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Sample records for fe iii citrate

  1. Fe(III-Citrate-Complex-Induced Photooxidation of 3-Methylphenol in Aqueous Solution

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    N. Seraghni

    2012-01-01

    Full Text Available The photodegradation process of m-cresol (3-methylphenol, induced by Fe(III-Cit complex, was investigated upon irradiation at 365 nm in natural water. The composition and photochemical properties of Fe(III-Cit complex were studied by UV-Visible absorption spectrophotometer for optimizing the stoichiometry of the complex and photolysis under irradiation at 365 nm, respectively. A dark investigation of the system was performed before studying the photochemical behavior. The photooxidation efficiencies of m-cresol were dependent on the pH value, optimized at pH 2.86, oxygen, initial concentrations of Fe(III-Cit complex, and m-cresol. Additionally, to look into the mechanism of m-cresol degradation using Fe(III-Cit, tertiobutanol alcohol was used as scavenger for hydroxyl radicals and the result suggested that hydroxyl radical attack was the main pathway of m-cresol degradation. Besides, oxygen can enhance the photolysis of Fe(III-Citrate complex by trapping the electron on the carbon centered radical formed after the photoredox process. Then O2•− formed reacts rapidly leading finally to formation of •OH radical. In absence of oxygen, less reactive species are formed; consequently the disappearance of m-cresol was strongly inhibited. Our work shows that the presence of Fe(III-Citrate complex could have a considerable impact on the fate of organic pollutant in aquatic environment.

  2. 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

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    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.

  3. The interaction of phenolic acids with Fe(III) in the presence of citrate as studied by isothermal titration calorimetry.

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    Yang, Senpei; Bai, Guangling; Chen, Lingli; Shen, Qun; Diao, Xianmin; Zhao, Guanghua

    2014-08-15

    Under physiological conditions, exogenous chelators such as polyphenols might interact with non-protein bound ferric complexes, such as Fe(III)-citrate. Additionally, Fe(III) and citrate are widely distributed in various fruits and vegetables which are also rich in phenolic acids. In this study, we focus on the interaction between phenolic acids (gallic acid, methyl gallate and protocatechuic acid) and Fe(III) in the presence of excessive citrate by isothermal titration calorimetry (ITC) for thermodynamic studies, and stopped-flow absorption spectrometry for fast kinetic studies. Results reveal that all of these three phenolic acids can bind to the Fe(III) with the same stoichiometry (3:1). Moreover, the binding constants of these three compounds with Fe(III) are greatly dependent on ligand structure, and are much higher than that of Fe(III)-citrate. Based on their stoichiometry and superhigh binding constants, it is most likely that these three phenolic acids can displace the citrate to bind with one iron(III) ion to form a stable octahedral geometric structure, albeit at different rates. These findings shed light on the interaction between phenolic acids and Fe(III) in the presence of citrate under either physiological conditions or in a food system. Copyright © 2014 Elsevier Ltd. All rights reserved.

  4. Photodegradation of parabens by Fe(III)-citrate complexes at circumneutral pH: matrix effect and reaction mechanism.

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    Feng, Xiaonan; Chen, Yong; Fang, Yuan; Wang, Xiaoyue; Wang, Zongping; Tao, Tao; Zuo, Yuegang

    2014-02-15

    The photodegradation of four parabens including methyl-, ethyl-, propyl-, and butyl-paraben in the presence of Fe(III)-citrate complexes under simulated sunlight was investigated. The degradation of parabens increased with decreasing pH within the range of 5.0-8.0 at the Fe(III)-to-citrate ratio of 10:150 (μM). The addition of low-molecular-weight carboxylic acids showed different effects on the photodegradation of methylparaben. The low-photoreactive carboxylic acids inhibited the photodegradation of methylparaben in the order of formic acid>succinic acid>acetic acid>malonic acid. In contrast, oxalic acid enhanced the photodegradation and exhibited appreciable synergistic effect with Fe(III)-citrate at concentration higher than 500 μM. Up to 99.0% of substrate was degraded after 30 min at pH6.0 in the Fe(III)-citrate-oxalate system. The various fractions of fulvic acid inhibited the photodegradation of methylparaben. The inhibition increased with increasing nominal molecular weight of fractionated fulvic acid. Moreover, the photodegradation of methylparaben was inhibited in natural waters in the order of Liangzi Lake

  5. Retention Mechanisms of Citric Acid in Ternary Kaolinite-Fe(III)-Citrate Acid Systems Using Fe K-edge EXAFS and L3,2-edge XANES Spectroscopy

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    Yang, Jianjun; Wang, Jian; Pan, Weinan; Regier, Tom; Hu, Yongfeng; Rumpel, Cornelia; Bolan, Nanthi; Sparks, Donald

    2016-05-01

    Organic carbon (OC) stability in tropical soils is strongly interlinked with multivalent cation interaction and mineral association. Low molecular weight organic acids (LMWOAs) represent the readily biodegradable OC. Therefore, investigating retention mechanisms of LMWOAs in mineral-cation-LMWOAs systems is critical to understanding soil C cycling. Given the general acidic conditions and dominance of kaolinite in tropical soils, we investigated the retention mechanisms of citric acid (CA) in kaolinite-Fe(III)-CA systems with various Fe/CA molar ratios at pH ~3.5 using Fe K-edge EXAFS and L3,2-edge XANES techniques. With Fe/CA molar ratios >2, the formed ferrihydrite mainly contributed to CA retention through adsorption and/or coprecipitation. With Fe/CA molar ratios from 2 to 0.5, ternary complexation of CA to kaolinite via a five-coordinated Fe(III) bridge retained higher CA than ferrihydrite-induced adsorption and/or coprecipitation. With Fe/CA molar ratios ≤0.5, kaolinite-Fe(III)-citrate complexation preferentially occurred, but less CA was retained than via outer-sphere kaolinite-CA complexation. This study highlighted the significant impact of varied Fe/CA molar ratios on CA retention mechanisms in kaolinite-Fe(III)-CA systems under acidic conditions, and clearly showed the important contribution of Fe-bridged ternary complexation on CA retention. These findings will enhance our understanding of the dynamics of CA and other LMWOAs in tropical soils.

  6. Adaptative biochemical pathways and regulatory networks in Klebsiella oxytoca BAS-10 producing a biotechnologically relevant exopolysaccharide during Fe(III-citrate fermentation

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    Gallo Giuseppe

    2012-11-01

    Full Text Available Abstract 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 reduction to Fe(II and showing unusual physiological characteristics. In fact, under this growth condition, BAS-10 produces an exopolysaccharide (EPS having a high rhamnose content and metal-binding properties, whose biotechnological applications were proven as very relevant. Results Further phylogenetic analysis, based on 16S rDNA sequence, definitively confirmed that BAS-10 belongs to K. oxytoca species. In order to rationalize the biochemical peculiarities of this unusual enterobacteriun, combined 2D-Differential Gel Electrophoresis (2D-DIGE analysis and mass spectrometry procedures were used to investigate its proteomic changes: i under aerobic or anaerobic cultivation with Fe(III-citrate as sole carbon source; ii under anaerobic cultivations using Na(I-citrate or Fe(III-citrate as sole carbon source. Combining data from these differential studies peculiar levels of outer membrane proteins, key regulatory factors of carbon and nitrogen metabolism and enzymes involved in TCA cycle and sugar biosynthesis or required for citrate fermentation and stress response during anaerobic growth on Fe(III-citrate were revealed. The protein differential regulation seems to ensure efficient cell growth coupled with EPS production by adapting metabolic and biochemical processes in order to face iron toxicity and to optimize energy production. Conclusion Differential proteomics provided insights on the molecular mechanisms necessary for anaeorobic utilization of Fe(III-citrate in a biotechnologically promising enterobacteriun, also revealing genes that can be targeted for the rational design of high-yielding EPS producer strains.

  7. Pulsed ELDOR spectroscopy of the Mo(V)/Fe(III) state of sulfite oxidase prepared by one-electron reduction with Ti(III) citrate.

