While the EW-Fe{sup 0} ignites spontaneously when exposed to air, the CTO-Fe{sup 0} was still in zero valence state after exposure to air over 2-month period as shown by X-ray powder diffraction patterns. Batch experiments demonstrated that the maximum Cr(VI) reduction rates for CTO-Fe{sup 0} was about 3 times higher than EW-Fe{sup 0}. Characterizations with high-resolution X-ray photoelectron spectroscopy (HR-XPS) revealed that Cr(VI) was reduced to Cr(III) and Fe(III) was the only component present on the Fe{sup 0} nanoparticles surface. Additionally, chitosan can inhibited the formation of Fe(III)-Cr(III) precipitation due to its high ability to chelate Fe(III) which resulted in k{sub obs} for CTO-Fe{sup 0} was about 1-3 times higher than EW-Fe{sup 0}. Due to the fast reaction kinetics and good stability against oxidation in air, the chitosan-stabilized Fe{sup 0} nanoparticles have the potential to become an effective agent for in situ subsurface environment remediation.

  9. Structure of Fe(III) precipitates generated by Fe(0) electrocoagulation in the presence of groundwater ions

    Science.gov (United States)

    van Genuchten, C. M.; Pena, J.; Addy, S. E.; Gadgil, A. J.

    2012-12-01

    Electrocoagulation (EC) using Fe(0) electrodes is an inexpensive and efficient technology capable of removing a variety of contaminants from water supplies. Because of its ease of use and modest electricity and Fe(0) requirements, EC has potential as an arsenic-removal technology for rural South Asia, where millions drink groundwater contaminated by arsenic. In EC, a small external voltage applied to a sacrificial Fe(0) anode in contact with an electrolyte (e.g. pumped groundwater containing arsenic) promotes the oxidative dissolution of Fe ions, which polymerize and create reactive hydrous ferric oxides (HFO) in-situ with a high affinity for binding contaminants. The chemical composition of the electrolyte influences EC performance. For example, major inorganic ions present in groundwater (e.g. Ca, Mg, P, As(V), Si) alter the pathway by which FeO6 oligomers polymerize to form crystalline Fe (oxyhydr)oxide minerals. Because the precipitate structure largely determines properties that govern the efficiency of EC systems (e.g. precipitate reactivity and colloidal stability), it is essential to understand the individual and interdependent structural effects of common groundwater ions. In this work, we integrate Fe K-edge EXAFS spectroscopy with the Pair Distribution Function (PDF) technique to create a detailed description of EC precipitate structure as a function of electrolyte chemistry. EC precipitate samples were generated in a range of individual and combined concentrations of Ca, Mg, P, As(V), and Si, encompassing most of the typical levels found in natural groundwater. Combining complementary EXAFS and PDF techniques with batch uptake experiments and general chemical reasoning, we obtain structural representations of EC precipitates that are inaccessible with any single characterization technique. Our results indicate that the presence of As(V), P, and Si oxyanions promote the formation of nanoscale material bearing similar, but not identical, intermediate

  10. Simultaneous absorption of NO and SO{sub 2} into Fe-II-EDTA solution coupled with the Fe-II-EDTA regeneration catalyzed by activated carbon

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, H.S.; Mao, Y.P.; Yang, X.J.; Chen, Y.; Long, X.L.; Yuan, W.K. [East China University of Science & Technology, Shanghai (China)

    2010-07-30

    The simultaneous removal of NO and SO{sub 2} from flue gases can be realized with Fe(II)-ethylenediamineteraacetate (EDTA) solution. Activated carbon is used to catalyze the reduction of Fe-III-EDTA to Fe-II-EDTA to maintain the capability of removing NO of the Fe-EDTA solution. The reductant is the sulfite/bisulfite ions produced by SO{sub 2} dissolving into the aqueous solution. Experiments have been performed to determine the effects of activated carbon of coconut shell, Fe-II-EDTA concentration, Fe/EDTA molar ratio, SO{sub 2} partial pressure, NO partial pressure and SO{sub 4}{sup 2-} concentration on the combined elimination of NO and SO{sub 2} with Fe-II-EDTA solution coupled with the Fe-II-EDTA regeneration catalyzed by activated carbon. According to the experimental results, activated carbon not only catalyzes the reduction of Fe-III-EDTA by sulfite/bisulfite greatly but also avoids the release of N{sub 2}O. The NO removal efficiency increases with the initial Fe-II-EDTA concentration and SO{sub 2} partial pressure. The ratio of Fe/EDTA and the SO{sub 4}{sup 2-} concentration has little effect on the catalytic reduction of Fe-III-EDTA. The optimal initial NO concentration range is from 600 ppm to 900 ppm. The experimental results manifest that the Fe-II-EDTA solution coupled with catalytic regeneration of Fe-II-EDTA can maintain high nitric oxide removal efficiency for a long period of time.

  11. Liquid-liquid extraction (LLE) of Fe(III) and Ti(IV) by bis-(2-ethyl-hexyl) phosphoric acid (D2EHPA) in sulfuric acid medium; Extracao liquido-liquido de ferro (III) e titanio (IV) pelo acido bis-(2-etil-hexil) fosforico (D2EHPA) em meio de acido sulfurico

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Glauco Correa da; Cunha, Jose Waldemar Silva Dias da [Instituto de Engenharia Nuclear (IEN), Rio de Janeiro, RJ (Brazil). Dept. de Quimica e Materiais Nucleares; Dweck, Jo [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Escola de Quimica. Dept. de Processos Inorganicos; Afonso, Julio Carlos [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Inst. de Quimica. Dept. de Quimica Analitica]. E-mail: julio@iq.ufrj.br

    2008-07-01

    This work presents a study on the separation of Fe(III) and Ti(IV) from sulfuric acid leaching solutions of ilmenite (FeTiO{sub 3}) using liquid-liquid extraction with D2EHPA in n-dodecane as extracting agent. The distribution coefficients (K{sub D}) of the elements related to free acidity and concentration of Fe(III) and Ti(IV) were determined. Free acidity was changed from 3x10{sup -2} to 11.88 mol L{sup -1} and D2EHPA concentration was fixed at 1.5 mol L{sup 1}. Recovery of final products as well as recycling of wastes generated in the process were also investigated. The LLE process as a feasible alternative to obtain high-purity TiO{sub 2}. (author)

  12. Sorption of chromium(VI) and chromium(III) on aluminium hydroxide

    International Nuclear Information System (INIS)

    Music, S.

    1986-01-01

    Factors that influence the sorption of Cr(VI) and Cr(III) on aluminium hydroxide were investigated. The sorption of chromates decreases as the pH of the suspension increases. The mechanism of CrOsub(4)sup(2-) sorption was interpreted in terms of reactions between chromates and -OH and/or Hsub(2)O groups at the hydroxide/liquid interface. It was shown that chromates are more tightly sorbed on aluminium hydroxide compared to other anions, e.g. chlorides. On the other hand, specifically absorbed anions, such as molybdates, compete strongly with chromates for the sorption sites. The sorption of chromium(III) increases with the pH of the suspension. Also, the sorption of chromium(III) is suppressed in the presence of citrate ions. The best conditions for the fixation of Cr(VI) and Cr(III) by aluminium hydroxide are presented. (author)

  13. Diffuse abdominal gallium-67 citrate uptake in salmonella infections

    International Nuclear Information System (INIS)

    Garty, I.; Koren, A.

    1987-01-01

    Two pediatric patients with salmonella infections (one with typhoid fever and the second with salmonella C2 gastroenteritis), had a diffuse abdominal uptake of Ga-67 citrate. The possible explanation for this finding is discussed. Salmonella infection should be included as a cause in the differential diagnosis of diffuse accumulation of Ga-67 citrate

  14. Comparative genomics and transcriptome analysis of Aspergillus niger and metabolic engineering for citrate production

    Science.gov (United States)

    Yin, Xian; Shin, Hyun-dong; Li, Jianghua; Du, Guocheng; Liu, Long; Chen, Jian

    2017-01-01

    Despite a long and successful history of citrate production in Aspergillus niger, the molecular mechanism of citrate accumulation is only partially understood. In this study, we used comparative genomics and transcriptome analysis of citrate-producing strains—namely, A. niger H915-1 (citrate titer: 157 g L−1), A1 (117 g L−1), and L2 (76 g L−1)—to gain a genome-wide view of the mechanism of citrate accumulation. Compared with A. niger A1 and L2, A. niger H915-1 contained 92 mutated genes, including a succinate-semialdehyde dehydrogenase in the γ-aminobutyric acid shunt pathway and an aconitase family protein involved in citrate synthesis. Furthermore, transcriptome analysis of A. niger H915-1 revealed that the transcription levels of 479 genes changed between the cell growth stage (6 h) and the citrate synthesis stage (12 h, 24 h, 36 h, and 48 h). In the glycolysis pathway, triosephosphate isomerase was up-regulated, whereas pyruvate kinase was down-regulated. Two cytosol ATP-citrate lyases, which take part in the cycle of citrate synthesis, were up-regulated, and may coordinate with the alternative oxidases in the alternative respiratory pathway for energy balance. Finally, deletion of the oxaloacetate acetylhydrolase gene in H915-1 eliminated oxalate formation but neither influence on pH decrease nor difference in citrate production were observed. PMID:28106122

  15. Scintiscanning of lung cancer with 67Ga-citrate

    International Nuclear Information System (INIS)

    Abe, Mitsunobu; Ohyama, Shiro; Ohtsuka, Hassau; Hoshina, Toshifumi; Takanashi, Shuko

    1982-01-01

    The clinical value of scintigram with 67 Ga-citrate in 58 patients with primary lung cancer was investigated and discussed. The results are as follows: 1) Positive 67 Ga-scintigram was obtained in 83% of patients with primary lung cancer. The histologically confirmed positive ratios were 74% in adenocarcinoma, 94% in squamous cell carcinoma, 80% in small cell carcinoma and 100% in large cell carcinoma. 2) The positive ratios according to T category of TNM classification was 0% (0/1) in T1, 83% (20/24) in T2 and 85% (28/33) in T3. 3) According to rules for classification of lung cancer (TNM UICC 1978,) T2 cases were divided into two groups. a) In patients with hilar involvements on chest X-ray, positive accumulation to the hilar region was 88% (7/8). b) In patients without the evidence of hilar involvements on chest X-ray, the positive accumulation to the hilar region was 81% (13/16). 4) All cases extending to the mediastinum showed abnormal 67 Ga-citrate accumulation regardless of histological type. 67 Ga-citrate scanning is useful in evaluating the extent of lung cancer, especially with hilar and mediastinal involvements. Therefore 67 Ga-citrate scanning seems to be very useful for planning the radiotherapy for lung cancer. (author)

  16. Ammonium iron(III phosphate(V fluoride, (NH40.5[(NH40.375K0.125]FePO4F, with ammonium partially substituted by potassium

    Directory of Open Access Journals (Sweden)

    Lei Wang

    2009-01-01

    Full Text Available The title compound, ammonium potassium iron(III phosphate fluoride, (NH40.875K0.125FePO4F, is built from zigzag chains ∞1{[FeO4F2]7−}, with Fe3+ in a distorted octahedral coordination, extending along both the [011] and [0overline{1}1] directions. These chains are made up of alternating trans-[FeO4F2] and cis-[FeO4F2] octahedra via shared F-atom corners, and are linked by PO4 tetrahedra, resulting in an open-framework structure with channels along the [010] and [100] directions. There are two crystallographically independent ammonium sites: one in the [010] channels and the other, partially substituted by K+ ions, in the [100] channels. The ammonium in the [010] channels is fixed to the framework via eight hydrogen bonds (six N—H...O and two N—H...F.

  17. Single-ion anisotropy and exchange interactions in the cyano-bridged trimers MnIII2MIII(CN)6 (MIII = Co, Cr, Fe) species incorporating [Mn(5-Brsalen)]+ units: an inelastic neutron scattering and magnetic susceptibility study

    DEFF Research Database (Denmark)

    Tregenna-Piggott, Philip L W; Sheptyakov, Denis; Keller, Lukas

    2009-01-01

    expectations based on the unquenched orbital angular momentum of the [Fe(CN)(6)](3-) anion, giving rise to an M(s) approximately +/-9/2 ground state, isolated by approximately 11.5 cm(-1) from the higher-lying levels. The reported INS and magnetic data should now serve as a benchmark against which theoretical...... interactions that define the low-lying states of the Mn-M(III)-Mn trimeric units. Despite the presence of an antiferromagnetic intertrimer interaction, the experimental evidence supports the classification of both the Cr(III) and Fe(III) compounds as single-molecule magnets. The value of 17(2) cm(-1...

  18. Comparison of the therapeutic effects of sildenafil citrate, heparin and neuropeptides in a rat model of acetic acid-induced gastric ulcer.

    Science.gov (United States)

    Kalayci, Mehmet; Kocdor, Mehmet Ali; Kuloglu, Tuncay; Sahin, İbrahim; Sarac, Mehmet; Aksoy, Aziz; Yardim, Meltem; Dalkilic, Semih; Gursu, Onur; Aydin, Suna; Akkoc, Ramazan Fazil; Ugras, Meltem; Artas, Gokhan; Ozercan, İbrahim Hanifi; Ugur, Kader; Aydin, Suleyman

    2017-10-01

    The purpose of our investigative work has been to determine whether there can be therapeutic roles in the administration of sildenafil citrate, heparin and several neuropeptides on an animal model where gastric ulcers were induced with acetic acid, and to compare their efficacy. The animals were divided into 13 groups, with 4 animals in each. Gastric ulcers was induced in the animals of 12 groups with one untreated group being left as the control (Group I - control; given normal saline (NS)). The other groups were: Group II (ulcer+NS); Group III (5mg/kg sildenafil citrate, low dose); Group IV (10mg/kg sildenafil citrate, high dose); Group V (0.6mg/kg heparin, low dose); Group VI (6mg/kg heparin, high dose); Group VII (20nmol/kg des-acyl ghrelin); Group VIII (40nmol/kg des-acyl ghrelin); Group IX (4nmol/kg acyl ghrelin); Group X (8nmol/kg acly ghrelin); Group XI (20pmol/kg Nesfatin-1); Group XII (15nmol/kg Obestatin) and Group XIII (5nmol/kg Neuropeptide Y). Gastric neuropeptide expression was measured using an immunohistochemical method, and the amount in circulation was detected using ELISA. To compare with no treatment, the controls and other treatment groups, we recorded loss of the surface epithelium of the stomach, erosion, bleeding and inflammatory cell infiltration in the upper halves of the gastric glands. The muscularis and the layers beneath it were, however, apparently normal. The gastric mucosa healed with little or no inflammation when sildenafil citrate, low dose heparin, ghrelin, NUCB2/Nesfatin-1, obestatin, Neuropeptide Y were administered. Overall the data indicate that low dose heparin, and especially sildenafil citrate and neuropeptides, can be used clinically as an alternative approach in the treatment of the gastric ulcer. Copyright © 2017 Elsevier Inc. All rights reserved.

  19. Desulfovibrio frigidus sp. nov. and Desulfovibrio ferrireducens sp. nov., psychrotolerant bacteria isolated from Arctic fjord sediments (Svalbard) with the ability to reduce Fe(III)

    DEFF Research Database (Denmark)

    Vandieken, Verona; Knoblauch, Christian; Jørgensen, Bo Barker

    2006-01-01

    fermentation products such as hydrogen, formate and lactate with sulfate as the electron acceptor. Sulfate could be replaced by sulfite, thiosulfate or elemental sulfur. Poorly crystalline and soluble Fe(III) compounds were reduced in sulfate-free medium, but no growth occurred under these conditions...

  20. Fe electron transfer and atom exchange in goethite: influence of Al-substitution and anion sorption.

    Science.gov (United States)

    Latta, Drew E; Bachman, Jonathan E; Scherer, Michelle M

    2012-10-02

    The reaction of Fe(II) with Fe(III) oxides and hydroxides is complex and includes sorption of Fe(II) to the oxide, electron transfer between sorbed Fe(II) and structural Fe(III), reductive dissolution coupled to Fe atom exchange, and, in some cases mineral phase transformation. Much of the work investigating electron transfer and atom exchange between aqueous Fe(II) and Fe(III) oxides has been done under relatively simple aqueous conditions in organic buffers to control pH and background electrolytes to control ionic strength. Here, we investigate whether electron transfer is influenced by cation substitution of Al(III) in goethite and the presence of anions such as phosphate, carbonate, silicate, and natural organic matter. Results from (57)Fe Mössbauer spectroscopy indicate that both Al-substitution (up to 9%) and the presence of common anions (PO(4)(3-), CO(3)(2-), SiO(4)(4-), and humic acid) does not inhibit electron transfer between aqueous Fe(II) and Fe(III) in goethite under the conditions we studied. In contrast, sorption of a long-chain phospholipid completely shuts down electron transfer. Using an enriched isotope tracer method, we found that Al-substitution in goethite (10%), does, however, significantly decrease the extent of atom exchange between Fe(II) and goethite (from 43 to 12%) over a month's time. Phosphate, somewhat surprisingly, appears to have little effect on the rate and extent of atom exchange between aqueous Fe(II) and goethite. Our results show that electron transfer between aqueous Fe(II) and solid Fe(III) in goethite can occur under wide range of geochemical conditions, but that the extent of redox-driven Fe atom exchange may be dependent on the presence of substituting cations such as Al.