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    Codd, Rachel; Astashkin, Andrei V; Pacheco, Andrew; Raitsimring, Arnold M; Enemark, John H

    2002-03-01

    The titration of chicken liver sulfite oxidase (SO) with the one-electron reductant Ti(III) citrate, at pH 7.0, results in nearly quantitative selective reduction of the Mo(VI) center to Mo(V), while the b-type heme center remains in the fully oxidized Fe(III) state. The selective reduction of the Mo(VI/V) couple has been established from electronic and EPR spectra. The electronic spectrum of the Fe(III) heme center is essentially unchanged during the titration, and the continuous wave (CW)-EPR spectrum shows the appearance of the well-known Mo(V) signal due to the low pH ( lpH) form of SO. Further confirmation of the selective formation of the Mo(V)/Fe(III) form of SO is provided by the approximately 1:1 ratio of the integrated intensities of the Mo(V) and low-spin Fe(III) EPR signals after addition of one equivalent of Ti(III). The selective generation of the Mo(V)/Fe(III) form of SO is unexpected, considering that previous microcoulometry and flash photolysis investigations have indicated that the Mo(VI/V) and Fe(III/II) couples of SO have similar reduction potentials at pH 7. The nearly quantitative preparation of the one-electron reduced Mo(V)/Fe(III) form of SO by reduction with Ti(III) has enabled the interaction between these two paramagnetic metal centers, which are linked by a flexible loop with no secondary structure, to be investigated for the first time by variable-frequency pulsed electron-electron double resonance (ELDOR) spectroscopy. The ELDOR kinetics were obtained from frozen solutions at 4.2 K at several microwave frequencies by pumping on the narrow Mo(V) signal and observing the effect on the Fe(III) primary echo at both higher and lower frequencies within the microwave C-band region. The ELDOR data indicate that freezing the solution of one-electron reduced SO produces localized regions where the concentration of SO approaches that in the crystal structure, which results in the interpair interactions being the dominant dipolar interaction

  8. DEGRADATION OF 3-METHYLPHENOL PHOTOINDUCED BY THE COMPLEX Fe (III-CITRATE IN THE PRESENCE OF HYDROGEN PEROXIDE

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    N SERAGHNI

    2014-07-01

    Full Text Available The study of 3-methylphenol (m-cresol photodegradation has been achieved in two system, UV / Fe(III-Cit and UV / Fe(III-Cit / H2O2 in natural (pH = 6.5. The presence of H2O2 in UV / Fe(III-Cit system  reduce the efficiency of m-cresol degradation  at low concentration, however for the high level of H2O2 the process is improved. The optimal concentration of H2O2 was found to be 5 mM. This can be probably explained by a low Fe(II formation of in this system. The result shows in the both systems that the acidic media is favorable for this kind of reaction. The Comparison between the aquacomplexes and Fe(III-Cit complex  in the presence or absence of H2O2 have confirmed that the best condition of m-cresol degradation was achieved with the addition of  H2O2. Additionally, the use of 1.0 % of tertiobutanol as a scavenger confirmed the intervention of hydroxyl radicals in the m-cresol photodegradation.

  9. Shewanella putrefaciens produces an Fe(III)-solubilizing organic ligand during anaerobic respiration on insoluble Fe(III) oxides.

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    Taillefert, Martial; Beckler, Jordon S; Carey, Elizabeth; Burns, Justin L; Fennessey, Christine M; DiChristina, Thomas J

    2007-11-01

    The mechanism of Fe(III) reduction was investigated using voltammetric techniques in anaerobic incubations of Shewanella putrefaciens strain 200 supplemented with Fe(III) citrate or a suite of Fe(III) oxides as terminal electron acceptor. Results indicate that organic complexes of Fe(III) are produced during the reduction of Fe(III) at rates that correlate with the reactivity of the Fe(III) phase and bacterial cell density. Anaerobic Fe(III) solubilization activity is detected with either Fe(III) oxides or Fe(III) citrate, suggesting that the organic ligand produced is strong enough to destabilize Fe(III) from soluble or solid Fe(III) substrates. Results also demonstrate that Fe(III) oxide dissolution is not controlled by the intrinsic chemical reactivity of the Fe(III) oxides. Instead, the chemical reaction between the endogenous organic ligand is only affected by the number of reactive surface sites available to S. putrefaciens. This report describes the first application of voltammetric techniques to demonstrate production of soluble organic-Fe(III) complexes by any Fe(III)-reducing microorganism and is the first report of a Fe(III)-solubilizing ligand generated by a metal-reducing member of the genus Shewanella.

  10. Mechanisms of Sb(III) Photooxidation by the Excitation of Organic Fe(III) Complexes.

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    Kong, Linghao; He, Mengchang

    2016-07-05

    Organic Fe(III) complexes are widely distributed in the aqueous environment, which can efficiently generate free radicals under light illumination, playing a significant role in heavy metal speciation. However, the potential importance of the photooxidation of Sb(III) by organic Fe(III) complexes remains unclear. Therefore, the photooxidation mechanisms of Sb(III) were comprehensively investigated in Fe(III)-oxalate, Fe(III)-citrate and Fe(III)-fulvic acid (FA) solutions by kinetic measurements and modeling. Rapid photooxidation of Sb(III) was observed in an Fe(III)-oxalate solution over the pH range of 3 to 7. The addition of tert-butyl alcohol (TBA) as an ·OH scavenger quenched the Sb(III) oxidation, suggesting that ·OH is an important oxidant for Sb(III). However, the incomplete quenching of Sb(III) oxidation indicated the existence of other oxidants, presumably an Fe(IV) species in irradiated Fe(III)-oxalate solution. In acidic solutions, ·OH may be formed by the reaction of Fe(II)(C2O4) with H2O2, but a hypothetical Fe(IV) species may be generated by the reaction of Fe(II)(C2O4)2(2-) with H2O2 at higher pH. Kinetic modeling provides a quantitative explanation of the results. Evidence for the existence of ·OH and hypothetical Fe(IV) was also observed in an irradiated Fe(III)-citrate and Fe(III)-FA system. This study demonstrated an important pathway of Sb(III) oxidation in surface waters.

  11. Dissimilatory Fe(III) Reduction by the Marine Microorganism Desulfuromonas acetoxidans

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    Roden, Eric E.; Lovley, Derek R.

    1993-01-01

    The ability of the marine microorganism Desulfuromonas acetoxidans to reduce Fe(III) was investigated because of its close phylogenetic relationship with the freshwater dissimilatory Fe(III) reducer Geobacter metallireducens. Washed cell suspensions of the type strain of D. acetoxidans reduced soluble Fe(III)-citrate and Fe(III) complexed with nitriloacetic acid. The c-type cytochrome(s) of D. acetoxidans was oxidized by Fe(III)-citrate and Mn(IV)-oxalate, as well as by two electron acceptors...

  12. Effect of ferri(III)citrate and potassium hexacyanoferrate(III) on growth of the moss Bryum argenteum Hedw. (Bryaceae) in vitro

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    Vukojević Vanja; Sabovljević Aneta; Sabovljević Marko S.

    2004-01-01

    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(III)citrate 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 es...

  13. Citrate influences microbial Fe hydroxide reduction via a dissolution-disaggregation mechanism

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    Braunschweig, Juliane; Klier, Christine; Schröder, Christian; Händel, Matthias; Bosch, Julian; Totsche, Kai U.; Meckenstock, Rainer U.

    2014-08-01

    Microbial reduction of ferric iron is partly dependent on Fe hydroxide particle size: nanosized Fe hydroxides greatly exceed the bioavailability of their counterparts larger than 1 μm. Citrate as a low molecular weight organic acid can likewise stabilize colloidal suspensions against aggregation by electrostatic repulsion but also increase Fe bioavailability by enhancing Fe hydroxide solubility. The aim of this study was to see whether adsorption of citrate onto surfaces of large ferrihydrite aggregates results in the formation of a stable colloidal suspension by electrostatic repulsion and how this effect influences microbial Fe reduction. Furthermore, we wanted to discriminate between citrate-mediated colloid stabilization out of larger aggregates and ferrihydrite dissolution and their influence on microbial Fe hydroxide reduction. Dissolution kinetics of ferrihydrite aggregates induced by different concentrations of citrate and humic acids were compared to microbial reduction kinetics with Geobacter sulfurreducens. Dynamic light scattering results showed the formation of a stable colloidal suspension and colloids with hydrodynamic diameters of 69 (±37) to 165 (± 65) nm for molar citrate:Fe ratios of 0.1 to 0.5 and partial dissolution of ferrihydrite at citrate:Fe ratios ⩾ 0.1. No dissolution or colloid stabilization was detected in the presence of humic acids. Adsorption of citrate, necessary for dissolution, reversed the surface charge and led to electrostatic repulsion between sub-aggregates of ferrihydrite and colloid stabilization when the citrate:Fe ratio was above a critical value (⩽ 0.1). Lower ratios resulted in stronger ferrihydrite aggregation instead of formation of a stable colloidal suspension, owing to neutralization of the positive surface charge. At the same time, microbial ferrihydrite reduction increased from 0.029 to 0.184 mM h-1 indicating that colloids stabilized by citrate addition enhanced microbial Fe reduction. Modelling of

  14. 21 CFR 184.1298 - Ferric citrate.