  1. Ultrasound-assisted biodiesel production by a novel composite of Fe(III)-based MOF and phosphotangestic acid as efficient and reusable catalyst.

    Science.gov (United States)

    Nikseresht, Ahmad; Daniyali, Asra; Ali-Mohammadi, Mahdi; Afzalinia, Ahmad; Mirzaie, Abbas

    2017-07-01

    In this work, esterification of oleic acid by various alcohols is achieved with high yields under ultrasonic irradiation. This reaction performed with a novel heterogeneous catalyst that fabricated by heteropoly acid and Fe(III)-based MOF, namely MIL-53 (Fe). Syntheses of MIL-53 and encapsulation process carry out by ultrasound irradiation at ambient temperature and atmospheric pressure. The prepared composite was characterized by various techniques such as XRD, FT-IR, SEM, BET and ICP that demonstrate excellent catalytic activities, while being highly convenient to synthesize. The obtained results revealed that ultrasound irradiation could be used for the appropriate and rapid biodiesel production. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Non-transferrin-bound iron (NTBI uptake by T lymphocytes: evidence for the selective acquisition of oligomeric ferric citrate species.

    Directory of Open Access Journals (Sweden)

    Joao Arezes

    Full Text Available Iron is an essential nutrient in several biological processes such as oxygen transport, DNA replication and erythropoiesis. Plasma iron normally circulates bound to transferrin. In iron overload disorders, however, iron concentrations exceed transferrin binding capacity and iron appears complexed with low molecular weight molecules, known as non-transferrin-bound iron (NTBI. NTBI is responsible for the toxicity associated with iron-overload pathologies but the mechanisms leading to NTBI uptake are not fully understood. Here we show for the first time that T lymphocytes are able to take up and accumulate NTBI in a manner that resembles that of hepatocytes. Moreover, we show that both hepatocytes and T lymphocytes take up the oligomeric Fe3Cit3 preferentially to other iron-citrate species, suggesting the existence of a selective NTBI carrier. These results provide a tool for the identification of the still elusive ferric-citrate cellular carrier and may also open a new pathway towards the design of more efficient iron chelators for the treatment of iron overload disorders.

  3. CoFeRh alloys

    Energy Technology Data Exchange (ETDEWEB)

    Tabakovic, Ibro [Seagate Technology, Research and Development, Bloomington, MN 55435 (United States)], E-mail: ibro.m.tabakovic@seagate.com; Qiu Jiaoming; Riemer, Steve; Sun Ming; Vas' ko, Vlad; Kief, Mark [Seagate Technology, Research and Development, Bloomington, MN 55435 (United States)

    2008-01-01

    The electrochemical behavior of Rh(III) species in CoFe solution containing RhCl{sub 3}, NH{sub 4}Cl, H{sub 3}BO{sub 3}, CoSO{sub 4}, FeSO{sub 4}, saccharin, and NaLS (Na lauryl sulfate) has been investigated. The electrochemistry of Rh(III) species is influenced by each of the compounds present in CoFe plating solution, but especially by addition of saccharin and H{sub 3}BO{sub 3} to the RhCl{sub 3}-NH{sub 4}Cl solution. The nucleation and growth of Rh on GC (glassy carbon), Ru, and Cu electrodes from NH{sub 4}Cl solution was studied using the potentiostatic current-transient methods. The results support a predominantly progressive nucleation of Rh on all three-electrode surfaces. The nucleation kinetic parameters ANo (steady state nucleation rate) and Ns (saturation nuclear number density) were found to vary with potential and are electrode-dependent in order: GC > Ru{approx}Cu. The electrodeposited Rh films obtained from NH{sub 4}Cl solution and nonmagnetic CoFeRh film obtained from CoFe solution were characterized in terms of the following properties: morphology, surface roughness, crystal structure and chemical composition. The origin of light elements found in Rh and CoFeRh films (O, Cl, S, C, N) was discussed.

  4. Optimization of reaction conditions in selective oxidation of styrene over fine crystallite spinel-type CaFe2O4 complex oxide catalyst

    International Nuclear Information System (INIS)

    Pardeshi, Satish K.; Pawar, Ravindra Y.

    2010-01-01

    The CaFe 2 O 4 spinel-type catalyst was synthesized by citrate gel method and well characterized by thermogravimetric analysis, atomic absorption spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction and transmission electron microscopy. The crystallization temperature of the spinel particle prepared by citrate gel method was 600 o C which was lower than that of ferrite prepared by other methods. CaFe 2 O 4 catalysts prepared by citrate gel method show better activity for styrene oxidation in the presence of dilute H 2 O 2 (30%) as an oxidizing agent. In this reaction the oxidative cleavage of carbon-carbon double bond of styrene takes place selectively with 38 ± 2 mol% conversion. The major product of the reaction is benzaldehyde up to 91 ± 2 mol% and minor product phenyl acetaldehyde up to 9 ± 2 mol%, respectively. The products obtained in the styrene oxidation reaction were analyzed by gas chromatography and mass spectroscopy. The influence of the catalyst, reaction time, temperature, amount of catalyst, styrene/H 2 O 2 molar ratio and solvents on the conversion and product distribution were studied.

  5. Sildenafil citrate (Viagra) enhances vasodilatation by atrial natriuretic peptide in normal dogs.

    Science.gov (United States)

    Ishikura, Fuminobu; Beppu, Shintaro; Asanuma, Toshihiko; Seward, James B; Khandheria, Bijoy K

    2007-12-01

    Sildenafil citrate (Viagra) is a selective inhibitor of cyclic guanosine monophosphate (cGMP)-specific phosphodiesterase type 5, which might enhance the vasorelaxant and natriuretic actions of atrial natriuretic peptide (ANP) in patients with heart failure. The objective of this study was to examine the combined effect of Viagra on hemodynamic changes during infusion of exogenous ANP. Healthy male beagles were used to assess systemic blood pressure, pulmonary artery pressure (PAP), and plasma levels of cGMP. After hemodynamic variables were measured, 0.1 microg.kg(-1).min(-1) of ANP was given during this study. One hour after initiating infusion of ANP, 2 mg/kg of sildenafil citrate or vehicle was given orally via a nasogastric tube. Hemodynamic changes were measured before and 1 h after these administrations. Mean systemic and PAP decreased during infusion of ANP, and further decreased after sildenafil citrate administration, however, mean systemic blood pressure decreased within 10 mmHg. Plasma levels of cGMP also increased after sildenafil citrate administration. In normal dogs, sildenafil citrate enhances the vasodilator effect of ANP by increasing the cGMP level, however, the concomitant use of sildenafil citrate with ANP will not induce severe hypotension.

  6. Effect of Fe substitution on multiferroic hexagonal YMnO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Zaghrioui, M., E-mail: zaghrioui@univ-tours.f [Laboratoire d' electrodynamique des materiaux avances, UMR CNRS 6157 - CEA Universite F. Rabelais-IUT de Blois, 3 place Jean Jaures, C. S. 2903, 41029 Blois Cedex - France (France); Greneche, J.M. [Laboratoire de Physique de l' Etat Condense, UMR CNRS 6087, Universite du Maine, Avenue Olivier Messiaen, 72085 Le Mans (France); Autret-Lambert, C.; Gervais, M. [Laboratoire d' electrodynamique des materiaux avances, UMR CNRS 6157 - CEA Universite F. Rabelais-IUT de Blois, 3 place Jean Jaures, C. S. 2903, 41029 Blois Cedex (France)

    2011-03-15

    Polycrystalline YMn{sub 1-x}Fe{sub x}O{sub 3} (x=0.02-0.20) powders were synthesized by means of modified citrate method. Powder X-ray diffraction gives evidence that all the samples are single phase and exhibit hexagonal structure with P6{sub 3}cm space group as observed for YMnO{sub 3}. The solubility limit of Fe was determined as about 6 wt.%. Cell parameter values were found to increase with Fe content, since Fe{sup 3+} and Mn{sup 3+} have the same ionic radii. This can be attributed to the increase of the tilting of MnO{sub 5} bipyramid and the buckling of Y atoms. In addition, {sup 57}Fe Moessbauer spectrometry provides evidence of two Fe{sup 3+} sites attributed to two different nearest atomic neighbours. Magnetic properties reveal a paramagnetic-to-antiferromagnetic transition, a possible increase of the magnetic anisotropy, and a competition between ferromagnetic and antiferromagnetic interactions. - Research highlights: The increase of the tilting of MnO{sub 5} bipyramid and the buckling of Y atoms leads to the increase of cell parameter in YMn{sub 1-x}Fe{sub x}O{sub 3}. {sup 57}Fe Moessbauer spectrometry provides evidence of two Fe{sup 3+} sites.

  7. Fe(III)-EDDHA and -EDDHMA sorption on Ca-montmorillonite, ferrihydrite, and peat.

    Science.gov (United States)

    Hernández-Apaolaza, L; Lucena, J J

    2001-11-01

    The effectiveness of Fe chelates as Fe sources and carriers in soil can be severely limited by the adsorption of Fe chelates or chelating agents in the solid phase. To study this phenomenon, well-characterized peat, Ca-montmorillonite, and ferrihydrite were used as model compounds, and the adsorption of Fe-EDDHA and Fe-EDDHMA chelates were studied. Sorption isotherms for the meso and racemic isomers of these chelates on the soil materials are described. The variability of sorption with pH in peat and ferrihydrite was also determined because both have variable surface charge at different pH values. In montmorillonite, at low concentrations, the retention of Fe from the Fe-EDDHMA chelate is greater than the one of the Fe-EDDHA chelate. As well as the concentration increased, the inverse situation occurs. The behavior of both meso and racemic isomers of chelates in contact with Ca-montmorillonite is similar. The Fe-meso-EDDHA isomer was highly adsorbed on ferrihydrite, but the racemic isomer is not significantly retained by this oxide. For Fe-EDDHMA isomers, the racemic isomer was more retained by the oxide, but a small sorption of the racemic isomer was also observed. Results suggest that Fe-EDDHA chelates were more retained in peat than Fe-EDDHMA chelates. The most retained isomer of Fe-EDDHA was the meso isomer. For Fe-EDDHMA, the adsorption was very low for both racemic and meso isomers.

  8. Artificial citrate operon and Vitreoscilla hemoglobin gene enhanced mineral phosphate solubilizing ability of Enterobacter hormaechei DHRSS.

    Science.gov (United States)

    Yadav, Kavita; Kumar, Chanchal; Archana, G; Kumar, G Naresh

    2014-10-01

    Mineral phosphate solubilization by bacteria is mediated through secretion of organic acids, among which citrate is one of the most effective. To overproduce citrate in bacterial systems, an artificial citrate operon comprising of genes encoding NADH-insensitive citrate synthase of E. coli and Salmonella typhimurium sodium-dependent citrate transporter was constructed. In order to improve its mineral phosphate solubilizing (MPS) ability, the citrate operon was incorporated into E. hormaechei DHRSS. The artificial citrate operon transformant secreted 7.2 mM citric acid whereas in the native strain, it was undetectable. The transformant released 0.82 mM phosphate in flask studies in buffered medium containing rock phosphate as sole P source. In fermenter studies, similar phenotype was observed under aerobic conditions. However, under microaerobic conditions, no citrate was detected and P release was not observed. Therefore, an artificial citrate gene cluster containing Vitreoscilla hemoglobin (vgb) gene under its native promoter, along with artificial citrate operon under constitutive tac promoter, was constructed and transformed into E. hormaechei DHRSS. This transformant secreted 9 mM citric acid under microaerobic conditions and released 1.0 mM P. Thus, incorporation of citrate operon along with vgb gene improves MPS ability of E. hormaechei DHRSS under buffered, microaerobic conditions mimicking rhizospheric environment.

  9. Formation and Stabilization of Environmentally Persistent Free Radicals Induced by the Interaction of Anthracene with Fe(III)-Modified Clays.

    Science.gov (United States)

    Jia, Hanzhong; Nulaji, Gulimire; Gao, Hongwei; Wang, Fu; Zhu, Yunqing; Wang, Chuanyi

    2016-06-21

    Environmentally persistent free radicals (EPFRs) are occasionally detected in Superfund sites but the formation of EPFRs induced by polycyclic aromatic hydrocarbons (PAHs) is not well understood. In the present work, the formation of EPFRs on anthracene-contaminated clay minerals was quantitatively monitored via electron paramagnetic resonance (EPR) spectroscopy, and surface/interface-related environmental influential factors were systematically explored. The obtained results suggest that EPFRs are more readily formed on anthracene-contaminated Fe(III)-montmorillonite than in other tested systems. Depending on the reaction condition, more than one type of organic radicals including anthracene-based radical cations with g-factors of 2.0028-2.0030 and oxygenic carbon-centered radicals featured by g-factors of 2.0032-2.0038 were identified. The formed EPFRs are stabilized by their interaction with interlayer surfaces, and such surface-bound EPFRs exhibit slow decay with 1/e-lifetime of 38.46 days. Transformation pathway and possible mechanism are proposed on the basis of experimental results and quantum mechanical simulations. Overall, the formation of EPFRs involves single-electron-transfer from anthracene to Fe(III) initially, followed by H2O addition on formed aromatic radical cation. Because of their potential exposure in soil and atmosphere, such clay surface-associated EPFRs might induce more serious toxicity than PAHs and exerts significant impacts on human health.

  10. Citrate and malonate increase microbial activity and alter microbial community composition in uncontaminated and diesel-contaminated soil microcosms

    Science.gov (United States)

    Martin, Belinda C.; George, Suman J.; Price, Charles A.; Shahsavari, Esmaeil; Ball, Andrew S.; Tibbett, Mark; Ryan, Megan H.

    2016-09-01

    Petroleum hydrocarbons (PHCs) are among the most prevalent sources of environmental contamination. It has been hypothesized that plant root exudation of low molecular weight organic acid anions (carboxylates) may aid degradation of PHCs by stimulating heterotrophic microbial activity. To test their potential implication for bioremediation, we applied two commonly exuded carboxylates (citrate and malonate) to uncontaminated and diesel-contaminated microcosms (10 000 mg kg-1; aged 40 days) and determined their impact on the microbial community and PHC degradation. Every 48 h for 18 days, soil received 5 µmol g-1 of (i) citrate, (ii) malonate, (iii) citrate + malonate or (iv) water. Microbial activity was measured daily as the flux of CO2. After 18 days, changes in the microbial community were assessed by a community-level physiological profile (CLPP) and 16S rRNA bacterial community profiles determined by denaturing gradient gel electrophoresis (DGGE). Saturated PHCs remaining in the soil were assessed by gas chromatography-mass spectrometry (GC-MS). Cumulative soil respiration increased 4- to 6-fold with the addition of carboxylates, while diesel contamination resulted in a small, but similar, increase across all carboxylate treatments. The addition of carboxylates resulted in distinct changes to the microbial community in both contaminated and uncontaminated soils but only a small increase in the biodegradation of saturated PHCs as measured by the n-C17 : pristane biomarker. We conclude that while the addition of citrate and malonate had little direct effect on the biodegradation of saturated hydrocarbons present in diesel, their effect on the microbial community leads us to suggest further studies using a variety of soils and organic acids, and linked to in situ studies of plants, to investigate the role of carboxylates in microbial community dynamics.

  11. Effect of the tether on the Mg(II), Ca(II), Cu(II) and Fe(III) stability constants and pM values of chelating agents related to EDDHA.

    Science.gov (United States)

    Sierra, Miguel A; Gómez-Gallego, Mar; Alcázar, Roberto; Lucena, Juan J; Yunta, Felipe; García-Marco, Sonia

    2004-11-07

    The effect of the length and the structure of the tether on the chelating ability of EDDHA-like chelates have not been established. In this work, PDDHA (propylenediamine-N,N'-bis(o-hydroxyphenyl)acetic acid), BDDHA (butylenediamine-N,N'-bis(o-hydroxyphenyl)acetic acid) and XDDHA (p-xylylenediamine-N,N'-bis(o-hydroxyphenyl)acetic acid) have been obtained and their chemical behaviour has been studied and compared with that of EDDHA following our methodology. The purity of the chelating agents, and their protonation, Ca(II), Mg(II), Fe(III) and Cu(II) stability constants and pM values have been determined. The stability constants and pM values indicate that EDDHA forms the most stable chelates followed by PDDHA. However, the differences among the pFe values are small when a nutrient solution is used, and in these conditions the XDDHA/Fe(III) chelate is the most stable. The results obtained in this work indicate that all the chelating agents studied can be used as iron chlorosis correctors and they can be applied to soil/plant systems.

  12. Synthesis of Cd/(Al+Fe) layered double hydroxides and characterization of the calcination products

    International Nuclear Information System (INIS)

    Perez, M.R.; Barriga, C.; Fernandez, J.M.; Rives, V.; Ulibarri, M.A.

    2007-01-01

    Layered double hydroxides (LDHs) containing Cd(II), Al(III), and Fe(III) in the brucite-like layers with different starting Fe/Al atomic ratios and with nitrate as counteranion have been prepared following the coprecipitation method at a constant pH value of 8. An additional Cd(II),Al(III)-LDH sample interlayered with hexacyanoferrate(III) ions has been prepared by ionic exchange at pH 9. The samples have been characterized by elemental chemical analysis, powder X-ray diffraction (PXRD), and FT-IR spectroscopy. Their thermal stability has been assessed by thermogravimetric and differential thermal analyses (TG-DTA) and mass spectrometric analysis of the evolved gases. The PXRD patterns of the solids calcined at 800 deg. C show diffraction lines corresponding to Cd(Al)O and spinel-type materials, which precise nature (CdAl 2 O 4 , Cd 1-x Fe 2+x O 4 , or Cd x Fe 2.66 O 4 ) depends on location and concentration of iron in the parent material or precursor. - Graphical abstract: Layered double hydroxides (LDHs) containing Cd(II), Al(III), and Fe(III) in the brucite-like layers with different starting Fe/Al atomic ratios and with nitrate as counteranion have been prepared following the coprecipitation method. An additional Cd(II),Al(III)-LDH sample interlayered with hexacyanoferrate(III) ions has been prepared by ionic exchange. Calcination at 800 deg. C shows diffraction lines corresponding to CdO and to spinel-type materials. SEM micrograph of sample CdAlFe-N-0

  13. Kinetics and Products of Chromium(VI) Reduction by Iron(II/III)-Bearing Clay Minerals.

    Science.gov (United States)

    Joe-Wong, Claresta; Brown, Gordon E; Maher, Kate

    2017-09-05

    Hexavalent chromium is a water-soluble pollutant, the mobility of which can be controlled by reduction of Cr(VI) to less soluble, environmentally benign Cr(III). Iron(II/III)-bearing clay minerals are widespread potential reductants of Cr(VI), but the kinetics and pathways of Cr(VI) reduction by such clay minerals are poorly understood. We reacted aqueous Cr(VI) with two abiotically reduced clay minerals: an Fe-poor montmorillonite and an Fe-rich nontronite. The effects of ionic strength, pH, total Fe content, and the fraction of reduced structural Fe(II) [Fe(II)/Fe(total)] were examined. The last variable had the largest effect on Cr(VI) reduction kinetics: for both clay minerals, the rate constant of Cr(VI) reduction varies by more than 3 orders of magnitude with Fe(II)/Fe(total) and is described by a linear free energy relationship. Under all conditions examined, Cr and Fe K-edge X-ray absorption near-edge structure spectra show that the main Cr-bearing product is a Cr(III)-hydroxide and that Fe remains in the clay structure after reacting with Cr(VI). This study helps to quantify our understanding of the kinetics of Cr(VI) reduction by Fe(II/III)-bearing clay minerals and may improve predictions of Cr(VI) behavior in subsurface environments.

  14. Fe(II)–Al(III) layered double hydroxides prepared by ultrasound-assisted co-precipitation method for the reduction of bromate

    International Nuclear Information System (INIS)

    Zhong, Yu; Yang, Qi; Luo, Kun; Wu, Xiuqiong; Li, Xiaoming; Liu, Yang; Tang, Wangwang; Zeng, Guangming; Peng, Bo

    2013-01-01

    Highlights: ► Fe(II)–Al(III) LDHs were synthesized by ultrasound-assisted co-precipitation method. ► The Fe–Al (30 min) exhibited highly reduction reactivity on bromate. ► Pseudo-first-order model described the experimental data well. ► The mechanisms of bromate removal were proposed. -- Abstract: Bromate is recognized as an oxyhalide disinfection byproduct in drinking water. In this paper, Fe(II)–Al(III) layered double hydroxides (Fe–Al LDHs) prepared by the ultrasound-assisted co-precipitation method were used for the reduction of bromate in solution. The Fe–Al LDHs particles were characterized by X-ray diffractometer, scanning electron microscopy and thermogravimetry–differential scanning calorimetry. It was found that ultrasound irradiation assistance promoted the formation of the hydrotalcite-like phase and then improved the removal efficiency of bromate. In addition, the effects of solid-to-solution ratio, contact time, initial bromate concentration, initial pH, coexisting anions on the bromate removal were investigated. The results showed the bromate with an initial concentration of 1.56 μmol/L could be completely removed from solution by Fe–Al LDHs within 120 min. When the initial bromate concentration was 7.81 μmol/L, the Fe–Al LDHs with irradiation time of 30 min exhibited the optimum removal efficiency and the bromate removal capacity (q e ) was 6.80 μmol/g. In addition, the appearance of sulfate and production of bromide were observed simultaneously in this process, which suggested that ion-exchange between sulfate and bromate, and the reduction of bromate to bromide by Fe 2+ were the main mechanisms responsible for the bromate removal by Fe–Al LDHs

  15. Solid-Phase Fe Speciation along the Vertical Redox Gradients in Floodplains using XAS and Mössbauer Spectroscopies

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Chunmei [Department; Kukkadapu, Ravi K. [Environmental; Lazareva, Olesya [Department; Sparks, Donald L. [Department

    2017-06-30

    Properties of Fe minerals are poorly understood in natural soils and sediments with variable redox conditions. In this study, we combined 57Fe Mössbauer and Fe K-edge X-ray absorption spectroscopic techniques to assess solid-phase Fe speciation along the vertical redox gradients of floodplain profiles, which exhibited a succession of oxic, anoxic and suboxic-oxic zones with increasing depth along the vertical profiles. The anoxic conditions at the intermediate horizon (55-80 cm) of the eastern floodplain resulted in extensive depletion of Fe(III)-oxides including both ferrihydrite and goethite, concurrent with a corresponding reduction of phyllosilicates(PS)-Fe(III) to PS-Fe(II). In addition, the anoxic conditions increased the crystallinity of Fe(III)-oxides in this reduced zone, relative to the oxic zones. In the most reduced intermediate sediments at 80-120cm of the western floodplain, the anoxic conditions drove the complete reductive dissolution of Fe(III) oxides, as well as the greatest reduction (48-55%) in PS-Fe(III). In both oxic near-surface horizon and oxic-suboxic gravel aquifers beneath the soil horizons, Fe(III)-oxides were mainly present as ferrihydrite with a less amount of goethite, which preferentially occurred as nanogoethite or Al/Si-substituted goethite. Ferrihydrite with varying crystallinity or impurities such as organic matter, Al or Si, persisted under suboxic-oxic conditions in the floodplain. This study indicates that vertical redox gradients exert a major control on the quantity and speciation of Fe(III) oxides as well as the oxidation state of structural Fe in PS, which could significantly affect nutrient cycling and carbon (de)stabilization.

  16. Nanoparticulate iron(III) oxo-hydroxide delivers safe iron that is well absorbed and utilised in humans

    Science.gov (United States)

    Pereira, Dora I.A.; Bruggraber, Sylvaine F.A.; Faria, Nuno; Poots, Lynsey K.; Tagmount, Mani A.; Aslam, Mohamad F.; Frazer, David M.; Vulpe, Chris D.; Anderson, Gregory J.; Powell, Jonathan J.

    2014-01-01

    Iron deficiency is the most common nutritional disorder worldwide with substantial impact on health and economy. Current treatments predominantly rely on soluble iron which adversely affects the gastrointestinal tract. We have developed organic acid-modified Fe(III) oxo-hydroxide nanomaterials, here termed nano Fe(III), as alternative safe iron delivery agents. Nano Fe(III) absorption in humans correlated with serum iron increase (P solubility. The most promising preparation (iron hydroxide adipate tartrate: IHAT) showed ~80% relative bioavailability to Fe(II) sulfate in humans and, in a rodent model, IHAT was equivalent to Fe(II) sulfate at repleting haemoglobin. Furthermore, IHAT did not accumulate in the intestinal mucosa and, unlike Fe(II) sulfate, promoted a beneficial microbiota. In cellular models, IHAT was 14-fold less toxic than Fe(II) sulfate/ascorbate. Nano Fe(III) manifests minimal acute intestinal toxicity in cellular and murine models and shows efficacy at treating iron deficiency anaemia. From the Clinical Editor This paper reports the development of novel nano-Fe(III) formulations, with the goal of achieving a magnitude less intestinal toxicity and excellent bioavailability in the treatment of iron deficiency anemia. Out of the tested preparations, iron hydroxide adipate tartrate met the above criteria, and may become an important tool in addressing this common condition. PMID:24983890

  17. Chemical and toxicological assessment of arsenic sorption onto Fe-sericite composite powder and beads.

    Science.gov (United States)

    Kim, Jiwon; Lee, Cheongho; Lee, Seung Mok; Lalhmunsiama; Jung, Jinho

    2018-01-01

    Batch sorption and leaching of arsenic (1-30mgL -1 ) on Fe-sericite composite powder and beads were investigated in this study. Fe-sericite composite powder was made from natural sericite modified with iron, and alginate was used to transform the powder into beads. The maximum sorption capacities of the Fe-sericite composite powder (15.04 and 13.21mgg -1 for As(III) and As(V), respectively) were higher than those of the corresponding beads (9.02 and 7.11mgg -1 for As(III) and As(V), respectively) owing to the higher specific surface area of the powder. In addition, the leaching amounts of As(III) from Fe-sericite composite beads (≤ 15.03%) were higher than those of the corresponding powder (≤ 5.71%). However, acute toxicity of As(III)-sorbed Fe-sericite composite beads toward Daphnia magna was not significantly different from that of the corresponding powder (p > 0.05). Considering higher uptake of the powder particles by the daphnids, Fe-sericite composite beads seem to be a more appropriate and safer sorbent for arsenic removal in practical application. Based on Fe content, Fe-sericite composite beads had similar or higher maximum sorption capacities (71.19 and 56.11mgg -1 Fe for As(III) and As(V), respectively) than those of previously reported sorbents. Copyright © 2017 Elsevier Inc. All rights reserved.

  18. Fe-Impregnated Mineral Colloids for Peroxide Activation: Effects of Mineral Substrate and Fe Precursor.

    Science.gov (United States)

    Li, Yue; Machala, Libor; Yan, Weile

    2016-02-02

    Heterogeneous iron species at the mineral/water interface are important catalysts for the generation of reactive oxygen species at circumneutral pH. One significant pathway leading to the formation of such species arises from deposition of dissolved iron onto mineral colloids due to changes in redox conditions. This study investigates the catalytic properties of Fe impregnated on silica, alumina, and titania nanoparticles (as prototypical mineral colloids). Fe impregnation was carried out by immersing the mineral nanoparticles in dilute Fe(II) or Fe(III) solutions at pH 6 and 3, respectively, in an aerobic environment. The uptake of iron per unit surface area follows the order of nTiO2 > nAl2O3 > nSiO2 for both types of Fe precursors. Impregnation of mineral particles in Fe(II) solutions results in predominantly Fe(III) species due to efficient surface-mediated oxidation. The catalytic activity of the impregnated solids to produce hydroxyl radical (·OH) from H2O2 decomposition was evaluated using benzoic acid as a probe compound under dark conditions. Invariably, the rates of benzoic acid oxidation with different Fe-laden particles increase with the surface density of Fe until a critical density above which the catalytic activity approaches a plateau, suggesting active Fe species are formed predominantly at low surface loadings. The critical surface density of Fe varies with the mineral substrate as well as the aqueous Fe precursor. Fe impregnated on TiO2 exhibits markedly higher activity than its Al2O3 and SiO2 counterparts. The speciation of interfacial Fe is analyzed with diffuse reflectance UV-vis analysis and interpretation of the data in the context of benzoic oxidation rates suggests that the surface activity of the solids for ·OH generation correlates strongly with the isolated (i.e., mononuclear) Fe species. Therefore, iron dispersed on mineral colloids is a significant form of reactive iron surfaces in the aquatic environment.

  19. Clomiphene citrate therapy for male infertility.

    Science.gov (United States)

    Allag, I S; Alexander, N J

    1979-11-01

    We have summarized 697 reported cases of the use of clomiphene citrate for the improvement of semen quality. Basal levels of gonadotropins are useful criteria for the differential diagnosis of hypo- and hypergonadotropic hypogonadism. Patients with an intact hypothalamic-pituitary-gonadal axis are most likely to respond to clomiphene citrate. Twenty-five mg. per day, administered in a cyclic fashion for a period of six to nine months, caused the greatest improvement. A higher dose (50 mg. per day) may be effective in men who do not respond to 25 mg. During the course of therapy gonadotropin levels and semen samples should be analyzed periodically. This drug is not currently approved for use in men; the incidence of side effects, particularly with long-term treatment, is unknown.

  20. Solid-Phase Fe Speciation along the Vertical Redox Gradients in Floodplains using XAS and Mössbauer Spectroscopies.

    Science.gov (United States)

    Chen, Chunmei; Kukkadapu, Ravi K; Lazareva, Olesya; Sparks, Donald L

    2017-07-18

    Properties of Fe minerals are poorly understood in natural soils and sediments with variable redox conditions. In this study, we combined 57 Fe Mössbauer and Fe K-edge X-ray absorption spectroscopic (XAS) techniques to assess solid-phase Fe speciation along the vertical redox gradients of floodplains, which exhibited a succession of oxic, anoxic, and suboxic-oxic zones with increasing depth along the vertical profiles. The incised stream channel is bounded on the east by a narrow floodplain and a steep hillslope, and on the west by a broad floodplain. In the eastern floodplain, the anoxic conditions at the intermediate horizon (55-80 cm) coincided with lower Fe(III)-oxides (particularly ferrihydrite), in concurrence with a greater reduction of phyllosilicates(PS)-Fe(III) to PS-Fe(II), relative to the oxic near-surface and sandy gravel layers. In addition, the anoxic conditions in the eastern floodplain coincided with increased crystallinity of goethite, relative to the oxic layers. In the most reduced intermediate sediments at 80-120 cm of the western floodplain, no Fe(III)-oxides were detected, concurrent with the greatest PS-Fe(III) reduction (PS-Fe(II)/Fe(III) ratio ≈ 1.2 (Mössbauer) or 0.8 (XAS)). In both oxic near-surface horizon and oxic-suboxic gravel aquifers beneath the soil horizons, Fe(III)-oxides were mainly present as ferrihydrite with a much less amount of goethite, which preferentially occurred as nanogoethite or Al/Si-substituted goethite. Ferrihydrite with varying crystallinity or impurities such as organic matter, Al or Si, persisted under suboxic-oxic conditions in the floodplain. This study indicates that vertical redox gradients exert a major control on the quantity and speciation of Fe(III) oxides as well as the oxidation state of structural Fe in PS, which could significantly affect nutrient cycling and carbon (de)stabilization.

  1. Electrical and dielectric investigation of intercalated polypyrrole montmorillonite nanocomposite prepared by spontaneous polymerization of pyrrole into Fe(III)-montmorillonite

    Energy Technology Data Exchange (ETDEWEB)

    Zidi, Rabii, E-mail: rabiizidi@gmail.com [Physical Chemistry Laboratory for Mineral Materials and their Applications, National Center for Research in Materials Sciences (CNRSM), B.P.73, 8020 Soliman (Tunisia); Bekri-Abbes, Imene; Sdiri, Nasr [Physical Chemistry Laboratory for Mineral Materials and their Applications, National Center for Research in Materials Sciences (CNRSM), B.P.73, 8020 Soliman (Tunisia); Vimalanandan, Ashokanand; Rohwerder, Michael [Max-Planck-Institut für Eisenforschung GmbH, Düsseldorf (Germany); Srasra, Ezzeddine [Physical Chemistry Laboratory for Mineral Materials and their Applications, National Center for Research in Materials Sciences (CNRSM), B.P.73, 8020 Soliman (Tunisia)

    2016-10-15

    Highlights: • We have prepared and characterized a Fe-MMT/PPy nanocomposites. • Investigate electrical conductivity and dielectric properties of the nanocomposite. • Investigate the temperature and frequency dependencies of alternating current conductivity of nanocomposites. - Abstract: Pyrrole was introduced into Fe(III)-exchanged montmorillonite to spontaneously polymerize within the interlayer resulting in the formation of intercalated polypyrrole-montmorillonite nanocomposite. The molar proportion of pyrrole to interlayer Fe{sup 3+} (R) has been varied from 0.5 to 5. The nanocomposite has been characterized by X-ray diffraction, Scanning Electronic Microscope, FTIR spectroscopy and impedance spectroscopy. It has been shown that intercalated polypyrrole montmorillonite nanocomposite was obtained. The results showed that the dc conductivity and dielectric properties of polypyrrole depend on R. The alternating current (ac) conductivity of the polymer obeys the power law, i.e., σ{sub ac}(ω) = Aω{sup s}. The alternating conductivity of nanocomposite was controlled by the correlated barrier hopping model. The activation energy for alternating current mechanism decreases with increasing frequency which confirms the hopping conduction to the dominant mechanism as compared with the dc activation energy. The dielectric relaxation mechanism was explained on the basis of complex dielectric modulus.

  2. nanoparticles synthesized by citrate precursor m

    African Journals Online (AJOL)

    user

    (M=Co, Cu) nanoparticles synthesized by citrate precursor method ... The structural characterization was carried out using an X-ray Diffractometer (Rikagu Miniflex, Japan) ..... His current area of interest includes magnetic nanomaterials.

  3. Effect of sildenafil citrate (Viagra) on coronary flow in normal subjects.

    Science.gov (United States)

    Ishikura, Fuminobu; Beppu, Shintaro; Ueda, Hiroaki; Nehra, Ajay; Khandheria, Bijoy K

    2008-01-01

    The purpose of this study was to evaluate the effect of sildenafil citrate (Viagra) on coronary function in normal subjects. The study assessed mean blood pressure, left anterior descending coronary artery (LAD) flow, and echocardiographic variables before and 30 and 60 minutes after taking 50 mg of sildenafil citrate. The mean velocity of LAD flow was assessed with Doppler flow imaging. The study subjects were 6 healthy male volunteers (mean age 37 years). The mean velocity of LAD flow increased 60 minutes after taking sildenafil citrate, but there were no other changes. Two volunteers felt mild flashing and one had mild headache during the study. Sildenafil citrate caused vasodilatation in a normal coronary artery without systemic pressure drops. These results suggest that the agent itself did not have negative effects on the heart in normal subjects.