    Science.gov (United States)

    2010-04-01

    ... Substances Affirmed as GRAS § 184.1298 Ferric citrate. (a) Ferric citrate (iron (III) citrate, C6H5FeO7, CAS Reg. No. 2338-05-8) is prepared from reaction of citric acid with ferric hydroxide. It is a compound of indefinite ratio of citric acid and iron. (b) The ingredient must be of a purity suitable for...

  15. The influence of ferric (III citrate on ATP-hydrolases of Desulfuromonas acetoxidans ІМV В-7384

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    O. Maslovska

    2013-02-01

    Full Text Available Desulfuromonas acetoxidans obtains energy for growth by the anaerobic oxidation of organic compounds with the carbon dioxide formation. It was found that ferrum and manganese are used as terminal electron acceptors in the processes of anaerobic respiration, such as dissimilative Fe3+- and Mn4+-reduction, carried out by these bacteria (Lovely, 1991. D. acetoxidans ІМV B-7384 can be used as anode biocatalyst in microbial fuel cell with high electron recovery through acetate oxidation to the electric current as a result of electron transfer to the anode or 3d-type transition metals, such as ferrum and manganese, in the process of their reduction. Investigation of biochemical changes of D. acetoxidans ІМV B-7384 under the influence of Fe (III compounds is important for optimization of the process of bacterial electricity generation. ATP-hydrolase is located in cytoplasmic membrane, and its subunits are exposed to both the cytoplasm and the external environment. Therefore, the changes of that enzyme activity can be used as an indicator of various stress exposure. Presence of ferric iron ions in the bacterial growth medium could catalyze generation of organic reactive oxygen species, such as peroxyl (ROO- and alkoxyl (RO- radicals. Lipid peroxidation is one of the main reasons of cell damage and it’s following death under the influence of reactive oxygen metabolites. It is known that lipid peroxidation and membrane transport processes are somehow interrelated, but mechanisms of such interaction are still unidentified. In our previous researche we have shown the influence of ferric (III citrate on the intensity of lipid peroxidation of D. аcetoxidans ІМV В-7384. Significant increase of the content of lipid peroxidation products (lipid hydroperoxides, conjugated dienes and malondialdehyde in bacterial cells has been observed under the addition of ferric (III citrate into the cultural medium. The increase of the concentration of lipid

  16. Advanced experimental analysis of controls on microbial Fe(III) oxide reduction. First year progress report

    Energy Technology Data Exchange (ETDEWEB)

    Roden, E.E.; Urrutia, M.M.

    1997-07-01

    'The authors have made considerable progress toward a number of project objectives during the first several months of activity on the project. An exhaustive analysis was made of the growth rate and biomass yield (both derived from measurements of cell protein production) of two representative strains of Fe(III)-reducing bacteria (Shewanellaalga strain BrY and Geobactermetallireducens) growing with different forms of Fe(III) as an electron acceptor. These two fundamentally different types of Fe(III)-reducing bacteria (FeRB) showed comparable rates of Fe(III) reduction, cell growth, and biomass yield during reduction of soluble Fe(III)-citrate and solid-phase amorphous hydrous ferric oxide (HFO). Intrinsic growth rates of the two FeRB were strongly influenced by whether a soluble or a solid-phase source of Fe(III) was provided: growth rates on soluble Fe(III) were 10--20 times higher than those on solid-phase Fe(III) oxide. Intrinsic FeRB growth rates were comparable during reduction of HF0 and a synthetic crystalline Fe(III) oxide (goethite). A distinct lag phase for protein production was observed during the first several days of incubation in solid-phase Fe(III) oxide medium, even though Fe(III) reduction proceeded without any lag. No such lag between protein production and Fe(III) reduction was observed during growth with soluble Fe(III). This result suggested that protein synthesis coupled to solid-phase Fe(III) oxide reduction in batch culture requires an initial investment of energy (generated by Fe(III) reduction), which is probably needed for synthesis of materials (e.g. extracellular polysaccharides) required for attachment of the cells to oxide surfaces. This phenomenon may have important implications for modeling the growth of FeRB in subsurface sedimentary environments, where attachment and continued adhesion to solid-phase materials will be required for maintenance of Fe(III) reduction activity. Despite considerable differences in the rate and

  17. Phosphate inhibits in vitro Fe3+ loading into transferrin by forming a soluble Fe(III)-phosphate complex: a potential non-transferrin bound iron species.

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    Hilton, Robert J; Seare, Matthew C; Andros, N David; Kenealey, Zachary; Orozco, Catalina Matias; Webb, Michael; Watt, Richard K

    2012-05-01

    In chronic kidney diseases, NTBI can occur even when total iron levels in serum are low and transferrin is not saturated. We postulated that elevated serum phosphate concentrations, present in CKD patients, might disrupt Fe(3+) loading into apo-transferrin by forming Fe(III)-phosphate species. We report that phosphate competes with apo-transferrin for Fe(3+) by forming a soluble Fe(III)-phosphate complex. Once formed, the Fe(III)-phosphate complex is not a substrate for donating Fe(3+) to apo-transferrin. Phosphate (1-10mM) does not chelate Fe(III) from diferric transferrin under the conditions examined. Complexed forms of Fe(3+), such as iron nitrilotriacetic acid (Fe(3+)-NTA), and Fe(III)-citrate are not susceptible to this phosphate complexation reaction and efficiently deliver Fe(3+) to apo-transferrin in the presence of phosphate. This reaction suggests that citrate might play an important role in protecting against Fe(III), phosphate interactions in vivo. In contrast to the reactions of Fe(3+) and phosphate, the addition of Fe(2+) to a solution of apo-transferrin and phosphate lead to rapid oxidation and deposition of Fe(3+) into apo-transferrin. These in vitro data suggest that, in principle, elevated phosphate concentrations can influence the ability of apo-transferrin to bind iron, depending on the oxidation state of the iron.

  18. Dissimilatory Fe(III) reduction by the marine microorganism Desulfuromonas acetoxidans

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    Roden, E.E.; Lovley, D.R.

    1993-01-01

    The ability of the marine microorganism Desulfuromonas acetoxidans to reduce Fe(III) was investigated because of its close phylogenetic relationship with the freshwater dissimilatory Fe(III) reducer Geobacter metallireducens. Washed cell suspensions of the type strain of D. acetoxidans reduced soluble Fe(III)-citrate and Fe(III) complexed with nitriloacetic acid. The c-type cytochrome(s) of D. acetoxidans was oxidized by Fe(III)- citrate and Mn(IV)-oxalate, as well as by two electron acceptors known to support growth, colloidal sulfur and malate. D. acetoxidans grew in defined anoxic, bicarbonate-buffered medium with acetate as the sole electron donor and poorly crystalline Fe(III) or Mn(IV) as the sole electron acceptor. Magnetite (Fe3O4) and siderite (FeCO3) were the major end products of Fe(III) reduction, whereas rhodochrosite (MnCO3) was the end product of Mn(IV) reduction. Ethanol, propanol, pyruvate, and butanol also served as electron donors for Fe(III) reduction. In contrast to D. acetoxidans, G. metallireducens could only grow in freshwater medium and it did not conserve energy to support growth from colloidal S0 reduction. D. acetoxidans is the first marine microorganism shown to conserve energy to support growth by coupling the complete oxidation of organic compounds to the reduction of Fe(III) or Mn(IV). Thus, D. acetoxidans provides a model enzymatic mechanism for Fe(III) or Mn(IV) oxidation of organic compounds in marine and estuarine sediments. These findings demonstrate that 16S rRNA phylogenetic analyses can suggest previously unrecognized metabolic capabilities of microorganisms.