  4. Molecular [(Fe3)–(Fe3)] and [(Fe4)–(Fe4)] coordination cluster pairs as single or composite arrays.

    Science.gov (United States)

    Sañudo, E Carolina; Uber, Jorge Salinas; Pons Balagué, Alba; Roubeau, Olivier; Aromí, Guillem

    2012-08-06

    The synthesis of molecular cluster pairs is a challenge for coordination chemists due to the potential applications of these species in molecular spintronics or quantum computing. The ligand H(4)L, 1,3-bis-(3-oxo-3-(2-hydroxyphenyl)-propionyl)-2-methoxybenzene, has been successfully used to obtain a series of such complexes using the basic Fe(III) trinuclear carboxylates as starting materials. Synthetic control has allowed the isolation of the two molecular cluster pairs that form the composite [Fe(4)O(2)(PhCO(2))(6)(H(2)L)(pz)](2)[Fe(3)O(PhCO(2))(5)(py)(H(2)L)](2) (1). The dimers of trinuclear units, [Fe(3)O(PhCO(2))(5)(H(2)O)(H(2)L)](2) (2) and [Fe(3)O(o-MePhCO(2))(5)(H(2)L)(py)](2) (3), and the dimers of tetranuclear units, [Fe(4)O(2)(PhCO(2))(6)(H(2)L)(pz)](2) (4) and [Fe(4)O(2)(o-MePhCO(2))(6)(H(2)L)(pz)](2) (5), are presented here. The magnetic properties of the reported aggregates show that they are pairs of semi-independent clusters weakly interacting magnetically as required for two-qubit quantum gates.

  5. Immobilization of radionuclides and heavy metals through anaerobic bio-oxidation of Fe(II)

    International Nuclear Information System (INIS)

    Lack, J.G.; Chaudhuri, S.K.; Kelly, S.D.; Kemner, K.M.; O'Connor, S.M.; Coates, J.D.

    2002-01-01

    Adsorption of heavy metals and radionuclides (HMR) onto iron and manganese oxides has long been recognized as an important reaction for the immobilization of these compounds. However, in environments containing elevated concentrations of these HMR the adsorptive capacity of the iron and manganese oxides may well be exceeded, and the HMR can migrate as soluble compounds in aqueous systems. Here we demonstrate the potential of a bioremediative strategy for HMR stabilization in reducing environments based on the recently described anaerobic nitrate-dependent Fe(II) oxidation by Dechlorosoma species. Bio-oxidation of 10 mM Fe(II) and precipitation of Fe(III) oxides by these organisms resulted in rapid adsorption and removal of 55 μM uranium and 81 μM cobalt from solution. The adsorptive capacity of the biogenic Fe(III) oxides was lower than that of abiotically produced Fe(III) oxides (100 μM for both metals), which may have been a result of steric hindrance by the microbial cells on the iron oxide surfaces. The binding capacity of the biogenic oxides for different heavy metals was indirectly correlated to the atomic radius of the bound element. X-ray absorption spectroscopy indicated that the uranium was bound to the biogenically produced Fe(III) oxides as U(VI) and that the U(VI) formed bidentate and tridentate inner-sphere complexes with the Fe(III) oxide surfaces. Dechlorosoma suillum oxidation was specific for Fe(II), and the organism did not enzymatically oxidize U(IV) or Co(II). Small amounts (less than 2.5 μM) of Cr(III) were reoxidized by D. suillum; however, this appeared to be inversely dependent on the initial concentration of the Cr(III). The results of this study demonstrate the potential of this novel approach for stabilization and immobilization of HMR in the environment.

  6. Moessbauer spectroscopic study on valence-detrapping and trapping of mixed-valence trinuclear iron (III, III, II) fluorine-substitute benzoate complexes

    International Nuclear Information System (INIS)

    Sakai, Y.; Onaka, S.; Ogiso, R.; Takayama, T.; Takahashi, M.; Nakamoto, T.

    2012-01-01

    Four mixed-valence trinuclear iron(III, III, II) fluorine-substituted benzoate complexes were synthesized; Fe 3 O(C 6 F 5 COO) 6 (C 5 H 5 N) 3 ·CH 2 Cl 2 (1), Fe 3 O(C 6 F 5 COO) 6 (C 5 H 5 N) 3 (2), Fe 3 O(2H-C 6 F 4 COO) 6 (C 5 H 5 N) 3 (3), and Fe 3 O(4H-C 6 F 4 COO) 6 (C 5 H 5 N) 3 (4). By means of 57 Fe-Moessbauer spectroscopy, valence-detrapping and trapping phenomena have been investigated for the four mixed-valence complexes. The valence state of three iron ions is trapped at lower temperatures while it is fully detrapped at higher temperatures for 1. Valence detrapping is not observed for 2, 3, and 4 even at room temperature, although Moessbauer spectra for 3 and 4 show a complicated temperature dependence. (author)

  7. SERS substrates fabricated using ceramic filters for the detection of bacteria: Eliminating the citrate interference

    Science.gov (United States)

    Mosier-Boss, P. A.; Sorensen, K. C.; George, R. D.; Sims, P. C.; O'braztsova, A.

    2017-06-01

    It was found that spectra obtained for bacteria on SERS substrates fabricated by filtering citrate-generated Ag nanoparticles (NPs) onto rigid, ceramic filters exhibited peaks due to citrate as well as the bacteria. In many cases the citrate spectrum overwhelmed that of the bacteria. Given the simplicity of the method to prepare these substrates, means of eliminating this citrate interference were explored. It was found that allowing a mixture of bacteria suspension and citrate-generated Ag NPs to incubate prior to filtering onto the ceramic filter eliminated this interference.

  8. Uranium dioxide in Fe(III)-containing ionic liquids with DMSO: Dissolution, separation, and structural characterization

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Aining; Chu, Taiwei, E-mail: twchu@pku.edu.cn

    2016-11-15

    UO{sub 2} can be successfully dissolved in imidazolium-based Fe(III)-containing ionic liquids (ILs) with the help of DMSO. Spectroscopic studies and X-ray diffraction show that UO{sub 2}Cl{sub 4}{sup 2−} is the principal product. The dissolved uranyl species can be easily separated from the ILs via a combination of crystallization and solvent extraction. Moreover, even if 15.2 wt% of the rare-earth elements of Sm, Eu, and Gd, compared with the total amount of uranium and the rare-earth elements, exist in the IL, only uranium-containing crystals would be selectively formed and separated from the system. The solvents of acetone and acetonitrile could be used to separate the rare-earth elements from uranium in the IL with the help of imidazolium chloride. Considering the complete process from the dissolution of UO{sub 2} and some rare-earth oxides to the separation of uranium and rare-earth elements in the IL, the facile approach is promising for the spent nuclear fuel reprocessing. - Graphical abstract: UO{sub 2} can be successfully dissolved in Fe-containing ILs with the help of DMSO to form UO{sub 2}Cl{sub 4}{sup 2−}. The rare earth elements of Sm, Eu, and Gd can be separated from uranium in the IL, and meanwhile, the recovery of dissolved uranyl species and Fe-containing IL can also be achieved. - Highlights: • Dissolution of UO{sub 2} can be successfully achieved in imidazolium-based Fe-containing ILs with the help of DMSO without additional oxidants. • Compared with the total amount of uranium and the rare-earth elements, even if 15.2 wt% of the rare-earth elements of Sm, Eu, and Gd exist in the IL, only uranium-containing crystals would be selectively formed and separated from the system. • The separation of the rare-earth elements from uranium has also been achieved via a combination of crystallization and solvent extraction.

  9. Uranium dioxide in Fe(III)-containing ionic liquids with DMSO: Dissolution, separation, and structural characterization

    International Nuclear Information System (INIS)

    Yao, Aining; Chu, Taiwei

    2016-01-01

    UO_2 can be successfully dissolved in imidazolium-based Fe(III)-containing ionic liquids (ILs) with the help of DMSO. Spectroscopic studies and X-ray diffraction show that UO_2Cl_4"2"− is the principal product. The dissolved uranyl species can be easily separated from the ILs via a combination of crystallization and solvent extraction. Moreover, even if 15.2 wt% of the rare-earth elements of Sm, Eu, and Gd, compared with the total amount of uranium and the rare-earth elements, exist in the IL, only uranium-containing crystals would be selectively formed and separated from the system. The solvents of acetone and acetonitrile could be used to separate the rare-earth elements from uranium in the IL with the help of imidazolium chloride. Considering the complete process from the dissolution of UO_2 and some rare-earth oxides to the separation of uranium and rare-earth elements in the IL, the facile approach is promising for the spent nuclear fuel reprocessing. - Graphical abstract: UO_2 can be successfully dissolved in Fe-containing ILs with the help of DMSO to form UO_2Cl_4"2"−. The rare earth elements of Sm, Eu, and Gd can be separated from uranium in the IL, and meanwhile, the recovery of dissolved uranyl species and Fe-containing IL can also be achieved. - Highlights: • Dissolution of UO_2 can be successfully achieved in imidazolium-based Fe-containing ILs with the help of DMSO without additional oxidants. • Compared with the total amount of uranium and the rare-earth elements, even if 15.2 wt% of the rare-earth elements of Sm, Eu, and Gd exist in the IL, only uranium-containing crystals would be selectively formed and separated from the system. • The separation of the rare-earth elements from uranium has also been achieved via a combination of crystallization and solvent extraction.

  10. Size-Controlled Production of Gold Bionanoparticles Using the Extremely Acidophilic Fe(III-Reducing Bacterium, Acidocella aromatica

    Directory of Open Access Journals (Sweden)

    Intan Nurul Rizki

    2018-02-01

    Full Text Available Recycling of gold-bearing “urban mine” resources, such as waste printed circuit boards (PCBs, is attracting an increasing interest. Some of the gold leaching techniques utilize acidic lixiviants and in order to eventually target such acidic leachates, the utility of the acidophilic Fe(III-reducing heterotrophic bacterium, Acidocella (Ac. aromatica PFBC was evaluated for production of Au(0 bionanoparticles (bio-AuNPs. Au(III ions (as AuCl4−, initially 10 mg/L, were readily adsorbed onto the slightly-positively charged Ac. aromatica cell surface and transported into cytoplasm to successfully form intracellular bio-AuNPs in a simple one-step microbiological reaction. Generally, increasing the initial concentration of formate as e-donor corresponded to faster Au(III bioreduction and a greater number of Au(0 nucleation sites with less crystal growth within 40–60 h: i.e., use of 1, 5, 10, or 20 mM formate led to production of bio-AuNPs of 48, 24, 13, or 12 nm in mean particle size with 2.3, 17, 62, and 97 particles/cell, respectively. Addition of Cu2+ as an enzymatic inhibitor significantly decreased the number of Au(0 nucleation sites but enhanced crystal growth of individual particles. As a result, the manipulation of the e-donor concentration combined with an enzyme inhibitor enabled the 3-grade size-control of bio-AuNPs (nearly within a normal distribution at 48, 26 or 13 nm by use of 1 mM formate, 20 mM formate (+Cu2+ or 10 mM formate, respectively, from highly acidic, dilute Au(III solutions.

  11. Correlation of reactivity with structural factors in a series of Fe(II) substituted cobalt ferrites

    International Nuclear Information System (INIS)

    Sileo, Elsa E.; Garcia Rodenas, Luis; Paiva-Santos, Carlos O.; Stephens, Peter W.; Morando, Pedro J.; Blesa, Miguel A.

    2006-01-01

    A series of powdered cobalt ferrites, Co x Fe 3- x O 4 with 0.66≤x II , were synthesized by a mild procedure, and their Fe and Co site occupancies and structural characteristics were explored using X-ray anomalous scattering and the Rietveld refinement method. The dissolution kinetics, measured in 0.1 M oxalic acid aqueous solution at 70 deg. C, indicate in all cases the operation of a contracting volume rate law. The specific rates increased with the Fe II content following approximately a second-order polynomial expression. This result suggests that the transfer of Fe III controls the dissolution rate, and that the leaching of a first layer of ions Co II and Fe II leaves exposed a surface enriched in slower dissolving octahedral Fe III ions. Within this model, inner vicinal lattice Fe II accelerates the rate of Fe III transfer via internal electron hopping. A chain mechanism, involving successive electron transfers, fits the data very well. - Graphical abstract: The electron exchange between octahedral Fe II and Fe III ions has important consequences on the specific dissolution rates. Display Omitted

  12. Synthesis of a 3D lanthanum(III) MOFs as a multi-chemosensor to Cr(VI)-containing anion and Fe(III) cation based on a flexible ligand

    Science.gov (United States)

    Ma, Yang-Min; Liu, Tong; Huang, Wen-Huan

    2018-02-01

    Based on La(NO3)3·6H2O and 4,4‧-((5-carboxy-1,3-phenylene)bis(oxy))dibenzoic acid (H3cpbda), a 3D porous MOFs, [La(cpbda)(H2O)1.5]n (1), was synthesized by hydrothermal method and further characterized by single-crystal X-ray diffraction, power X-ray diffraction, IR spectroscopy, thermal-gravimetric analysis and fluorescence spectroscopy. Owing to its good stabilities and fluorescence property, the sensing experiments on sixteen cations and eleven anions were implemented. Moreover, the further titration processes show 1 can sensitively detect the Fe(III) cation and Cr(VI)-containing anions by quenching responses.

  13. Microstructural properties of electrochemically prepared Ni-Fe-W powders

    Energy Technology Data Exchange (ETDEWEB)

    Ribic-Zelenovic, L. [Faculty of Agronomy, University of Kragujevac, Cacak (Serbia); Cirovic, N. [Joint Laboratory for Advanced Materials of SASA, Technical Faculty Cacak, University of Kragujevac, Cacak (Serbia); Spasojevic, M. [Faculty of Agronomy, University of Kragujevac, Cacak (Serbia); Mitrovic, N., E-mail: nmitrov@tfc.kg.ac.rs [Joint Laboratory for Advanced Materials of SASA, Technical Faculty Cacak, University of Kragujevac, Cacak (Serbia); Maricic, A. [Joint Laboratory for Advanced Materials of SASA, Technical Faculty Cacak, University of Kragujevac, Cacak (Serbia); Pavlovic, V. [Faculty of Agriculture, University of Belgrade, Belgrade (Serbia)

    2012-07-16

    A nanostructured Ni-Fe-W powder was obtained by electrodeposition from ammonium citrate electrolyte within the current density range of 500-1000 mA cm{sup -2} at the electrolyte temperature of 50 Degree-Sign C-70 Degree-Sign C. XRD analysis shows that the powder contains an amorphous matrix having embedded nanocrystals of the FCC solid solution of iron and tungsten in nickel, with an average crystal grain size of 3.4 nm, a high internal microstrain value and a high density of chaotically distributed dislocations. EDS analysis exhibits that the chemical composition of the Ni-24%Fe-11%W powder does not depend upon current density and electrolyte temperature due to the diffusion control of the process of codeposition of nickel, iron and tungsten. SEM micrographs show that the electrodeposition results in the formation of two particle shapes: large cauliflower-like particles and small dendrite particles. The cauliflower-like particles contain deep cavities at hydrogen evolution sites. Cavity density increases with increasing deposition current density. Smaller powder particles are formed at higher temperatures and at higher current densities. During the first heating, relative magnetic permeability decreases reaching the Curie temperature at about 350 Degree-Sign C and after cooling exhibits a 12% increase due to the performed relaxation process. Following the second heating to 500 Degree-Sign C, the magnetic permeability of the powder is about 5% lower than that of the as-prepared powder due to crystallization of the amorphous phase of the powder and the crystal grain growth in FCC phase. - Highlights: Black-Right-Pointing-Pointer Electrodeposition Ni-Fe-W powder from ammonium citrate electrolyte (500-1000 mA cm{sup -2}). Black-Right-Pointing-Pointer Powder contains amorphous matrix and embedded nanocrystals 3.4 nm. Black-Right-Pointing-Pointer Chemical composition Ni-24%Fe-11%W do not depend upon current density and electrolyte temperature. Black

  14. Whole-body retention studies of /sup 169/Yb-citrate. Estimation of radiation dose to humans from /sup 169/Yb-citrate

    Energy Technology Data Exchange (ETDEWEB)

    Ando, A; Hiraki, T [Kanazawa Univ. (Japan). School of Paramedicine; Mori, H; Ando, I; Hisada, K

    1977-09-01

    For purpose of the estimation of the radiation dose to humans from /sup 169/Yb-citrate, the whole-body retention studies using five rats were carried out. Following intravenous administration of /sup 169/Yb-citrate, the whole-body activity was monitored for 40 days by the animal counter. The whole-body retention curve consisted of three components: the first with a 3.6 hours effective half-time, the second with an 154 hours effective half-time and the third with a 29.9 days effective half-time. Therefore it was assumed that 32% of the administered /sup 169/Yb-citrate clears from the kidney with a short biologic half-time (3.6 hours), 18% remains in the liver and other soft tissues with a relatively long biologic half-time (194 hours) and 50% remains in the bone with a long biologic half-time (850 days). Based on these biological data and the MIRD Committee method, the average dose to the bone and whole-body were 20.8 rads/mCi and 4.5 rads/mCi respectively.

  15. MgFe{sub 2}O{sub 4}/ZrO{sub 2} composite nanoparticles for hyperthermia applications

    Energy Technology Data Exchange (ETDEWEB)

    Rashid, Amin ur [Magnetism Laboratory, Department of Physics, COMSATS Institute of Information Technology, Islamabad (Pakistan); Department of Applied Physical and Material Sciences, University of Swat, Khyber Pakhtunkhwa (Pakistan); Humayun, Asif [Magnetism Laboratory, Department of Physics, COMSATS Institute of Information Technology, Islamabad (Pakistan); Manzoor, Sadia, E-mail: sadia_manzoor@comsats.edu.pk [Magnetism Laboratory, Department of Physics, COMSATS Institute of Information Technology, Islamabad (Pakistan)

    2017-04-15

    MgFe{sub 2}O{sub 4}/ZrO{sub 2} composites containing ZrO{sub 2} in different weight percentages from 0% to 80% were prepared via the citrate gel technique as potential candidate materials for magnetic hyperthermia. The biocompatible ceramic ZrO{sub 2} was introduced to prevent MgFe{sub 2}O{sub 4} nanoparticles from aggregation and to reduce their dipolar interactions in order to enhance the specific absorption rate (SAR). Structural and magnetic properties of the samples were studied using powder X-ray diffraction (XRD), transmission electron microscopy (TEM) and a vibrating sample magnetometer (VSM). Magnetically induced heating in radio frequency (RF) magnetic fields was observed in all samples. Most significantly, the sample with only 20 wt% MgFe{sub 2}O{sub 4} has been found to have a SAR that is larger than that of pure MgFe{sub 2}O{sub 4}. This is an important finding from the point of view of biomedical applications, because ZrO{sub 2} in known to have low toxicity and a higher biocompatibility as compared to ferrites. - Highlights: • MgFe{sub 2}O{sub 4} and ZrO{sub 2} composite nanoparticles with different weight percentages of ZrO{sub 2} were prepared via the citrate gel technique. • Significant variation in magnetic properties was observed with increasing the weight % of ZrO{sub 2}. • Magnetically induced heating was observed when the composites were subjected to RF magnetic field. • Most significantly, the sample 80 wt% ZrO{sub 2} has been found to have SAR that is larger than that of pure MgFe{sub 2}O{sub 4}. • The SAR was found to have a strong dependence on magnetic dipolar interactions.

  16. [Effect of glucose and lactose on the utilization of citrate by Lactobacillus casei subsp. rhamnosus ATCC 7469].

    Science.gov (United States)

    Benito de Cárdenas, I L; Medina, R; Oliver, G

    1992-01-01

    The utilization of citrate by Lactobacillus casei subsp. rhamnosus ATCC 7469 in a complex medium containing glucose, lactose or citrate was investigated, as an approach to the question of the transport of this acid and the possible relationship with the production of flavour compounds (diacetyl and acetoin). This lactobacillus uses citrate as an energy source in the absence of carbohydrates. External pH and growth increases when citrate is added to complex medium. The presence of citrate does not affect glucose uptake. L. casei ATCC 7469 possibly uses a transport system for citrate utilization, and citrate uptake seems to be under glucose or lactose control. Lactose only inhibits the entrance of citrate at high concentration while the utilization of this acid was negatively regulated by low glucose concentration.

  17. Phosphatase activity of Poa pratensis seeds. III. Effect of fluoride, citrate, urea and other substances on the activity of acid phosphatase Ia2 and Ia3

    Directory of Open Access Journals (Sweden)

    Irena Lorenc-Kubis

    2015-01-01

    Full Text Available Effects of fluoride, citrate, urea and other substances on the activity of acid phosphatase a2 and a3 toward p-nitrophenylphosphate and phenylphosphate were investigated. Both enzymes were inhibited by fluoride, p-chloromercuribenzoate and oxalate. Fluoride inhibited acid phosphatase a2 noncorapetitively with p-mitrophenylphosphate, whereas acid phosphatase a3 showed inhibition of mixed type. Hydrolysis of phenylphosphate by both acid phosphatases was activated by citrate. Cytosine and uridine inhibited the activity of phosphatase a2 toward p-nitrophenylphosphate and phenylphosphate, but no effect was observed in case of acid phosphatase a3. After 30 min. incubation with 4 M urea both enzymes lost about 30% of activity.

  18. The formation of light absorbing insoluble organic compounds from the reaction of biomass burning precursors and Fe(III)

    Science.gov (United States)

    Lavi, Avi; Lin, Peng; Bhaduri, Bhaskar; Laskin, Alexander; Rudich, Yinon

    2017-04-01

    Dust particles and volatile organic compounds from fuel or biomass burning are two major components that affect air quality in urban polluted areas. We characterized the products from the reaction of soluble Fe(III), a reactive transition metal originating from dust particles dissolution processes, with phenolic compounds , namely, guaiacol, syringol, catechol, o- and p- cresol that are known products of incomplete fuel and biomass combustion but also from other natural sources such as humic compounds degradation. We found that under acidic conditions comparable to those expected on a dust particle surface, phenolic compounds readily react with dissolved Fe(III), leading to the formation of insoluble polymeric compounds. We characterized the insoluble products by x-ray photoelectron microscopy, UV-Vis spectroscopy, mass spectrometry, elemental analysis and thermo-gravimetric analysis. We found that the major chromophores formed are oligomers (from dimers to pentamers) of the reaction precursors that efficiently absorb light between 300nm and 500nm. High variability of the mass absorption coefficient of the reaction products was observed with catechol and guaiacol showing high absorption at the 300-500nm range that is comparable to that of brown carbon (BrC) from biomass burning studies. The studied reaction is a potential source for the in-situ production of secondary BrC material under dark conditions. Our results suggest a reaction path for the formation of bio-available iron in coastal polluted areas where dust particles mix with biomass burning pollution plumes. Such mixing can occur, for instance in the coast of West Africa or North Africa during dust and biomass burning seasons

  19. Free Rhodium (II) citrate and rhodium (II) citrate magnetic carriers as potential strategies for breast cancer therapy

    Science.gov (United States)

    2011-01-01

    Background Rhodium (II) citrate (Rh2(H2cit)4) has significant antitumor, cytotoxic, and cytostatic activity on Ehrlich ascite tumor. Although toxic to normal cells, its lower toxicity when compared to carboxylate analogues of rhodium (II) indicates Rh2(H2cit)4 as a promising agent for chemotherapy. Nevertheless, few studies have been performed to explore this potential. Superparamagnetic particles of iron oxide (SPIOs) represent an attractive platform as carriers in drug delivery systems (DDS) because they can present greater specificity to tumor cells than normal cells. Thus, the association between Rh2(H2cit)4 and SPIOs can represent a strategy to enhance the former's therapeutic action. In this work, we report the cytotoxicity of free rhodium (II) citrate (Rh2(H2cit)4) and rhodium (II) citrate-loaded maghemite nanoparticles or magnetoliposomes, used as drug delivery systems, on both normal and carcinoma breast cell cultures. Results Treatment with free Rh2(H2cit)4 induced cytotoxicity that was dependent on dose, time, and cell line. The IC50 values showed that this effect was more intense on breast normal cells (MCF-10A) than on breast carcinoma cells (MCF-7 and 4T1). However, the treatment with 50 μM Rh2(H2cit)4-loaded maghemite nanoparticles (Magh-Rh2(H2cit)4) and Rh2(H2cit)4-loaded magnetoliposomes (Lip-Magh-Rh2(H2cit)4) induced a higher cytotoxicity on MCF-7 and 4T1 than on MCF-10A (p rhodium (II) citrate-loaded maghemite nanoparticles and magnetoliposomes induced more specific cytotoxicity on breast carcinoma cells than on breast normal cells, which is the opposite of the results observed with free Rh2(H2cit)4 treatment. Thus, magnetic nanoparticles represent an attractive platform as carriers in Rh2(H2cit)4 delivery systems, since they can act preferentially in tumor cells. Therefore, these nanopaticulate systems may be explored as a potential tool for chemotherapy drug development. PMID:21443799

  20. Effects and mechanisms of action of sildenafil citrate in human chorionic arteries

    Directory of Open Access Journals (Sweden)

    Lynch Tadhg

    2009-04-01

    Full Text Available Abstract Objectives Sildenafil citrate, a specific phosphodiesterase-5 inhibitor, is increasingly used for pulmonary hypertension in pregnancy. Sildenafil is also emerging as a potential candidate for the treatment of intra-uterine growth retardation and for premature labor. Its effects in the feto-placental circulation are not known. Our objectives were to determine whether phosphodiesterase-5 is present in the human feto-placental circulation, and to characterize the effects and mechanisms of action of sildenafil citrate in this circulation. Study Design Ex vivo human chorionic plate arterial rings were used in all experiments. The presence of phosphodiesterase-5 in the feto-placental circulation was determined by western blotting and immunohistochemical staining. In a subsequent series of pharmacologic studies, the effects of sildenafil citrate in pre-constricted chorionic plate arterial rings were determined. Additional studies examined the role of cGMP and nitric oxide in mediating the effects of sildenafil. Results Phosphodiesterase-5 mRNA and protein was demonstrated in human chorionic plate arteries. Immunohistochemistry demonstrated phosphodiesterase-5 within the arterial muscle layer. Sildenafil citrate produced dose dependent vasodilatation at concentrations at and greater than 10 nM. Both the direct cGMP inhibitor methylene blue and the cGMP-dependent protein kinase inhibitor Rp-8-Br-PET-cGMPS significantly attenuated the vasodilation produced by sildenafil citrate. Inhibition of NO production with L-NAME did not attenuate the vasodilator effects of sildenafil. In contrast, sildenafil citrate significantly enhanced the vasodilation produced by the NO donor sodium nitroprusside. Conclusion Phosphodiesterase-5 is present in the feto-placental circulation. Sildenafil citrate vasodilates the feto-placental circulation via a cGMP dependent mechanism involving increased responsiveness to NO.

  1. Effects and mechanisms of action of sildenafil citrate in human chorionic arteries.

    LENUS (Irish Health Repository)

    Maharaj, Chrisen H

    2009-01-01

    OBJECTIVES: Sildenafil citrate, a specific phosphodiesterase-5 inhibitor, is increasingly used for pulmonary hypertension in pregnancy. Sildenafil is also emerging as a potential candidate for the treatment of intra-uterine growth retardation and for premature labor. Its effects in the feto-placental circulation are not known. Our objectives were to determine whether phosphodiesterase-5 is present in the human feto-placental circulation, and to characterize the effects and mechanisms of action of sildenafil citrate in this circulation. STUDY DESIGN: Ex vivo human chorionic plate arterial rings were used in all experiments. The presence of phosphodiesterase-5 in the feto-placental circulation was determined by western blotting and immunohistochemical staining. In a subsequent series of pharmacologic studies, the effects of sildenafil citrate in pre-constricted chorionic plate arterial rings were determined. Additional studies examined the role of cGMP and nitric oxide in mediating the effects of sildenafil. RESULTS: Phosphodiesterase-5 mRNA and protein was demonstrated in human chorionic plate arteries. Immunohistochemistry demonstrated phosphodiesterase-5 within the arterial muscle layer. Sildenafil citrate produced dose dependent vasodilatation at concentrations at and greater than 10 nM. Both the direct cGMP inhibitor methylene blue and the cGMP-dependent protein kinase inhibitor Rp-8-Br-PET-cGMPS significantly attenuated the vasodilation produced by sildenafil citrate. Inhibition of NO production with L-NAME did not attenuate the vasodilator effects of sildenafil. In contrast, sildenafil citrate significantly enhanced the vasodilation produced by the NO donor sodium nitroprusside. CONCLUSION: Phosphodiesterase-5 is present in the feto-placental circulation. Sildenafil citrate vasodilates the feto-placental circulation via a cGMP dependent mechanism involving increased responsiveness to NO.

  2. Characterization of the surfaceome of the metal-reducing bacterium Desulfotomaculum reducens

    Directory of Open Access Journals (Sweden)

    Elena eDalla Vecchia

    2014-08-01

    Full Text Available Desulfotomaculum reducens strain MI-1 is a Gram-positive, sulfate-reducing bacterium also capable of reducing Fe(III. Metal reduction in Gram-positive bacteria is poorly understood. Here, we investigated Fe(III reduction with lactate, a non-fermentable substrate, as the electron donor. Lactate consumption is concomitant to Fe(III reduction, but does not support significant growth, suggesting that little energy can be conserved from this process and that it may occur fortuitously. D. reducens can reduce both soluble (Fe(III-citrate and insoluble (hydrous ferric oxide, HFO Fe(III. Because physically inaccessible HFO was not reduced, we concluded that reduction requires direct contact under these experimental conditions. This implies the presence of a surface exposed reductase capable of transferring electrons from the cell to the extracellular electron acceptor. With the goal of characterizing the role of surface proteins in D. reducens and of identifying candidate Fe(III reductases, we carried out an investigation of the surface proteome (surfaceome of D. reducens. Cell surface exposed proteins were extracted by trypsin cell shaving or by lysozyme treatment, and analyzed by liquid chromatography-tandem mass spectrometry. This investigation revealed that the surfaceome fulfills many functions, including solute transport, protein export, maturation and hydrolysis, peptidoglycan synthesis and modification, and chemotaxis. Furthermore, a few redox-active proteins were identified. Among these, three are putatively involved in Fe(III reduction, i.e., a membrane-bound hydrogenase 4Fe-4S cluster subunit (Dred_0462, a heterodisulfide reductase subunit A (Dred_0143 and a protein annotated as alkyl hydroperoxide reductase but likely functioning as a thiol-disulfide oxidoreductase (Dred_1533.

  3. Organic carbon and reducing conditions lead to cadmium immobilization by secondary Fe mineral formation in a pH-neutral soil.

    Science.gov (United States)

    Muehe, E Marie; Adaktylou, Irini J; Obst, Martin; Zeitvogel, Fabian; Behrens, Sebastian; Planer-Friedrich, Britta; Kraemer, Ute; Kappler, Andreas

    2013-01-01

    Cadmium (Cd) is of environmental relevance as it enters soils via Cd-containing phosphate fertilizers and endangers human health when taken up by crops. Cd is known to associate with Fe(III) (oxyhydr)oxides in pH-neutral to slightly acidic soils, though it is not well understood how the interrelation of Fe and Cd changes under Fe(III)-reducing conditions. Therefore, we investigated how the mobility of Cd changes when a Cd-bearing soil is faced with organic carbon input and reducing conditions. Using fatty acid profiles and quantitative PCR, we found that both fermenting and Fe(III)-reducing bacteria were stimulated by organic carbon-rich conditions, leading to significant Fe(III) reduction. The reduction of Fe(III) minerals was accompanied by increasing soil pH, increasing dissolved inorganic carbon, and decreasing Cd mobility. SEM-EDX mapping of soil particles showed that a minor fraction of Cd was transferred to Ca- and S-bearing minerals, probably carbonates and sulfides. Most of the Cd, however, correlated with a secondary iron mineral phase that was formed during microbial Fe(III) mineral reduction and contained mostly Fe, suggesting an iron oxide mineral such as magnetite (Fe3O4). Our data thus provide evidence that secondary Fe(II) and Fe(II)/Fe(III) mixed minerals could be a sink for Cd in soils under reducing conditions, thus decreasing the mobility of Cd in the soil.

  4. Reductive immobilization of U(VI) in Fe(III) oxide-reducing subsurface sediments: Analysis of coupled microbial-geochemical processes in experimental reactive transport systems. Final Scientific/Technical Report-EMSP 73914

    International Nuclear Information System (INIS)

    Eric E. Roden Matilde M. Urrutia Mark O. Barnett Clifford R. Lange

    2005-01-01

    The purpose of this research was to provide information to DOE on microbiological and geochemical processes underlying the potential use of dissimilatory metal-reducing bacteria (DMRB) to create subsurface redox barriers for immobilization of uranium and other redox-sensitive metal/radionuclide contaminants that were released to the environment in large quantities during Cold War nuclear weapons manufacturing operations. Several fundamental scientific questions were addressed in order to understand and predict how such treatment procedures would function under in situ conditions in the subsurface. These questions revolved the coupled microbial-geochemical phenomena which are likely to occur within a redox barrier treatment zone, and on the dynamic interactions between hydrologic flux and biogeochemical process rates. First, we assembled a robust conceptual understanding and numerical framework for modeling the kinetics of microbial Fe(III) oxide reduction and associated DMRB growth in sediments. Development of this framework is a critical prerequisite for predicting the potential effectiveness of DMRB-promoted subsurface bioremediation, since Fe(III) oxides are expected to be the primary source of electron-accepting capacity for growth and maintenance of DMRB in subsurface environments. We also defined in detail the kinetics of microbial (enzymatic) versus abiotic, ferrous iron-promoted reduction of U(VI) in the presence and absence of synthetic and natural Fe(III) oxide materials. The results of these studies suggest that (i) the efficiency of dissolved U(VI) scavenging may be influenced by the kinetics of enzymatic U(VI) reduction in systems with relative short fluid residence times; (2) association of U(VI) with diverse surface sites in natural soils and sediments has the potential to limit the rate and extent of microbial U(VI) reduction, and in turn modulate the effectiveness of in situ U(VI) bioremediation; and (3) abiotic, ferrous iron (Fe(II)) drive n U

  5. Evaluating the efficacy of citrate anticoagulation during CRRT in cardiac patients

    Directory of Open Access Journals (Sweden)

    А. М. Караськов

    2015-10-01

    Full Text Available Systemic anticoagulation during renal replacement therapy in cardiac patients increases the risk of postoperative complications. Citrate anticoagulation is a promising alternative. The objective of our study was to evaluate the efficacy of citrate anticoagulation and its influence on the parameters of hemostasis and complications.