  19. Effects of Sodium Citrate Concentration on Electroless Ni-Fe Bath Stability and Deposition

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    Jung, Myung-Won; Kang, Sung K.; Lee, Jae-Ho

    2014-01-01

    In this research, electroless Ni-Fe bath stability and deposition characteristics were investigated for various sodium citrate concentrations. Complexing agents such as sodium citrate are one of the main components of such electroless plating baths. Since they could play various roles such as maintaining pH stability, preventing precipitation of metal salts, and reducing the concentrations of free metal ions, the concentration of complexing agents in the plating bath is an important parameter for electroless deposition processes. In this research, unstable baths were obtained for insufficient sodium citrate concentrations, and these phenomena were analyzed with ChemEQL. Moreover, the deposition characteristics of electroless Ni-Fe for under bump metallurgy diffusion barriers were also investigated using energy-dispersive spectroscopy and field-emission scanning electron microscopy.

  20. Outer cell surface components essential for Fe(III) oxide reduction by Geobacter metallireducens.

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    Smith, Jessica A; Lovley, Derek R; Tremblay, Pier-Luc

    2013-02-01

    Geobacter species are important Fe(III) reducers in a diversity of soils and sediments. Mechanisms for Fe(III) oxide reduction have been studied in detail in Geobacter sulfurreducens, but a number of the most thoroughly studied outer surface components of G. sulfurreducens, particularly c-type cytochromes, are not well conserved among Geobacter species. In order to identify cellular components potentially important for Fe(III) oxide reduction in Geobacter metallireducens, gene transcript abundance was compared in cells grown on Fe(III) oxide or soluble Fe(III) citrate with whole-genome microarrays. Outer-surface cytochromes were also identified. Deletion of genes for c-type cytochromes that had higher transcript abundance during growth on Fe(III) oxides and/or were detected in the outer-surface protein fraction identified six c-type cytochrome genes, that when deleted removed the capacity for Fe(III) oxide reduction. Several of the c-type cytochromes which were essential for Fe(III) oxide reduction in G. metallireducens have homologs in G. sulfurreducens that are not important for Fe(III) oxide reduction. Other genes essential for Fe(III) oxide reduction included a gene predicted to encode an NHL (Ncl-1-HT2A-Lin-41) repeat-containing protein and a gene potentially involved in pili glycosylation. Genes associated with flagellum-based motility, chemotaxis, and pili had higher transcript abundance during growth on Fe(III) oxide, consistent with the previously proposed importance of these components in Fe(III) oxide reduction. These results demonstrate that there are similarities in extracellular electron transfer between G. metallireducens and G. sulfurreducens but the outer-surface c-type cytochromes involved in Fe(III) oxide reduction are different.

  1. Metallocoenzyme-mediated reductive transformation of carbon tetrachloride in titanium (III) citrate aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Chiu, P.C.; Reinhard, M. [Stanford Univ., CA (United States)

    1995-03-01

    Transformation pathways for carbon tetrachloride (CCl{sub 4}) catalyzed by hematin or vitamin B{sub 12} in aqueous titanium(III) citrate solution are proposed. The reaction of CCl{sub 4} with B{sub 12} was zero order in CCl{sub 4} and first order in B{sub 12}, and the rate constant was measured from pH 7.3 to pH 10.3. The proposed rate-limiting step is the reduction of the stable trichloromethylcobalamin (CCl{sub 3}-Cbl) intermediate by titanium(III) citrate at alkaline pH and the sterically induced CCl{sub 3}-Cbl decomposition at neutral pH. The reaction kinetics can be described by a modified Michaelis-Menten model in the saturated regime. With hematin, only the pseudo-first-order rate constant was determined due to the significant deactivation of the coenzyme. The turnover number of hematin (molecules of CCl{sub 4} transformed/molecule of hematin deactivated) was 27 at pH 8.0 and 42 at pH 9.9. Vitamin B{sub 12} was a more stable and more effective catalyst (on a molar basis) than hematin with respect to CCl{sub 4}. Chloroform (CHCl{sub 3}) was the primary product in titanium(III) citrate solution, and the yield was a function of pH, Ti(III) concentration, and organic content regardless of whether a coenzyme was present or which coenzyme was used. Although B{sub 12} and hematin can both enhance the CCl{sub 4} transformation rate, they have little effect on the CHCl{sub 3} yield. Titanium(III) citrate, on the other hand, controls not only the transformation rate but also CHCl{sub 3} formation. 77 refs., 10 figs.

  2. Mitochondrial DNA damage associated with lipid peroxidation of the mitochondrial membrane induced by Fe2+-citrate

    OpenAIRE

    2006-01-01

    Iron imbalance/accumulation has been implicated in oxidative injury associated with many degenerative diseases such as hereditary hemochromatosis, beta-thalassemia, and Friedreich's ataxia. Mitochondria are particularly sensitive to iron-induced oxidative stress - high loads of iron cause extensive lipid peroxidation and membrane permeabilization in isolated mitochondria. Here we detected and characterized mitochondrial DNA damage in isolated rat liver mitochondria exposed to a Fe2+-citrate c...

  3. Fe(III INVOLVEMENT IN THE PHOTODEGRADATION OF ASPIRIN IN HOMOGENEOUS AND HETEROGENEOUS PHASE

    Directory of Open Access Journals (Sweden)

    Y MAMERI

    2014-07-01

    Full Text Available The photocatalytic degradation of Aspirin (ASP induced by Fe(III in homogeneous (ASP-Fe(III-citrate complex and heterogeneous phase (ASP-Goethite was studied in aqueous solution up on irradiation at 365nm and by solar light.  A dark investigation of system containing a mixture of aspirin and Fe (III reveals no interaction in homogeneous phase but in heterogeneous phase, the interaction observed was traduced by aspirin adsorption on Goethite in aqueous solution. Under irradiation, Fe(III-Citrate complex enhance the photooxidation of ASP; a pseudo-first order kinetic model was employed to discuss the results. Against in heterogeneous phase, kinetics is slower and the process is accelerated at acidic pH. The involvement of HO● radicals has been established because of the influence of tertiobutanol used as a scavenger. The photodegradation of ASP in the mixture ASP-Fe(III-Cit and ASP-Goethite under solar light was significantly accelerated in comparison with artificial irradiation at 365nm.

  4. Bacillus cereus iron uptake protein fishes out an unstable ferric citrate trimer

    OpenAIRE

    Fukushima, Tatsuya; Sia, Allyson K.; Allred, Benjamin E.; Nichiporuk, Rita; Zhou, Zhongrui; Andersen, Ulla N.; Raymond, Kenneth N.

    2012-01-01

    Citrate is a common biomolecule that chelates Fe(III). Many bacteria and plants use ferric citrate to fulfill their nutritional requirement for iron. Only the Escherichia coli ferric citrate outer-membrane transport protein FecA has been characterized; little is known about other ferric citrate-binding proteins. Here we report a unique siderophore-binding protein from the Gram-positive pathogenic bacterium Bacillus cereus that binds multinuclear ferric citrate complexes. We have demonstrated ...

  5. Interactions Between Fe(III)-oxides and Fe(III)-phyllosilicates During Microbial Reduction 2: Natural Subsurface Sediments

    Energy Technology Data Exchange (ETDEWEB)

    Wu, T.; Griffin, A. M.; Gorski, C. A.; Shelobolina, E. S.; Xu, H.; Kukkadapu, R. K.; Roden, E. E.