  6. Influence of iron redox transformations on plutonium sorption to sediments

    Energy Technology Data Exchange (ETDEWEB)

    Hixon, A.E.; Powell, B.A. [Environmental Engineering and Earth Sciences, Clemson Univ., Clemson, SC (United States); Hu, Y.J.; Nitsche, H. [Dept. of Chemistry, Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab., Berkeley, CA (United States); Kaplan, D.I. [Savannah River National Lab., Aiken, SC (United States); Kukkadapu, R.K.; Qafoku, O. [Pacific Northwest National Lab., Richland, WA (United States)

    2010-07-01

    Plutonium subsurface mobility is primarily controlled by its oxidation state, which in turn is loosely coupled to the oxidation state of iron in the system. Experiments were conducted to examine the effect of sediment iron mineral composition and oxidation state on plutonium sorption and reduction. A pH 6.3 vadose zone sediment containing iron oxides and iron-containing phyllosilicates was treated with various complexants (ammonium oxalate) and reductants (hydroxylamine hydrochloride and dithionite-citrate-bicarbonate (DCB)) to selectively leach and/or reduce iron oxide and phyllosilicate/clay Fe(III). {sup 57}Fe-Moessbauer spectroscopy was used to identify initial iron mineral composition of the sediment and monitor dissolution and reduction of iron oxides and reduction of phyllosilicate Fe(III). {sup 57}Fe-Moessbauer spectroscopy showed that the Fe-mineral composition of the untreated sediment is: 25-30% hematite, 60-65% small-particle/Al-goethite, and < 10% Fe(III) in phyllosilicate; there was no detectable Fe(II). Upon reduction with a strong chemical reductant (dithionite-citrate-bicarbonate buffer), much of the hematite and goethite was removed. Partial reduction of phyllosilicate Fe(III) was evident in the sediments subjected to DCB treatment. Sorption of Pu(V) was monitored over one week for the untreated and each of five treated sediment fractions. Plutonium oxidation state speciation in the aqueous and solid phases was monitored using solvent extraction, coprecipitation, and XANES. The rate of sorption appears to correlate with the fraction of Fe(II) in the sediment (untreated or treated). Pu(V) was the only oxidation state measured in the aqueous phase, irrespective of treatment, whereas Pu(IV) and much smaller amounts of Pu(V) and Pu(VI) were measured in the solid phase. Surface-mediated reduction of Pu(V) to Pu(IV) occurred in treated and untreated sediment samples; Pu(V) remained on untreated sediment surface for two days before reducing to Pu

  7. A comparative study of nitrite reduction by synthetic and biogenic Fe(II-III) hydroxysalts green rusts: Evidence for hydroxyl-nitrite green rust formation as an intermediate reaction product.

    Science.gov (United States)

    Ona-Nguema, G.; Guerbois, D.; Morin, G.; Zhang, Y.; Noel, V.; Brest, J.

    2013-12-01

    The occurrence of high nitrite concentrations as a result of anthropogenic activities is an important water quality concern as it is highly toxic to human and fauna, and it is used as a nitrogen source for the assimilation process. The toxicity of nitrite is related to its transformation into carcinogenic N-nitroso compounds, which are suspected to be responsible for some gastric cancers, and to its ability to convert the hemoglobin to methaemoglobin what is then unable to fix oxygen and to transport it to the tissues, involving hypoxia and the blue-baby syndrome [1]. To reduce the adverse effect of nitrite on human health and on macroalgal blooms, any process enhancing the transformation of nitrite ions to nitrogen gas is of interest for the remediation of natural environments. To achieve this purpose the use of processes involving Fe(II)-containing minerals could be considered as one of the best options. Green-rusts are mixed Fe(II-III) layered double hydroxides commonly found in anoxic zones of natural environments such as sediments and hydromorphic soils. In such anoxic environments, green rust minerals play an important role in the biogeochemical redox cycling of iron and nitrogen, and can affect the speciation and mobility of many organic and inorganic contaminants. The present study investigates the reduction of nitrite by two synthetic and two biogenic green rusts. On the one hand, Fe(II-III) hydroxychloride and Fe(II-III) hydroxycarbonate green rusts were used as synthetic interlayer forms of GR, which are referred to as ';syn-GR(CO3)' and ';syn-GR(Cl)', respectively. On the other hand, the study was performed with biogenic Fe(II-III) hydroxycarbonate green rusts obtained from the bioreduction of two ferric precursors, either Fe(III)-oxyhydroxycarbonate or lepidocrocite; these biogenic green rusts are referred to as ';bio-GR(CO3)F' and ';bio-GR(CO3)L', respectively. For synthetic green rusts, results showed that the oxidation of both syn-GR(CO3) and syn

  8. Solid Phase Extraction of Trace Al(III), Fe(II), Co(II), Cu(II), Cd(II) and Pb(II) Ions in Beverages on Functionalized Polymer Microspheres Prior to Flame Atomic Absorption Spectrometric Determinations.

    Science.gov (United States)

    Berber, Hale; Alpdogan, Güzin

    2017-01-01

    In this study, poly(glycidyl methacrylate-methyl methacrylate-divinylbenzene) was synthesized in the form of microspheres, and then functionalized by 2-aminobenzothiazole ligand. The sorption properties of these functionalized microspheres were investigated for separation, preconcentration and determination of Al(III), Fe(II), Co(II), Cu(II), Cd(II) and Pb(II) ions using flame atomic absorption spectrometry. The optimum pH values for quantitative sorption were 2 - 4, 5 - 8, 6 - 8, 4 - 6, 2 - 6 and 2 - 3 for Al(III), Fe(II), Co(II), Cu(II), Cd(II) and Pb(II), respectively, and also the highest sorption capacity of the functionalized microspheres was found to be for Cu(II) with the value of 1.87 mmol g -1 . The detection limits (3σ; N = 6) obtained for the studied metals in the optimal conditions were observed in the range of 0.26 - 2.20 μg L -1 . The proposed method was successfully applied to different beverage samples for the determination of Al(III), Fe(II), Co(II), Cu(II), Cd(II) and Pb(II) ions, with the relative standard deviation of <3.7%.

  9. Arsenic sorption to nanoparticulate mackinawite (FeS): An examination of phosphate competition.

    Science.gov (United States)

    Niazi, Nabeel Khan; Burton, Edward D

    2016-11-01

    Nanoparticulate mackinawite (FeS) can be an important host-phase for arsenic (As) in sulfidic, subsurface environments. Although not previously investigated, phosphate (PO 4 3- ) may compete with As for available sorption sites on FeS, thereby enhancing As mobility in FeS-bearing soils, sediments and groundwater systems. In this study, we examine the effect of PO 4 3- on sorption of arsenate (As(V)) and arsenite (As(III)) to nanoparticulate FeS at pH 6, 7 and 9. Results show that PO 4 3- (at 0.01-1.0 mM P) did not significantly affect sorption of either As(V) or As(III) to nanoparticulate FeS at initial aqueous As concentrations ranging from 0.01 to 1.0 mM. At pH 9 and 7, sorption of both As(III) and As(V) to nanoparticulate FeS was similar, with distribution coefficient (K d ) values spanning 0.76-15 L g -1 (which corresponds to removal of 87-98% of initial aqueous As(III) and As(V) concentrations). Conversely, at pH 6, the sorption of As(III) was characterized by substantially higher K d values (6.3-93.4 L g -1 ) than those for As(V) (K d  = 0.21-0.96 L g -1 ). Arsenic K-edge X-ray absorption near edge structure (XANES) spectroscopy indicated that up to 52% of the added As(V) was reduced to As(III) in As(V) sorption experiments, as well as the formation of minor amounts of an As 2 S 3 -like species. In As(III) sorption experiments, XANES spectroscopy also demonstrated the formation of an As 2 S 3 -like species and the partial oxidation of As(III) to As(V) (despite the strictly O 2 -free experimental conditions). Overall, the XANES data indicate that As sorption to nanoparticulate FeS involves several redox transformations and various sorbed species, which display a complex dependency on pH and As loading but that are not influenced by the co-occurrence of PO 4 3- . This study shows that nanoparticulate FeS can help to immobilize As(III) and As(V) in sulfidic subsurface environments where As co-exists with PO 4 3- . Copyright © 2016 Elsevier Ltd. All

  10. Synthesis of Fe3O4 poly(styrene-glycidyl methacrylate) magnetic porous microspheres and application in the immobilization of Klebsiella sp. FD-3 to reduce Fe(III)EDTA in a NO(x) scrubbing solution.

    Science.gov (United States)

    Wang, Xiaoyan; Zhou, Zuoming; Jing, Guohua

    2013-02-01

    Magnetic poly(styrene-glycidyl methacrylate) porous microspheres (MPPM) with high magnetic contents were prepared by surfactant reverse micelles and emulsion polymerization of monomers, in which the well-dispersed Fe(3)O(4) nanoparticles were modified by polyethylene glycol (PEG) and oleic acid (OA) respectively. The characterizations showed that both of the OA-MPPM and the PEG-MPPM were ferromagnetic, however, the OA-MPPM was used to immobilize the bacteria for more advantages. Therefore, the effects of monomer ratio, surfactant, crosslinker and amount of Fe(3)O(4) on the structure, morphology and magnetic contents of the OA-MPPM were investigated. Then, the OA-MPPM was utilized to immobilize Klebsiella sp. FD-3, an iron-reducing bacterium for Fe(III)EDTA reduction applied in NO(x) removal. Compared with free bacteria, the immobilized FD-3 showed a better tolerance to the unbeneficial pH and temperature conditions. Copyright © 2012 Elsevier Ltd. All rights reserved.

  11. Identification and Spectroscopic Characterization of Nonheme Iron(III) Hypochlorite Intermediates**

    Science.gov (United States)

    Draksharapu, Apparao; Angelone, Davide; Quesne, Matthew G; Padamati, Sandeep K; Gómez, Laura; Hage, Ronald; Costas, Miquel; Browne, Wesley R; de Visser, Sam P

    2015-01-01

    FeIII–hypohalite complexes have been implicated in a wide range of important enzyme-catalyzed halogenation reactions including the biosynthesis of natural products and antibiotics and post-translational modification of proteins. The absence of spectroscopic data on such species precludes their identification. Herein, we report the generation and spectroscopic characterization of nonheme FeIII–hypohalite intermediates of possible relevance to iron halogenases. We show that FeIII-OCl polypyridylamine complexes can be sufficiently stable at room temperature to be characterized by UV/Vis absorption, resonance Raman and EPR spectroscopies, and cryo-ESIMS. DFT methods rationalize the pathways to the formation of the FeIII-OCl, and ultimately FeIV=O, species and provide indirect evidence for a short-lived FeII-OCl intermediate. The species observed and the pathways involved offer insight into and, importantly, a spectroscopic database for the investigation of iron halogenases. PMID:25663379

  12. Structure of short-range-ordered iron(III)-precipitates formed by iron(II) oxidation in water containing phosphate, silicate, and calcium

    Science.gov (United States)

    Voegelin, A.; Frommer, J.; Vantelon, D.; Kaegi, R.; Hug, S. J.

    2009-04-01

    The oxidation of Fe(II) in water leads to the formation of Fe(III)-precipitates that strongly affect the fate of nutrients and contaminants in natural and engineered systems. Examples include the cycling of As in rice fields irrigated with As-rich groundwater or the treatment of drinking water for As removal. Knowledge of the types of Fe(III)-precipitates forming in such systems is essential for the quantitative modeling of nutrient and contaminant dynamics and for the optimization of water purification techniques on the basis of a mechanistic understanding of the relevant biogeochemical processes. In this study, we investigated the local coordination of Fe, P, and Ca in Fe(III)-precipitates formed by aeration of synthetic Fe(II)-containing groundwater with variable composition (pH 7, 2-30 mg/L Fe(II), 2-20 mg/L phosphate-P, 2-20 mg/L silicate-Si, 8 mM Na-bicarbonate or 2.5 mM Ca-&1.5 mM Mg-bicarbonate). After 4 hours of oxidation, Fe(III)-precipitates were collected on 0.2 µm nylon filters and dried. The precipitates were analyzed by Fe K-edge EXAFS (XAS beamline, ANKA, Germany) and by P and Ca K-edge XANES spectroscopy (LUCIA beamline, SLS, Switzerland). The Fe K-edge EXAFS spectra indicated that local Fe coordination in the precipitates systematically shifted with water composition. As long as water contained P, mainly short-range-ordered Fe(III)-phosphate formed (with molar P/Fe ~0.5). In the absence of P, Fe(III) precipitated as hydrous ferric oxide at high Si/Fe>0.5, as ferrihydrite at intermediate Si/Fe, and mainly as lepidocrocite at Si/Fe<0.2. Analysis of the EXAFS by shell-fitting indicated that Fe(III)-phosphates mainly contained mono- or oligomeric (edge- or corner-sharing) Fe and that the linkage between neighboring Fe(III)-octahedra changed from predominantly edge-sharing in Si-rich hydrous ferric oxide to edge- and corner-sharing in ferrihydrite. Electron microscopic data showed that changes in local precipitate structure were systematically

  13. Effect of clomifene citrate plus metformin and clomifene citrate plus placebo on induction of ovulation in women with newly diagnosed polycystic ovary syndrome: randomised double blind clinical trial

    NARCIS (Netherlands)

    Moll, Etelka; Bossuyt, Patrick M. M.; Korevaar, Johanna C.; Lambalk, Cornelis B.; van der Veen, Fulco

    2006-01-01

    OBJECTIVE: To compare the effectiveness of clomifene citrate plus metformin and clomifene citrate plus placebo in women with newly diagnosed polycystic ovary syndrome. DESIGN: Randomised clinical trial. SETTING: Multicentre trial in 20 Dutch hospitals. PARTICIPANTS: 228 women with polycystic ovary

  14. SILDENAFIL CITRATE INDUCED RETINAL TOXICITY-ELECTRORETINOGRAM, OPTICAL COHERENCE TOMOGRAPHY, AND ADAPTIVE OPTICS FINDINGS.

    Science.gov (United States)

    Yanoga, Fatoumata; Gentile, Ronald C; Chui, Toco Y P; Freund, K Bailey; Fell, Millie; Dolz-Marco, Rosa; Rosen, Richard B

    2018-02-27

    To report a case of persistent retinal toxicity associated with a high dose of sildenafil citrate intake. Single retrospective case report. A 31-year-old white man with no medical history presented with complaints of bilateral multicolored photopsias and erythropsia (red-tinted vision), shortly after taking sildenafil citrate-purchased through the internet. Patient was found to have cone photoreceptor damage, demonstrated using electroretinogram, optical coherence tomography, and adaptive optics imaging. The patient's symptoms and the photoreceptor structural changes persisted for several months. Sildenafil citrate is a widely used erectile dysfunction medication that is typically associated with transient visual symptoms in normal dosage. At high dosage, sildenafil citrate can lead to persistent retinal toxicity in certain individuals.

  15. The first iron(III) complexes with cyclin-dependent kinase inhibitors: Magnetic, spectroscopic (IR, ES+ MS, NMR, Fe-57 Mossbauer), theoretical, and biological activity studies

    Czech Academy of Sciences Publication Activity Database

    Trávníček, Zdeněk; Popa, Igor; Čajan, Michal; Zbořil, R.; Kryštof, Vladimír; Mikulík, J.

    2010-01-01

    Roč. 104, č. 4 (2010), s. 405-417 ISSN 0162-0134 R&D Projects: GA MŠk 1M0512; GA ČR GA301/08/1649 Institutional research plan: CEZ:AV0Z50380511 Keywords : Iron(III) complexes * 57Fe Mössbauer spectroscopy * CDK inhibition Subject RIV: CA - Inorganic Chemistry Impact factor: 3.317, year: 2010

  16. Redox characterization of the Fe(II)-catalyzed transformation of ferrihydrite to goethite

    Science.gov (United States)

    Jones, Adele M.; Collins, Richard N.; Waite, T. David

    2017-12-01

    The reduction potential of Fe(II)-Fe(III) (oxyhydr)oxide systems provides an important control on the biogeochemical cycling of redox-sensitive elements such as carbon and nitrogen as well as trace metals and organic contaminants in natural systems. As such, an in-depth understanding of the factors controlling the reduction potential of such systems is critical to predicting the likely transformation, transport and fate of these species in natural and perturbed environments. In this study the mineralogy and reduction potential of ferrihydrite suspensions at pH 6.50 and pH 7.00 were determined over the course of their Fe(II)-catalyzed transformation to lepidocrocite and goethite using X-ray absorption spectroscopy and mediated electrochemical approaches. The measured reduction potentials were compared to those of analogous Fe(II)-Fe(III) (oxyhydr)oxide suspensions reacted for 5 min containing pure ferrihydrite (Fh), lepidocrocite (L) and goethite (Gt). The reduction potentials of the pure Fe(II)-Fe(III) (oxyhydr)oxide suspensions were, respectively, +47.5, -13.5 and -122.3 mV vs. SHE at pH 6.5, and -22.9, -84.1 and -189.7 mV vs. SHE at pH 7. These values are in good agreement with reduction potentials calculated using the Nernst equation and reported thermodynamic solubility products indicating that these suspensions had reached equilibrium within 5 min. The reduction potential of the pH 6.50 Fe(II)-ferrihydrite suspension decreased from +47.4 mV to -126.4 mV over a week, and from -20.1 mV to -188.4 mV (all vs. SHE) after 24 h at pH 7. The changes in reduction potential over time matched well to those calculated from the relative proportion of each pure Fe(III) (oxyhydr)oxide present suggesting that Fe3+ activity was influenced by the mix of iron oxides present rather than the most insoluble solid species. Finally, evidence is provided that adsorbed Fe(II) has the capacity to reduce a significantly larger fraction of a reducible species than the aqueous Fe

  17. Iron Isotope Fractionation during Fe(II) Oxidation Mediated by the Oxygen-Producing Marine Cyanobacterium Synechococcus PCC 7002

    Energy Technology Data Exchange (ETDEWEB)

    Swanner, E. D.; Bayer, T.; Wu, W.; Hao, L.; Obst, M.; Sundman, A.; Byrne, J. M.; Michel, F. M.; Kleinhanns, I. C.; Kappler, A.; Schoenberg, R.