    2016-04-19

    Dissimilatory microbial reduction of solid-phase Fe(III)-oxides and Fe(III)-bearing phyllosilicates (Fe(III)-phyllosilicates) is an important process in anoxic soils, sediments, and subsurface materials. Although various studies have documented the relative extent of microbial reduction of single-phase Fe(III)-oxides and Fe(III)-phyllosilicates, detailed information is not available on interaction between these two processes in situations where both phases are available for microbial reduction. The goal of this research was to use the model dissimilatory iron-reducing bacterium (DIRB) Geobacter sulfurreducens to study Fe(III)-oxide vs. Fe(III)-phyllosilicate reduction in a range of subsurface materials and Fe(III)-oxide stripped versions of the materials. Low temperature (12K) Mossbauer spectroscopy was used to infer changes in the relative abundances of Fe(III)-oxide, Fe(III)-phyllosilicate, and phyllosilicate-associated Fe(II) (Fe(II)-phyllosilicate). A Fe partitioning model was employed to analyze the fate of Fe(II) and assess the potential for abiotic Fe(II)-catalyzed reduction of Fe(III)-phyllosilicates. The results showed that in most cases Fe(III)- oxide utilization dominated (70-100 %) bulk Fe(III) reduction activity, and that electron transfer from oxide-derived Fe(II) played only a minor role (ca. 10-20 %) in Fe partitioning. In addition, the extent of Fe(III)-oxide reduction was positively correlated to surface area-normalized cation exchange capacity and the phyllosilicate-Fe(III)/total Fe(III) ratio, which suggests that the phyllosilicates in the natural sediments promoted Fe(III)-oxide reduction by binding of oxide-derived Fe(II), thereby enhancing Fe(III)-oxide reduction by reducing or delaying the inhibitory effect that Fe(II) accumulation on oxide and DIRB cell surfaces has on Fe(III)-oxide reduction. In general our results suggest that although Fe(III)-oxide reduction is likely to dominate bulk Fe(III) reduction in most subsurface sediments, Fe

  6. Aqueous complexation of citrate with neodymium(III) and americium(III): a study by potentiometry, absorption spectrophotometry, microcalorimetry, and XAFS.

    Science.gov (United States)

    Brown, M Alex; Kropf, A Jeremy; Paulenova, Alena; Gelis, Artem V

    2014-05-07

    The aqueous complexation of Nd(III) and Am(III) with anions of citrate was studied by potentiometry, absorption spectrophotometry, microcalorimetry, and X-ray absorption fine structure (XAFS). Using potentiometric titration data fitting the metal-ligand (L) complexes that were identified for Nd(III) were NdHL, NdL, NdHL2, and NdL2; a review of trivalent metal-citrate complexes is also included. Stability constants for these complexes were calculated from potentiometric and spectrophotometric titrations. Microcalorimetric results concluded that the entropy term of complex formation is much more dominant than the enthalpy. XAFS results showed a dependence in the Debye-Waller factor that indicated Nd(iii)-citrate complexation over the pH range of 1.56-6.12.

  7. 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

    In oxic oceans, most of the dissolved iron (Fe) exists as complexes with siderophore-like, strongly coordinating organic ligands. Thus, the isotope composition of the little amount of free inorganic Fe that is available for precipitation and preservation in the geological record may largely...... differently complexed Fe(III) pools were separated by addition of Na2CO3, which led to immediate precipitation of the inorganic Fe without causing significant dissociation of Fe-desferrioxamine complexes. Experiments using enriched 57Fe tracer showed that isotopic equilibration between the 57Fe......(III)-bearing environments, such as soils and rivers, and may, for example, largely control the Fe isotope composition of marine Fe–Mn crusts....

  8. Mitochondrial DNA damage associated with lipid peroxidation of the mitochondrial membrane induced by Fe2+-citrate

    Directory of Open Access Journals (Sweden)

    Andréa M. Almeida

    2006-09-01

    Full Text Available Iron imbalance/accumulation has been implicated in oxidative injury associated with many degenerative diseases such as hereditary hemochromatosis, beta-thalassemia, and Friedreich's ataxia. Mitochondria are particularly sensitive to iron-induced oxidative stress - high loads of iron cause extensive lipid peroxidation and membrane permeabilization in isolated mitochondria. Here we detected and characterized mitochondrial DNA damage in isolated rat liver mitochondria exposed to a Fe2+-citrate complex, a small molecular weight complex. Intense DNA fragmentation was induced after the incubation of mitochondria with the iron complex. The detection of 3' phosphoglycolate ends at the mtDNA strand breaks by a 32P-postlabeling assay, suggested the involvement of hydroxyl radical in the DNA fragmentation induced by Fe2+-citrate. Increased levels of 8-oxo-7,8-dihydro-2'-deoxyguanosine also suggested that Fe2+-citrate-induced oxidative stress causes mitochondrial DNA damage. In conclusion, our results show that iron-mediated lipid peroxidation was associated with intense mtDNA damage derived from the direct attack of reactive oxygen species.Desequilíbrio/acúmulo de ferro tem sido implicado em injúria oxidativa associada a diversas doenças degenerativas tais como, hemocromatose hereditária, beta-talassemia e ataxia de Friedreich. As mitocôndrias são particularmente sensíveis a estresse oxidativo induzido por ferro - um carregamento alto de ferro em mitocôndrias isoladas pode causar uma extensiva peroxidação lipídica e a permeabilização de membrana. Nesse estudo, nós detectamos e caracterizamos danos do DNA mitocondrial em mitocôndrias isoladas de fígado de rato, expostas ao complexo Fe2+-citrato, um dos complexos de baixo peso molecular. A intensa fragmentação do DNA foi induzida após a incubação das mitocôndrias com o complexo de ferro. A detecção de finais 3' de fosfoglicolato nas quebras de fitas de DNA mitocondrial pelo ensaio 32

  9. Extracellular electron transfer to Fe(III) oxides by the hyperthermophilic archaeon Geoglobus ahangari via a direct contact mechanism.

    Science.gov (United States)

    Manzella, Michael P; Reguera, Gemma; Kashefi, Kazem

    2013-08-01

    The microbial reduction of Fe(III) plays an important role in the geochemistry of hydrothermal systems, yet it is poorly understood at the mechanistic level. Here we show that the obligate Fe(III)-reducing archaeon Geoglobus ahangari uses a direct-contact mechanism for the reduction of Fe(III) oxides to magnetite at 85°C. Alleviating the need to directly contact the mineral with the addition of a chelator or the electron shuttle anthraquinone-2,6-disulfonate (AQDS) stimulated Fe(III) reduction. In contrast, entrapment of the oxides within alginate beads to prevent cell contact with the electron acceptor prevented Fe(III) reduction and cell growth unless AQDS was provided. Furthermore, filtered culture supernatant fluids had no effect on Fe(III) reduction, ruling out the secretion of an endogenous mediator too large to permeate the alginate beads. Consistent with a direct contact mechanism, electron micrographs showed cells in intimate association with the Fe(III) mineral particles, which once dissolved revealed abundant curled appendages. The cells also produced several heme-containing proteins. Some of them were detected among proteins sheared from the cell's outer surface and were required for the reduction of insoluble Fe(III) oxides but not for the reduction of the soluble electron acceptor Fe(III) citrate. The results thus support a mechanism in which the cells directly attach and transfer electrons to the Fe(III) oxides using redox-active proteins exposed on the cell surface. This strategy confers on G. ahangari a competitive advantage for accessing and reducing Fe(III) oxides under the extreme physical and chemical conditions of hot ecosystems.

  10. Dissimilatory Reduction of Fe(III) and Other Electron Acceptors by a Thermus Isolate

    Energy Technology Data Exchange (ETDEWEB)

    Kieft, T. L. [New Mexico Inst. of Mining and Technology, Socorro, NM (United States); Fredrickson, J. K. [Pacific Northwest National Lab., Richland, WA (United States); Onstott, T. C. [Princeton Univ., NJ (United States). Dept. of Geological and Geophysical Sciences; Gorby, Y. A. [Pacific Northwest National Lab., Richland, WA (United States); Kostandarithes, H. M. [Pacific Northwest National Lab., Richland, WA (United States); Bailey, T. J. [Pacific Northwest National Lab., Richland, WA (United States); Kennedy, D. W. [Pacific Northwest National Lab., Richland, WA (United States); Li, S. W. [Pacific Northwest National Lab., Richland, WA (United States); Plymale, A. E. [Pacific Northwest National Lab., Richland, WA (United States); Spadoni, C. M. [Pacific Northwest National Lab., Richland, WA (United States); Gray, M. S. [Pacific Northwest National Lab., Richland, WA (United States)

    1995-10-25

    A thermophilic bacterium that could use O{sub 2}, NO{sub 3}{sup -}, Fe(III), or S{sup o} as terminal electron acceptors for growth was isolated from groundwater sampled at 3.2 km depth in a South African gold mine. This organism, designated SA-01, clustered most closely with members of the genus Thermus, as determined by 16S rDNA gene sequence analysis. The 16S rDNA sequence of SA-01 was >98% similar to that of Thermus strain NMX2 A.1, which was previously isolated by other investigators from a thermal spring in New Mexico. Strain NMX2 A.1 was also able to reduce Fe(III) and other electron acceptors, whereas Thermus aquaticus (ATCC 25104) and Thermus filiformis (ATCC 43280) did not reduce NO{sub 3}{sup -} or Fe(III). Neither SA-01 nor NMX2 A.1 grew fermentatively, i.e., addition of an external electron acceptor was required for anaerobic growth. Thermus SA-01 reduced soluble Fe(III) complexed with citrate or nitrilotriacetic acid (NTA); however, it could only reduce relatively small quantities (0.5 mM) of hydrous ferric oxide (HFO) except when the humic acid analog 2,6-anthraquinone disulfonate (AQDS) was added as an electron shuttle, in which case 10 mM Fe(III) was reduced. Fe(III)-NTA was reduced quantitatively to Fe(II), was coupled to the oxidation of lactate, and could support growth through three consecutive transfers. Suspensions of Thermus SA-01 cells also reduced Mn(IV), Co(III)-EDTA, Cr(VI), and AQDS. Mn(IV)-oxide was reduced in the presence of either lactate or H{sub 2}. Both strains were also able to mineralize NTA to CO{sub 2} and to couple its oxidation to Fe(III) reduction and growth. The optimum temperature for growth and Fe(III) reduction by Thermus SA-01 and NMX2 A.1 is approximately 65 C; optimum pH is 6.5 to 7.0. This is the first report of a Thermus sp. being able to couple the oxidation of organic compounds to the reduction of Fe, Mn or S.

  11. Dissimilatory Reduction of Fe(III) and Other Electron Acceptors by a Thermus Isolate

    Energy Technology Data Exchange (ETDEWEB)

    Kieft, T. L. [New Mexico Inst. of Mining and Technology, Socorro, NM (United States); Fredrickson, J. K. [Pacific Northwest National Lab., Richland, WA (United States); Onstott, T. C. [Princeton Univ., NJ (United States). Dept. of Geological and Geophysical Sciences; Gorby, Y. A. [Pacific Northwest National Lab., Richland, WA (United States); Kostandarithes, H. M. [Pacific Northwest National Lab., Richland, WA (United States); Bailey, T. J. [Pacific Northwest National Lab., Richland, WA (United States); Kennedy, D. W. [Pacific Northwest National Lab., Richland, WA (United States); Li, S. W. [Pacific Northwest National Lab., Richland, WA (United States); Plymale, A. E. [Pacific Northwest National Lab., Richland, WA (United States); Spadoni, C. M. [Pacific Northwest National Lab., Richland, WA (United States); Gray, M. S. [Pacific Northwest National Lab., Richland, WA (United States)

    1995-10-25

    A thermophilic bacterium that could use O{sub 2}, NO{sub 3}{sup -}, Fe(III), or S{sup o} as terminal electron acceptors for growth was isolated from groundwater sampled at 3.2 km depth in a South African gold mine. This organism, designated SA-01, clustered most closely with members of the genus Thermus, as determined by 16S rDNA gene sequence analysis. The 16S rDNA sequence of SA-01 was >98% similar to that of Thermus strain NMX2 A.1, which was previously isolated by other investigators from a thermal spring in New Mexico. Strain NMX2 A.1 was also able to reduce Fe(III) and other electron acceptors, whereas Thermus aquaticus (ATCC 25104) and Thermus filiformis (ATCC 43280) did not reduce NO{sub 3}{sup -} or Fe(III). Neither SA-01 nor NMX2 A.1 grew fermentatively, i.e., addition of an external electron acceptor was required for anaerobic growth. Thermus SA-01 reduced soluble Fe(III) complexed with citrate or nitrilotriacetic acid (NTA); however, it could only reduce relatively small quantities (0.5 mM) of hydrous ferric oxide (HFO) except when the humic acid analog 2,6-anthraquinone disulfonate (AQDS) was added as an electron shuttle, in which case 10 mM Fe(III) was reduced. Fe(III)-NTA was reduced quantitatively to Fe(II), was coupled to the oxidation of lactate, and could support growth through three consecutive transfers. Suspensions of Thermus SA-01 cells also reduced Mn(IV), Co(III)-EDTA, Cr(VI), and AQDS. Mn(IV)-oxide was reduced in the presence of either lactate or H{sub 2}. Both strains were also able to mineralize NTA to CO{sub 2} and to couple its oxidation to Fe(III) reduction and growth. The optimum temperature for growth and Fe(III) reduction by Thermus SA-01 and NMX2 A.1 is approximately 65 C; optimum pH is 6.5 to 7.0. This is the first report of a Thermus sp. being able to couple the oxidation of organic compounds to the reduction of Fe, Mn or S.

  12. Rapid photooxidation of Sb(III) in the presence of different Fe(III) species

    Science.gov (United States)

    Kong, Linghao; He, Mengchang; Hu, Xingyun

    2016-05-01

    The toxicity and mobility of antimony (Sb) are strongly influenced by the redox processes associated with Sb. Dissolved iron (Fe) is widely distributed in the environment as different species and plays a significant role in Sb speciation. However, the mechanisms of Sb(III) oxidation in the presence of Fe have remained unclear because of the complexity of Fe and Sb speciation. In this study, the mechanisms of Sb(III) photooxidation in the presence of different Fe species were investigated systematically. The photooxidation of Sb(III) occurred over a wide pH range, from 1 to 10. Oxygen was not a predominant or crucial factor in the Sb(III) oxidation process. The mechanism of Sb(III) photooxidation varied depending on the Fe(III) species. In acidic solution (pH 1-3), dichloro radicals (radCl2-) and hydroxyl radicals (radOH) generated by the photocatalysis of FeCl2+ and FeOH2+ were the main oxidants for Sb(III) oxidation. Fe(III) gradually transformed into the colloid ferric hydroxide (CFH) and ferrihydrite in circumneutral and alkaline solutions (pH 4-10). Photooxidation of Sb(III) occurred through electron transfer from Sb(III) to Fe(III) along with the reduction of Fe(III) to Fe(II) through a ligand-to-metal charge-transfer (LMCT) process. The photocatalysis of different Fe(III) species may play an important role in the geochemical cycle of Sb(III) in surface soil and aquatic environments.

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

    Science.gov (United States)

    Lovley, Derek R; Holmes, Dawn E; Nevin, Kelly P

    2004-01-01

    Dissimilatory Fe(III) and Mn(IV) reduction has an important influence on the geochemistry of modern environments, and Fe(III)-reducing microorganisms, most notably those in the Geobacteraceae family, can play an important role in the bioremediation of subsurface environments contaminated with organic or metal contaminants. Microorganisms with the capacity to conserve energy from Fe(III) and Mn(IV) reduction are phylogenetically dispersed throughout the Bacteria and Archaea. The ability to oxidize hydrogen with the reduction of Fe(III) is a highly conserved characteristic of hyperthermophilic microorganisms and one Fe(III)-reducing Archaea grows at the highest temperature yet recorded for any organism. Fe(III)- and Mn(IV)-reducing microorganisms have the ability to oxidize a wide variety of organic compounds, often completely to carbon dioxide. Typical alternative electron acceptors for Fe(III) reducers include oxygen, nitrate, U(VI) and electrodes. Unlike other commonly considered electron acceptors, Fe(III) and Mn(IV) oxides, the most prevalent form of Fe(III) and Mn(IV) in most environments, are insoluble. Thus, Fe(III)- and Mn(IV)-reducing microorganisms face the dilemma of how to transfer electrons derived from central metabolism onto an insoluble, extracellular electron acceptor. Although microbiological and geochemical evidence suggests that Fe(III) reduction may have been the first form of microbial respiration, the capacity for Fe(III) reduction appears to have evolved several times as phylogenetically distinct Fe(III) reducers have different mechanisms for Fe(III) reduction. Geobacter species, which are representative of the family of Fe(III) reducers that predominate in a wide diversity of sedimentary environments, require direct contact with Fe(III) oxides in order to reduce them. In contrast, Shewanella and Geothrix species produce chelators that solubilize Fe(III) and release electron-shuttling compounds that transfer electrons from the cell surface to

  14. 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......In oxic oceans, most of the dissolved iron (Fe) exists as complexes with siderophore-like, strongly coordinating organic ligands. Thus, the isotope composition of the little amount of free inorganic Fe that is available for precipitation and preservation in the geological record may largely...... for the slower stage, indicating that approximately 40% reequilibration may take place during the separation of the two pools. To further test if the induced precipitation leads to experimental artefacts, the fractionation during precipitation of inorganic Fe was determined. Assuming a Rayleigh...