    2017-04-11

    In this study, we couple iron isotope analysis to microscopic and mineralogical investigation of iron speciation during circumneutral Fe(II) oxidation and Fe(III) precipitation with photosynthetically produced oxygen. In the presence of the cyanobacterium Synechococcus PCC 7002, aqueous Fe(II) (Fe(II)aq) is oxidized and precipitated as amorphous Fe(III) oxyhydroxide minerals (iron precipitates, Feppt), with distinct isotopic fractionation (ε56Fe) values determined from fitting the δ56Fe(II)aq (1.79‰ and 2.15‰) and the δ56Feppt (2.44‰ and 2.98‰) data trends from two replicate experiments. Additional Fe(II) and Fe(III) phases were detected using microscopy and chemical extractions and likely represent Fe(II) and Fe(III) sorbed to minerals and cells. The iron desorbed with sodium acetate (FeNaAc) yielded heavier δ56Fe compositions than Fe(II)aq. Modeling of the fractionation during Fe(III) sorption to cells and Fe(II) sorption to Feppt, combined with equilibration of sorbed iron and with Fe(II)aq using published fractionation factors, is consistent with our resulting δ56FeNaAc. The δ56Feppt data trend is inconsistent with complete equilibrium exchange with Fe(II)aq. Because of this and our detection of microbially excreted organics (e.g., exopolysaccharides) coating Feppt in our microscopic analysis, we suggest that electron and atom exchange is partially suppressed in this system by biologically produced organics. These results indicate that cyanobacteria influence the fate and composition of iron in sunlit environments via their role in Fe(II) oxidation through O2 production, the capacity of their cell surfaces to sorb iron, and the interaction of secreted organics with Fe(III) minerals.

  18. Studies on sildenafil citrate (Viagra) interaction with DNA using electrochemical DNA biosensor.

    Science.gov (United States)

    Rauf, Sakandar; Nawaz, Haq; Akhtar, Kalsoom; Ghauri, Muhammad A; Khalid, Ahmad M

    2007-05-15

    The interaction of sildenafil citrate (Viagra) with DNA was studied by using an electrochemical DNA biosensor. The binding mechanism of sildenafil citrate was elucidated by using constant current potentiometry and differential pulse voltammetry at DNA-modified glassy carbon electrode. The decrease in the guanine oxidation peak area or peak current was used as an indicator for the interaction in 0.2M acetate buffer (pH 5). The binding constant (K) values obtained were 2.01+/-0.05 x 10(5) and 1.97+/-0.01 x 10(5)M(-1) with constant current potentiometry and differential pulse voltammetry, respectively. A linear dependence of the guanine peak area or peak current was observed within the range of 1-40 microM sildenafil citrate with slope=-2.74 x 10(-4)s/microM, r=0.989 and slope=-2.78 x 10(-3)microA/microM, r=0.995 by using constant current potentiometry and differential pulse voltammetry, respectively. Additionally, binding constant values for sildenafil citrate-DNA interaction were determined for the pH range of 4-8 and in biological fluids (serum and urine) at pH 5. The influence of sodium and calcium ions was also studied to elucidate the mechanism of sildenafil citrate-DNA interaction under different solution conditions. The present study may prove to be helpful in extending our understanding of the anticancer activity of sildenafil citrate from cellular to DNA level.

  19. Electromagnetic attenuation analysis of Ni{sub 0.4}Zn{sub 0.6}Fe{sub 2O4} obtained by citrate precursor method; Analise da atenuacao de radiacao eletromagnetica de Ni{sub 0.4}Zn{sub 0.6}Fe{sub 2O4} obtido pelo metodo de citrato precursor

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, K. [Centro Tecnico Aeroespacial (CTA-IAE), Sao Jose dos Campos, SP (Brazil). Inst. de Atividades Espaciais. Div. Materiais; Moura, A.E.G.; Nasar, R.S.; Nasar, M.C. [Universidade Federal do Rio Grande do Norte (UFRN), Natal (Brazil). Dept. de Quimica; Pereira, J.J. [Universidade de Taubate, SP (Brazil)

    2010-07-01

    In this work, two types of synthesized Ni{sub 0,4}Zn{sub 0,6}Fe{sub 2}O{sub 4} by citrate precursor method. The first type was calcined at 350 deg C for 3.5 h, and the second, after calcination, it was subjected to heat treatment at 600 deg C for 2h in argon atmosphere. Both types were analyzed by X-ray diffraction (XRD) and equipment waveguide. The data were investigated by Rietveld refinement method and showed the NiZn ferrite phase with crystallite size of 12.2 +- 0.1 nm (350 deg C) and 166.7 +- 3.6 nm (600 deg C). The heat treatment also influenced the values of electric permittivity and magnetic permeability, and attenuation of electromagnetic radiation in the frequency range in microwave (8-12 GHz). The sample treated attenuates more and allows its application with thinner, making it attractive its use as absorber material in this frequency range. (author)

  20. Fe II/Fe III mixed-valence state induced by Li-insertion into the metal-organic-framework Mil53(Fe): A DFT+U study

    Science.gov (United States)

    Combelles, C.; Ben Yahia, M.; Pedesseau, L.; Doublet, M.-L.

    The iron-based metal-organic-framework MIL53(Fe) has recently been tested as a cathode materials for Li-Ion batteries, leading to promising cycling life and rate capability. Despite a poor capacity of 70 mAh g -1 associated with the exchange of almost 0.5Li/Fe, this result is the first evidence of a reversible lithium insertion never observed in a MOF system. In the present study, the MIL53(Fe) redox mechanism is investigated through first-principles DFT+U calculations. The results show that MIL53(Fe) is a weak antiferromagnetic charge transfer insulator at T = 0 K, with iron ions in the high-spin S = 5/2 state. Its reactivity vs elemental lithium is then investigated as a function of lithium composition and distribution over the most probable Li-sites of the MOF structure. The redox mechanism is fully interpreted as a two-step insertion/conversion mechanism, associated with the stabilization of the Fe 3+/Fe 2+ mixed-valence state prior to the complete decomposition of the inorganic-organic interactions within the porous MOF architecture.

  1. Determination of element distributions between symplasm and apoplasm of cucumber plant parts

    International Nuclear Information System (INIS)

    Varga, A.; Zaray, G.; Fodor, F.

    2000-01-01

    Total reflection x-ray fluorescence analysis (TXRF) is a suitable method for determination of trace elements in biological samples due to its low detection limits, small sample demand, simple quantification and the absence of memory effects. In the present work the concentration of Pb, Cd, Ni, Mn and Fe was determined inside the cells (symplasm) and in the space among the cells (apoplasm) of cucumber plants. The cucumber seeds were grown in different nutrient solutions containing iron as Fe(III)-EDTA or Fe(III)-citrate, as well as Pb, Cd or Ni as contaminants in concentration of 10 -5 M. After growing period and the appropriate pretreatment (infiltration, leaching, washing and drying) the roots and the leaves were prepared for the analysis using a microwave assisted digestion system. The solutions obtained were spiked with Ni (in the case of the experiments with Pb) or Ga as internal standard. It was established that in the root the relative amount of lead in the symplasm related to the total absorbed amount (symplasm + apoplasm) is 2.5 % in presence of EDTA and 24% in presence of citrate. Studying its transport to the shoots, the amount of lead shows a decreasing tendency towards the young leaves and the symplasm/apoplasm ratio also changes: the ratio increased up to 66 % and 50 % in case of EDTA and citrate, respectively. Investigating of iron content similar phenomenon could be observed, however the presence of lead and complex forming agents did not result in any significant changes of the manganese distribution between symplasm and apoplasm. The results of experiments with Ni and Cd contaminants will be presented and discussed in the lecture. (author)

  2. 76 FR 19997 - Determination That FENTORA (Fentanyl Citrate) Buccal Tablet, 300 Micrograms, Was Not Withdrawn...

    Science.gov (United States)

    2011-04-11

    ...] Determination That FENTORA (Fentanyl Citrate) Buccal Tablet, 300 Micrograms, Was Not Withdrawn From Sale for... Food and Drug Administration (FDA) has determined that FENTORA (fentanyl citrate) buccal tablet, 300... allow FDA to approve abbreviated new drug applications (ANDAs) for fentanyl citrate buccal tablet, 300...

  3. Nitrate Protects Cucumber Plants Against Fusarium oxysporum by Regulating Citrate Exudation.

    Science.gov (United States)

    Wang, Min; Sun, Yuming; Gu, Zechen; Wang, Ruirui; Sun, Guomei; Zhu, Chen; Guo, Shiwei; Shen, Qirong

    2016-09-01

    Fusarium wilt causes severe yield losses in cash crops. Nitrogen plays a critical role in the management of plant disease; however, the regulating mechanism is poorly understood. Using biochemical, physiological, bioinformatic and transcriptome approaches, we analyzed how nitrogen forms regulate the interactions between cucumber plants and Fusarium oxysporum f. sp. cucumerinum (FOC). Nitrate significantly suppressed Fusarium wilt compared with ammonium in both pot and hydroponic experiments. Fewer FOC colonized the roots and stems under nitrate compared with ammonium supply. Cucumber grown with nitrate accumulated less fusaric acid (FA) after FOC infection and exhibited increased tolerance to chemical FA by decreasing FA absorption and transportation in shoots. A lower citrate concentration was observed in nitrate-grown cucumbers, which was associated with lower MATE (multidrug and toxin compound extrusion) family gene and citrate synthase (CS) gene expression, as well as lower CS activity. Citrate enhanced FOC spore germination and infection, and increased disease incidence and the FOC population in ammonium-treated plants. Our study provides evidence that nitrate protects cucumber plants against F. oxysporum by decreasing root citrate exudation and FOC infection. Citrate exudation is essential for regulating disease development of Fusarium wilt in cucumber plants. © The Author 2016. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

  4. Synthesis and characterization of polycrystalline brownmillerite cobalt doped Ca{sub 2}Fe{sub 2}O{sub 5}

    Energy Technology Data Exchange (ETDEWEB)

    Dhankhar, Suchita; Baskar, K.; Singh, Shubra, E-mail: shubra6@gmail.com [Crystal Growth Centre, Anna University, Chennai-600 025 (India); Bhalerao, Gopal [UGC-DAE CSR Kalpakkam node, Kalpakkam-603104 (India)

    2016-05-23

    Brownmillerite compounds with general formula A{sub 2}BB’O{sub 5} (BB’ = Mn, Al, Fe, Co) have attracted attention in wide range of applications such as in solid oxide fuel cell, oxygen separation membrane and photocatalysis. Brownmillerite compounds have unique structure with alternate layers of BO{sub 6} octahedral layers and BO{sub 4} tetrahedral layers. Presence of dopants like Co in place of Fe increases oxygen vacancies. In the present work we have synthesized polycrystalline Ca{sub 2}Fe{sub 2}O{sub 5} and Ca{sub 2}Fe{sub 1-x}Co{sub x}O{sub 5} (x = 0.01, 0.03) by citrate combustion route. The as prepared samples were characterized by XRD using PANalytical X’Pert System, DRS (Diffuse reflectance spectroscopy) and SEM (Scanning electron microscopy).

  5. Nano size crystals of goethite, α-FeOOH: Synthesis and thermal transformation

    International Nuclear Information System (INIS)

    Christensen, Axel Norlund; Jensen, Torben R.; Bahl, Christian R.H.; DiMasi, Elaine

    2007-01-01

    An aqueous suspension of amorphous iron(III) hydroxide was kept at room temperature (298 K) for 23 years. During this period of time the pH of the liquid phase changed from 4.3 to 2.85, and nano size crystals of goethite, α-FeOOH crystallised from the amorphous iron(III) hydroxide. Transmission electron microscopy (TEM) investigations, Moessbauer spectra, and powder X-ray diffraction using Co Kα radiation showed that the only iron containing crystalline phase present in the recovered product was α-FeOOH. The size of these nano particles range from 10 to 100 nm measured by TEM. The thermal decomposition of α-FeOOH was investigated by time-resolved in situ synchrotron radiation powder X-ray diffraction and the data showed that the sample of α-FeOOH transformed to α-Fe 2 O 3 in the temperature range 444-584 K. A quantitative phase analysis shows the increase in scattered X-ray intensity from α-Fe 2 O 3 to follow the decrease of intensity from α-FeOOH in agreement with the topotactic phase transition. - Graphical abstract: Nano size crystals of goethite, α-FeOOH formed from amorphous iron(III) hydroxide after 23 years, and transforms faster to α-Fe 2 O 3 upon heating

  6. Synthesis of Fe nanoparticles on polyaniline covered carbon nanotubes for oxygen reduction reaction

    Science.gov (United States)

    Hu, Tian-Hang; Yin, Zhong-Shu; Guo, Jian-Wei; Wang, Cheng

    2014-12-01

    Fe nanoparticles immobilized on polyaniline-covered carbon nanotube (CNT) surfaces (Fe NPs-PANI/CNT) are prepared by reducing FeCl3 in the mixing solution of aniline and CNT. Significantly, the structure of such composites can be effectively optimized by pretreating FeCl3 with sodium citrate (CA). In the absence of CNTs, we found these two routes have large differences in reduction behaviors and different PANI states with varied conductivities. Therefore, the self-assembly mechanism in the preparation is proposed and the controlled self-assembly manner in the pretreating route is disclosed. Under acid condition, both catalysts demonstrate high oxygen reduction reaction (ORR) activity with four-electron pathway, and high electrochemical durability, revealing a promising application in the proton exchange membrane fuel cells. However, the high Tafel slopes relating to the surface red-ox couple and porous conductivity are still the main obstacles to improve their ORR dynamic, and more efforts on these aspects are needed to drive non-noble catalyst application in future.

  7. Shewanella putrefaciens mtrB encodes an outer membrane protein required for Fe(III) and Mn(IV) reduction.

    Science.gov (United States)

    Beliaev, A S; Saffarini, D A

    1998-12-01

    Iron and manganese oxides or oxyhydroxides are abundant transition metals, and in aquatic environments they serve as terminal electron acceptors for a large number of bacterial species. The molecular mechanisms of anaerobic metal reduction, however, are not understood. Shewanella putrefaciens is a facultative anaerobe that uses Fe(III) and Mn(IV) as terminal electron acceptors during anaerobic respiration. Transposon mutagenesis was used to generate mutants of S. putrefaciens, and one such mutant, SR-21, was analyzed in detail. Growth and enzyme assays indicated that the mutation in SR-21 resulted in loss of Fe(III) and Mn(IV) reduction but did not affect its ability to reduce other electron acceptors used by the wild type. This deficiency was due to Tn5 inactivation of an open reading frame (ORF) designated mtrB. mtrB encodes a protein of 679 amino acids and contains a signal sequence characteristic of secreted proteins. Analysis of membrane fractions of the mutant, SR-21, and wild-type cells indicated that MtrB is located on the outer membrane of S. putrefaciens. A 5.2-kb DNA fragment that contains mtrB was isolated and completely sequenced. A second ORF, designated mtrA, was found directly upstream of mtrB. The two ORFs appear to be arranged in an operon. mtrA encodes a putative 10-heme c-type cytochrome of 333 amino acids. The N-terminal sequence of MtrA contains a potential signal sequence for secretion across the cell membrane. The amino acid sequence of MtrA exhibited 34% identity to NrfB from Escherichia coli, which is involved in formate-dependent nitrite reduction. To our knowledge, this is the first report of genes encoding proteins involved in metal reduction.

  8. Post-Dilution on Line Haemodiafiltration with Citrate Dialysate: First Clinical Experience in Chronic Dialysis Patients

    Directory of Open Access Journals (Sweden)

    Vincenzo Panichi

    2013-01-01

    Full Text Available Background. Citrate has anticoagulative properties and favorable effects on inflammation, but it has the potential hazards of inducing hypocalcemia. Bicarbonate dialysate (BHD replacing citrate for acetate is now used in chronic haemodialysis but has never been tested in postdilution online haemodiafiltration (OL-HDF. Methods. Thirteen chronic stable dialysis patients were enrolled in a pilot, short-term study. Patients underwent one week (3 dialysis sessions of BHD with 0.8 mmol/L citrate dialysate, followed by one week of postdilution high volume OL-HDF with standard bicarbonate dialysate, and one week of high volume OL-HDF with 0.8 mmol/L citrate dialysate. Results. In citrate OL-HDF pretreatment plasma levels of C-reactive protein and β2-microglobulin were significantly reduced; intra-treatment plasma acetate levels increased in the former technique and decreased in the latter. During both citrate techniques (OL-HDF and HD ionized calcium levels remained stable within the normal range. Conclusions. Should our promising results be confirmed in a long-term study on a wider population, then OL-HDF with citrate dialysate may represent a further step in improving dialysis biocompatibility.