  15. Bacillus cereus iron uptake protein fishes out an unstable ferric citrate trimer.

    Science.gov (United States)

    Fukushima, Tatsuya; Sia, Allyson K; Allred, Benjamin E; Nichiporuk, Rita; Zhou, Zhongrui; Andersen, Ulla N; Raymond, Kenneth N

    2012-10-16

    Citrate is a common biomolecule that chelates Fe(III). Many bacteria and plants use ferric citrate to fulfill their nutritional requirement for iron. Only the Escherichia coli ferric citrate outer-membrane transport protein FecA has been characterized; little is known about other ferric citrate-binding proteins. Here we report a unique siderophore-binding protein from the gram-positive pathogenic bacterium Bacillus cereus that binds multinuclear ferric citrate complexes. We have demonstrated that B. cereus ATCC 14579 takes up (55)Fe radiolabeled ferric citrate and that a protein, BC_3466 [renamed FctC (ferric citrate-binding protein C)], binds ferric citrate. The dissociation constant (K(d)) of FctC at pH 7.4 with ferric citrate (molar ratio 1:50) is 2.6 nM. This is the tightest binding observed of any B. cereus siderophore-binding protein. Nano electrospray ionization-mass spectrometry (nano ESI-MS) analysis of FctC and ferric citrate complexes or citrate alone show that FctC binds diferric di-citrate, and triferric tricitrate, but does not bind ferric di-citrate, ferric monocitrate, or citrate alone. Significantly, the protein selectively binds triferric tricitrate even though this species is naturally present at very low equilibrium concentrations.

  16. 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.

  17. Experimental assessment of the application possibility of radiopharmaceutical 68Ga-citrate for Pet-imaging of inflammation

    Directory of Open Access Journals (Sweden)

    Lun'yov A.S.

    2014-12-01

    Full Text Available The aim of the study is to compare of 67Ga- and 68Ga-citrate pharmacokinetics and prove their similarity. Prior i. v. injection of physiologically acceptable compound of Fe-citrate (III increases blood clearance and accumulation in inflammation. Materials and methods. 110 nonlinear rats-female with model of soft tissue inflammation were used in experiment. Animals i. v. were injected 67Ga- and 68Ga-citrate with premedication of Fe-citrate (III and without it. Results. Prior injection of Fe-citrate (III increases blood clearance, accumulation in inflammation (for 1 h past injection and intensive excretion of radiopharmaceutical. Conclusion. There is no statistically significant difference between biodistri-bution of radiopharmaceutical labeled different gallium isotopes. It's positive and promising for application possibility of 68Ga-citrate for PET-imaging of inflammation early (for 1 h past injection.

  18. Influence of chelating agents on biogenic uraninite reoxidation by Fe(III) (Hydr)oxides.

    Science.gov (United States)

    Stewart, Brandy D; Girardot, Crystal; Spycher, Nicolas; Sani, Rajesh K; Peyton, Brent M

    2013-01-02

    Microbially mediated reduction of soluble U(VI) to U(IV) with subsequent precipitation of uraninite, UO(2(S)), has been proposed as a method for limiting uranium (U) migration. However, microbially reduced UO(2) may be susceptible to reoxidation by environmental factors, with Fe(III) (hydr)oxides playing a significant role. Little is known about the role that organic compounds such as Fe(III) chelators play in the stability of reduced U. Here, we investigate the impact of citrate, DFB, EDTA, and NTA on biogenic UO(2) reoxidation with ferrihydrite, goethite, and hematite. Experiments were conducted in anaerobic batch systems in PIPES buffer (10 mM, pH 7) with bicarbonate for approximately 80 days. Results showed EDTA accelerated UO(2) reoxidation the most at an initial rate of 9.5 μM day(-1) with ferrihydrite, 8.6 μM day(-1) with goethite, and 8.8 μM day(-1) with hematite. NTA accelerated UO(2) reoxidation with ferrihydrite at a rate of 4.8 μM day(-1); rates were less with goethite and hematite (0.66 and 0.71 μM day(-1), respectively). Citrate increased UO(2) reoxidation with ferrihydrite at a rate of 1.8 μM day(-1), but did not increase the extent of reaction with goethite or hematite, with no reoxidation in this case. In all cases, bicarbonate increased the rate and extent of UO(2) reoxidation with ferrihydrite in the presence and absence of chelators. The highest rate of UO(2) reoxidation occurred when the chelator promoted both UO(2) and Fe(III) (hydr)oxide dissolution as demonstrated with EDTA. When UO(2) dissolution did not occur, UO(2) reoxidation likely proceeded through an aqueous Fe(III) intermediate with lower reoxidation rates observed. Reaction modeling suggests that strong Fe(II) chelators promote reoxidation whereas strong Fe(III) chelators impede it. These results indicate that chelators found in U contaminated sites may play a significant role in mobilizing U, potentially affecting bioremediation efforts.

  19. Cyanido-bridged Fe(III)-Mn(III) heterobimetallic materials built from Mn(III) Schiff base complexes and di- or tri-cyanido Fe(III) precursors.

    Science.gov (United States)

    Senapati, Tapas; Pichon, Céline; Ababei, Rodica; Mathonière, Corine; Clérac, Rodolphe

    2012-03-19

    The reaction of [Fe(III)L(CN)(3)](-) (L being bpca = bis(2-pyridylcarbonyl)amidate, pcq = 8-(pyridine-2-carboxamido)quinoline) or [Fe(III)(bpb)(CN)(2)](-) (bpb = 1,2-bis(pyridine-2-carboxamido)benzenate) ferric complexes with Mn(III) salen type complexes afforded seven new bimetallic cyanido-bridged Mn(III)-Fe(III) systems: [Fe(pcq)(CN)(3)Mn(saltmen)(CH(3)OH)]·CH(3)OH (1), [Fe(bpca)(CN)(3)Mn(3-MeO-salen)(OH(2))]·CH(3)OH·H(2)O (2), [Fe(bpca)(CN)(3)Mn(salpen)] (3), [Fe(bpca)(CN)(3)Mn(saltmen)] (4), [Fe(bpca)(CN)(3)Mn(5-Me-saltmen)]·2CHCl(3) (5), [Fe(pcq)(CN)(3)Mn(5-Me-saltmen)]·2CH(3)OH·0.75H(2)O (6), and [Fe(bpb)(CN)(2)Mn(saltmen)]·2CH(3)OH (7) (with saltmen(2-) = N,N'-(1,1,2,2-tetramethylethylene)bis(salicylideneiminato) dianion, salpen(2-) = N,N'-propylenebis(salicylideneiminato) dianion, salen(2-) = N,N'-ethylenebis(salicylideneiminato) dianion). Single crystal X-ray diffraction studies were carried out for all these compounds indicating that compounds 1 and 2 are discrete dinuclear [Fe(III)-CN-Mn(III)] complexes while systems 3-7 are heterometallic chains with {-NC-Fe(III)-CN-Mn(III)} repeating units. These chains are connected through π-π and short contact interactions to form extended supramolecular networks. Investigation of the magnetic properties revealed the occurrence of antiferromagnetic Mn(III)···Fe(III) interactions in 1-4 while ferromagnetic Mn(III)···Fe(III) interactions were detected in 5-7. The nature of these Mn(III)···Fe(III) magnetic interactions mediated by a CN bridge appeared to be dependent on the Schiff base substituent. The packing is also strongly affected by the nature of the substituent and the presence of solvent molecules, resulting in additional antiferromagnetic interdinuclear/interchain interactions. Thus the crystal packing and the supramolecular interactions induce different magnetic properties for these systems. The dinuclear complexes 1 and 2, which possess a paramagnetic S(T) = 3/2 ground state, interact

  20. Heterotrimetallic coordination polymers: {Cu(II)Ln(III)Fe(III)} chains and {Ni(II)Ln(III)Fe(III)} layers: synthesis, crystal structures, and magnetic properties.