  9. Are Fe and Co implanted ZnO and III-nitride semiconductors magnetic?

    CERN Document Server

    AUTHOR|(CDS)2081284; Bharuth-Ram, Krish

    The chemical nature, lattice site locations and magnetic behaviour of Fe and/or Co ions implanted in nitrides (GaN, AlN, and InN) and in ZnO have been investigated using Mössbauer spectroscopy and vibrating sample magnetometer (VSM) techniques. Mössbauer data on nitride and $^{56}$Fe pre-implanted ZnO samples were obtained from emission Mössbauer spectroscopy (eMS) measurements at the ISOLDE facility, CERN, following the implantation of radioactive $^{57}$Mn$^{*}$ which $\\beta$$^{-}$decays to the 14.4 keV Mössbauer state of $^{57}$Fe. In addition, conversion electron Mössbauer spectroscopy (CEMS) data were collected on ZnO single crystals co-implanted with $^{57}$Fe + $^{56}$Fe and $^{57}$Fe + $^{59}$Co ions in a box profile. Emission Mössbauer spectra obtained for GaN and AlN reveal magnetic structure in the ‘wings’ assigned to high spin Fe$^{3+}$ weakly coupled to the lattice showing spin-lattice relaxation effects. The observed spin-relaxation rate (τ$^{-1}$) closely follows a ${T}^{2}$ temperat...

  10. Stable Fe isotope fractionation during anaerobic microbial dissimilatory iron reduction at low pH

    Science.gov (United States)

    Chanda, P.; Amenabar, M. J.; Boyd, E. S.; Beard, B. L.; Johnson, C.

    2017-12-01

    In low-temperature anaerobic environments microbial dissimilatory iron reduction (DIR) plays an important role in Fe cycling. At neutral pH, sorption of aqueous Fe(II) (Fe(II)aq, produced by DIR) catalyzes isotopic exchange between Fe(II) and solid Fe(III), producing 56Fe/54Fe fractionations on the order of 3‰ during DIR[1,2,3]. At low pH, however, the absence of sorbed Fe(II) produces only limited abiologic isotopic exchange[4]. Here we investigated the scope of isotopic exchange between Fe(II)aq and ferric (hydr)oxides (ferrihydrite and goethite) and the associated stable Fe isotope fractionation during DIR by Acidianus strain DS80 at pH 3.0 and 80°C[5]. Over 19 days, 13% reduction of both minerals via microbial DIR was observed. The δ56Fe values of the fluid varied from -2.31 to -1.63‰ (ferrihydrite) and -0.45 to 0.02‰ (goethite). Partial leaching of bulk solid from each reactor with dilute HCl showed no sorption of Fe(II), and the surface layers of the solids were composed of Fe(III) with high δ56Fe values (ferrihydrite: 0.20 to 0.48‰ and goethite: 1.20 to 1.30‰). These results contrast with the lack of Fe isotope exchange in abiologic low-pH systems and indicate a key role for biology in catalyzing Fe isotope exchange between Fe(II)aq and Fe(III) solids, despite the absence of sorbed Fe(II). The estimated fractionation factor (ΔFeFe(III) -Fe(II)aq 2.6‰) from leaching of ferrihydrite is similar to the abiologic equilibrium fractionation factor ( 3.0‰)[3]. The fractionation factor (ΔFeFe(III) -Fe(II)aq 2.0‰) for goethite is higher than the abiologic fractionation factor ( 1.05‰)[2], but is consistent with the previously proposed "distorted surface layer" of goethite produced during the exchange with Fe(II)aq at neutral pH[1]. This study indicates that significant variations in Fe isotope compositions may be produced in low-pH environments where biological cycling of Fe occurs, in contrast to the expected lack of isotopic fractionation in

  11. Application of granular activated carbon/MnFe2O4 composite immobilized on C. glutamicum MTCC 2745 to remove As(III) and As(V): Kinetic, mechanistic and thermodynamic studies

    Science.gov (United States)

    Podder, M. S.; Majumder, C. B.

    2016-01-01

    The main objective of the present study was to investigate the efficiency of Corynebacterium glutamicum MTCC 2745 immobilized on granular activated carbon/MnFe2O4 (GAC/MnFe2O4) composite to treat high concentration of arsenic bearing wastewater. Non-linear regression analysis was done for determining the best-fit kinetic model on the basis of three correlation coefficients and three error functions and also for predicting the parameters involved in kinetic models. The results showed that Fractal-like mixed 1,2 order model for As(III) and Brouser-Weron-Sototlongo as well as Fractal-like pseudo second order models for As(V) were proficient to provide realistic description of biosorption/bioaccumulation kinetic. Applicability of mechanistic models in the current study exhibited that the rate governing step in biosorption/bioaccumulation of both As(III) and As(V) was film diffusion rather than intraparticle diffusion. The evaluated thermodynamic parameters ΔG0, ΔH0 and ΔS0 revealed that biosorption/bioaccumulation of both As(III) and As(V) was feasible, spontaneous and exothermic under studied conditions.

  12. High-temperature ferromagnetism in heavily Fe-doped ferromagnetic semiconductor (Ga,Fe)Sb

    International Nuclear Information System (INIS)

    Tu, Nguyen Thanh; Hai, Pham Nam; Anh, Le Duc; Tanaka, Masaaki

    2016-01-01

    We show high-temperature ferromagnetism in heavily Fe-doped ferromagnetic semiconductor (Ga_1_−_x,Fe_x)Sb (x = 23% and 25%) thin films grown by low-temperature molecular beam epitaxy. Magnetic circular dichroism spectroscopy and anomalous Hall effect measurements indicate intrinsic ferromagnetism of these samples. The Curie temperature reaches 300 K and 340 K for x = 23% and 25%, respectively, which are the highest values reported so far in intrinsic III-V ferromagnetic semiconductors.

  13. Lanthanide ions (III) as sensitizers of melatonin oxidation in reaction mixtures providing reactive species of oxygen and nitrogen

    Energy Technology Data Exchange (ETDEWEB)

    Kaczmarek, Małgorzata, E-mail: mkaczmar@amu.edu.pl

    2015-06-15

    Chemiluminescence (CL) of the reactive systems providing strong oxidants (reactive species of oxygen and nitrogen) containing lanthanide ions (III) and melatonin, was studied. Kinetic curves of emission decay and spectral distributions of chemiluminescence were obtained. Analysis of differences in the intensity of chemiluminescence and CL spectra proved that excitation of Tb(III) and Dy(III) ions takes place with the energy transfer from the products of melatonin oxidation: N{sup 1}-acetyl-N{sup 2}-formyl-5-methoxykynuramine (AFMK) and N{sup 1}-acetyl-5-methoxykynuramine (AMK) to the lanthanide ions. In the system Fe(II)/Fe(III)–H{sub 2}O{sub 2}–Mel–Tb(III) a linear correlation was established between the integrated CL intensity and melatonin concent. - Highlights: • Chemiluminescence (CL) of melatonin (Mel) oxidation by reactive species of oxygen and nitrogen. • Tb(III) and Dy(III) ions as sensitizers of a melatonin oxidation process. • New CL method for determination of melatonin in pharmaceutical preparations based on CL of Fe(II)/Fe(III)–H{sub 2}O{sub 2}–Mel–Tb(III) system.

  14. Time-dependent density functional theory/discrete reaction field spectra of open shell systems : The visual spectrum of [Fe-III(PyPepS)(2)](-) in aqueous solution

    NARCIS (Netherlands)

    van Duijnen, Piet Th.; Greene, Shannon N.; Richards, Nigel G. J.

    2007-01-01

    We report the calculated visible spectrum of [Fe-III(PyPepS)(2)](-) in aqueous solution. From all-classical molecular dynamics simulations on the solute and 200 water molecules with a polarizable force field, 25 solute/solvent configurations were chosen at random from a 50 ps production run and

  15. Effect of Eu(III) on the degradation of malic acid by Pseudomonas fluorescens

    International Nuclear Information System (INIS)

    Nankawa, T.; Ozaki, T.; Ohnuki, T.; Suzuki, Y.; Francis, A.J.

    2005-01-01

    Full text of publication follows: The transuranic elements, such as Am(III) and Cm(III), are highly toxic because they emit high-energy α particles and have long half-lives. To estimate their long-term environmental behavior, we need to elucidate degradation of actinide-organic complexes by microorganisms. We studied the biodegradation of Eu(III)-malic acid complexes by Pseudomonas fluorescens. Malic acid is ubiquitous in the environment and is one of the microbial metabolites that is part of the tri-carboxylic acid (TCA) cycle. Europium(III) is a good analogue for Am(III) and Cm(III). To investigate the effect of Eu(III) on the degradation of malic acid by P. fluorescens, we compared the degradation behavior of Eu(III)-malic acid complexes to that of Fe(III) and Al(III)-malic acid complexes. In the medium containing 1 mM malic acid and 0-0.5 mM Fe(III), malic acid was degraded completely. In the medium containing 1 mM malic acid and 0.05-0.5 mM Al(III), malic acid was degraded until the concentration of malic acid became equal to that of Al(III), indicating that Al(III)-malic acid complex with 1: 1 molar ratio was recalcitrant to biodegradation. In the medium containing 1 mM malic acid and 0.05-0.5 mM Eu(III), degradation of malic acid was not observed. The effect of metals on degradation of malic acid was in the order of Fe(III) < Al(III) < Eu(III). The stability constants of 1:1 Fe(III)-, Al(III)-, and Eu(III)-malic acid complexes are 7.1, 4.6, and 4.9, respectively. These results indicate that degradability of malic acid does not depend on the stability constants of metal-malic acid complexes. We found that 10 mM malic acid was degraded in the presence of 0.05 and 0.1 mM Eu(III) but 1 mM malic acid was not degraded in the presence of 0.05 and 0.1 mM Eu(III). The degradation rate of malic acid increased with a decreasing ratio of Eu(III) to malic acid. (authors)

  16. Feasibility of closed Fe(II)/Fe(III) system for product-reflux in Nitrox process

    International Nuclear Information System (INIS)

    Adachi, M.; Ishida, T.

    1981-01-01

    A concept of closed reflux system for stable isotope fractionation by chemical exchange method has been introduced. In a closed system a chemical agent used to convert one chemical species of an isotopic exchange reaction into the other at the product end is regenerated on site by means of an electrochemical or thermal process. It offers a convenience of eliminating the needs for transporting chemicals to and from the site and an advantage of allowing leniency in the degree of completeness of the reflux reaction. Feasibility of use of Fe(II) salt solutions in a closed reflux system for the Nitrox process for 15 N fractionation has been studied. Two of such systems, FeSO 4 in H 2 SO 4 and Fe(ClO 4 ) 2 in HClO 4 , are adopted for packed column operation. For both systems, the rate of reduction of nitric acid increases with increasing acid concentration, the solubility of the salts decreases with the increasing acid concentration, and the reflux reaction can be made to go to completion. Evaluation of such a closed reflux system will have to include that of performance of regenerative process

  17. Electrospray ionization of uranyl-citrate complexes

    Science.gov (United States)

    Somogyi, Árpád; Pasilis, Sofie P.; Pemberton, Jeanne E.

    2007-09-01

    Results presented here demonstrate the usefulness of electrospray ionization and gas-phase ion-molecule reactions to predict structural and electronic differences in complex inorganic ions. Electrospray ionization of uranyl citrate solutions generates positively and negatively charged ions that participate in further ion-molecule reactions in 3D ion trap and FT-ICR mass analyzers. Most ions observed are derived from the major solution uranyl-citrate complexes and involve species of {(UO2)2Cit2}2-, (UO2)3Cit2, and {(UO2)3Cit3}3-, where Cit indicates the citrate trianion, C6H5O73-. In a 3D ion trap operated at relatively high pressure, complex adducts containing solvent molecules, alkali and ammonium cations, and nitrate or chloride anions are dominant, and proton/alkali cation (Na+, K+) exchange is observed for up to six exchangeable protons in an excess of alkali cations. Adduct formation in a FT-ICR cell that is operated at lower pressures is less dominant, and direct detection of positive and negative ions of the major solution complexes is possible. Multiply charged ions are also detected, suggesting the presence of uranium in different oxidation states. Changes in uranium oxidation state are detected by He-CID and SORI-CID fragmentation, and certain fragments undergo association reactions in trapping analyzers, forming "exotic" species such as [(UO2)4O3]-, [(UO2)4O4]-, and [(UO2)4O5]-. Ion-molecule reactions with D2O in the FT-ICR cell indicate substantial differences in H/D exchange rate and D2O accommodation for different ion structures and charge states. Most notably, the positively charged ions [H2(UO2)2Cit2(H)]+ and [(UO2)2(Cit)]+ accommodate two and three D2O molecules, respectively, which reflects well the structural differences, i.e., tighter uranyl-citrate coordination in the former ion than in the latter. The corresponding negatively charged ions accommodate zero or two D2O molecules, which can be rationalized using suggested solution phase structures

  18. Fe/Ti co-pillared clay for enhanced arsenite removal and photo oxidation under UV irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yuan [School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Guang Dong Electric Power Design Institute, China Energy Engineering Group Co. Ltd., Guangzhou 510663 (China); Cai, Xiaojiao [School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Guo, Jingwei [School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); The 718th Research Institute of CSIC, Handan 056027 (China); Zhou, Shimin [School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Na, Ping, E-mail: naping@tju.edu.cn [School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China)

    2015-01-01

    Graphical abstract: - Highlights: • An iron and titanium co-pillared montmorillonite (Fe-Ti/MMT) was synthesized for arsenite removal. • Variety of characterization results indicated that Fe and Ti species were pillared in MMT. • A possible mechanism of arsenite adsorption/oxidation with UV light was established. • The participation of Fe component can promote the process of photocatalytic oxidation in Fe-Ti/MMT + As(III) system. • Fe-Ti/MMT can function as both photocatalyst and adsorbent for arsenite removal. - Abstract: A series of iron and titanium co-pillared montmorillonites (Fe-Ti/MMT) were prepared using hydrolysis of inserted titanium and different iron content in montmorillonite (MMT). The Fe-Ti/MMT were characterized by X-ray fluorescence, N{sub 2} adsorption and desorption, X-ray diffraction, scanning electron microscopy (SEM) and transmission electron microscopy (TEM), confirming the effective insertion of Fe species and TiO{sub 2} in the MMT. The Fe-Ti/MMT was used to remove arsenite (As(III)) from aqueous solutions under different conditions. The result of As(III) adsorption under UV irradiation showed that the photo activity can be enhanced by incorporating Fe and Ti in MMT. Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analysis indicated that the hydroxyl groups bonded to metal oxide (M–OH) played an important role in the adsorption of As(III)

  19. Spectroscopic studies on Titanium ion binding to the apo lactoferrin

    International Nuclear Information System (INIS)

    Moshtaghie, A.A.; Ani, M.; Arabi, M.H.

    2006-01-01

    Titanium is a relatively abundant element that has found growing applications in medical science and recently some of Titanium compounds are introduced as anticancer drugs. In spite of very limited data which exist on the Titanium metabolism, some proteins might be involved in the mechanism of action of Titanium up to our knowledge, there is not any report in the literature concerning binding of Titanium to apo lactoferrin. Binding of apo lactoferrin with Ti(IV)-citrate was studied by spectroflourimeterey and spectrophotometery techniques under physiological conditions. The spectroflourimeteric studies revealed a significant fluorescence quenching, that indicated binding of apo lactoferrin with Ti(IV). The same reaction was monitored through spectrophotometry technique; this represents a characteristic UV difference band at 267 nm, which is different from lac-Fe (III). Titration studies how that lactoferrin specifically binds two moles Ti(IV) as complex with citrate per mol protein. Spectroflourimeterey and spectrophotometery techniques indicated that Ti(IV) ions cause a reduction (13%-14%) in binding of Fe(III) to lactoferrin. In overall, we may come to this conclusion that this element might be involved in the iron metabolism

  20. Thermal and biological evolution of Fe(III)-Sulfanilamide complexes synthesized by green strategy

    Science.gov (United States)

    Prajapat, Garima; Rathore, Uma; Gupta, Rama; Bhojak, N.

    2018-05-01

    Sulfonamides belong to a category of sulfadrugs, that are widely used as antibiotic medicines. Their metal complexes, also called Metallodrugs, are known to have diverse pharmacological applications and are significantly used as therapeutic agents for treatment of several human diseases. Fe(III) complexes of two sulfonamides, namely Sulfanilamide and Sulfadiazine have been synthesized by the method of Microwave Assisted Organic Synthesis (MAOS), using acetone as solvent medium. Presence of excellent donor atoms such as N and O, induce these drugs to exhibit a chelating behavior with the metal ion, and to act as bidentate ligands. Both the complexes were found to have four coordinated, tetrahedral geometry with one molecule of water of crystallisation. Thermal decomposition studies were carried out in an inert nitrogen atmosphere by Thermogravimetric (TGA) and Derivative Thermogravimetric (DTA) analysis. Interpretation of thermograms have been done to evaluate various kinetic and thermodynamic parameters, using integral method of Coats and Redfern. The antibacterial activity for both complexes have been screened against E.coli, S. aureus and B. subtilis.