    Science.gov (United States)

    Alexandru, Maria-Gabriela; Visinescu, Diana; Andruh, Marius; Marino, Nadia; Armentano, Donatella; Cano, Joan; Lloret, Francesc; Julve, Miguel

    2015-03-27

    The use of the [Fe(III) (AA)(CN)4](-) complex anion as metalloligand towards the preformed [Cu(II) (valpn)Ln(III)](3+) or [Ni(II) (valpn)Ln(III) ](3+) heterometallic complex cations (AA=2,2'-bipyridine (bipy) and 1,10-phenathroline (phen); H2 valpn=1,3-propanediyl-bis(2-iminomethylene-6-methoxyphenol)) allowed the preparation of two families of heterotrimetallic complexes: three isostructural 1D coordination polymers of general formula {[Cu(II) (valpn)Ln(III) (H2O)3 (μ-NC)2 Fe(III) (phen)(CN)2 {(μ-NC)Fe(III) (phen)(CN)3}]NO3 ⋅7 H2O}n (Ln=Gd (1), Tb (2), and Dy (3)) and the trinuclear complex [Cu(II) (valpn)La(III) (OH2 )3 (O2 NO)(μ-NC)Fe(III) (phen)(CN)3 ]⋅NO3 ⋅H2O⋅CH3 CN (4) were obtained with the [Cu(II) (valpn)Ln(III)](3+) assembling unit, whereas three isostructural heterotrimetallic 2D networks, {[Ni(II) (valpn)Ln(III) (ONO2 )2 (H2 O)(μ-NC)3 Fe(III) (bipy)(CN)]⋅2 H2 O⋅2 CH3 CN}n (Ln=Gd (5), Tb (6), and Dy (7)) resulted with the related [Ni(II) (valpn)Ln(III) ](3+) precursor. The crystal structure of compound 4 consists of discrete heterotrimetallic complex cations, [Cu(II) (valpn)La(III) (OH2)3 (O2 NO)(μ-NC)Fe(III) (phen)(CN)3 ](+), nitrate counterions, and non-coordinate water and acetonitrile molecules. The heteroleptic {Fe(III) (bipy)(CN)4} moiety in 5-7 acts as a tris-monodentate ligand towards three {Ni(II) (valpn)Ln(III)} binuclear nodes leading to heterotrimetallic 2D networks. The ferromagnetic interaction through the diphenoxo bridge in the Cu(II)-Ln(III) (1-3) and Ni(II)-Ln(III) (5-7) units, as well as through the single cyanide bridge between the Fe(III) and either Ni(II) (5-7) or Cu(II) (4) account for the overall ferromagnetic behavior observed in 1-7. DFT-type calculations were performed to substantiate the magnetic interactions in 1, 4, and 5. Interestingly, compound 6 exhibits slow relaxation of the magnetization with maxima of the out-of-phase ac signals below 4.0 K in the lack of a dc field, the values of the pre

  1. [Anaerobic reduction of humus/Fe (III) and electron transport mechanism of Fontibacter sp. SgZ-2].

    Science.gov (United States)

    Ma, Chen; Yang, Gui-qin; Lu, Qin; Zhou, Shun-gui

    2014-09-01

    Humus and Fe(III) respiration are important extracellular respiration metabolism. Electron transport pathway is the key issue of extracellular respiration. To understand the electron transport properties and the environmental behavior of a novel Fe(III)- reducing bacterium, Fontibacter sp. SgZ-2, capacities of anaerobic humus/Fe(III) reduction and electron transport mechanisms with four electron acceptors were investigated in this study. The results of anaerobic batch experiments indicated that strain SgZ-2 had the ability to reduce humus analog [ 9,10-anthraquinone-2,6-disulfonic acid (AQDS) and 9,10-anthraquinone-2-sulfonic acid (AQS)], humic acids (HA), soluble Fe(III) (Fe-EDTA and Fe-citrate) and Fe(III) oxides [hydrous ferric oxide (HFO)]. Fermentative sugars (glucose and sucrose) were the most effective electron donors in the humus/Fe(III) reduction by strain SgZ-2. Additionally, differences of electron carrier participating in the process of electron transport with different electron acceptors (i. e. , oxygen, AQS, Fe-EDTA and HFO) were investigated using respiratory inhibitors. The results suggested that similar respiratory chain components were involved in the reducing process of oxygen and Fe-EDTA, including dehydrogenase, quinones and cytochromes b-c. In comparison, only dehydrogenase was found to participate in the reduction of AQS and HFO. In conclusion, different electron transport pathways may be employed by strain SgZ-2 between insoluble and soluble electron acceptors or among soluble electron acceptors. Preliminary models of electron transport pathway with four electron acceptors were proposed for strain SgZ-2, and the study of electron transport mechanism was explored to the genus Fontibacter. All the results from this study are expected to help understand the electron transport properties and the environmental behavior of the genus Fontibacter.

  2. 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.

  3. Geobacter luticola sp. nov., an Fe(III)-reducing bacterium isolated from lotus field mud.

    Science.gov (United States)

    Viulu, Samson; Nakamura, Kohei; Okada, Yurina; Saitou, Sakiko; Takamizawa, Kazuhiro

    2013-02-01

    A novel species of Fe(III)-reducing bacterium, designated strain OSK6(T), belonging to the genus Geobacter, was isolated from lotus field mud in Japan. Strain OSK6(T) was isolated using a solid medium containing acetate, Fe(III)-nitrilotriacetate (NTA) and gellan gum. The isolate is a strictly anaerobic, gram-negative, motile, straight rod-shaped bacterium, 0.6-1.9 µm long and 0.2-0.4 µm wide. The growth of the isolate occurred at 20-40 °C with optima of 30-37 °C and pH 6.5-7.5 in the presence of up to 0.5 g NaCl l(-1). The G+C content of the genomic DNA was determined by HPLC to be 59.7 mol%. The major respiratory quinone was MK-8. The major fatty acids were 16 : 1ω7c and 16 : 0. Strain OSK6(T) was able to grow with Fe(III)-NTA, ferric citrate, amorphous iron (III) hydroxide and nitrate, but not with fumarate, malate or sulfate as electron acceptors. Among examined substrates grown with Fe(III)-NTA, the isolate grew on acetate, lactate, pyruvate and succinate. Analysis of the near full-length 16S rRNA gene sequence revealed that strain OSK6(T) is closely related to Geobacter daltonii and Geobacter toluenoxydans with 95.6 % similarity to the type strains of these species. On the basis of phylogenetic analysis and physiological tests, strain OSK6(T) is described as a representative of a novel species, Geobacter luticola sp. nov.; the type strain is OSK6(T) ( = DSM 24905(T) = JCM 17780(T)).

  4. Iron Isotope Fractionations Reveal a Finite Bioavailable Fe Pool for Structural Fe(III) Reduction in Nontronite.

    Science.gov (United States)

    Shi, Bingjie; Liu, Kai; Wu, Lingling; Li, Weiqiang; Smeaton, Christina M; Beard, Brian L; Johnson, Clark M; Roden, Eric E; Van Cappellen, Philippe

    2016-08-16

    We report on stable Fe isotope fractionation during microbial and chemical reduction of structural Fe(III) in nontronite NAu-1. (56)Fe/(54)Fe fractionation factors between aqueous Fe(II) and structural Fe(III) ranged from -1.2 to +0.8‰. Microbial (Shewanella oneidensis and Geobacter sulfurreducens) and chemical (dithionite) reduction experiments revealed a two-stage process. Stage 1 was characterized by rapid reduction of a finite Fe(III) pool along the edges of the clay particles, accompanied by a limited release to solution of Fe(II), which partially adsorbed onto basal planes. Stable Fe isotope compositions revealed that electron transfer and atom exchange (ETAE) occurred between edge-bound Fe(II) and octahedral (structural) Fe(III) within the clay lattice, as well as between aqueous Fe(II) and structural Fe(III) via a transient sorbed phase. The isotopic fractionation factors decreased with increasing extent of reduction as a result of the depletion of the finite bioavailable Fe(III) pool. During stage 2, microbial reduction was inhibited while chemical reduction continued. However, further ETAE between aqueous Fe(II) and structural Fe(III) was not observed. Our results imply that the pool of bioavailable Fe(III) is restricted to structural Fe sites located near the edges of the clay particles. Blockage of ETAE distinguishes Fe(III) reduction of layered clay minerals from that of Fe oxyhydroxides, where accumulation of structural Fe(II) is much more limited.

  5. Photochemical Formation of Fe(II) in the Aqueous Solutions of Fe(III)- Dicarboxylates

    Science.gov (United States)

    Okada, K.; Arakaki, T.

    2007-12-01

    Although there have been many studies reporting the photochemical formation of Fe(II) in various aqueous-phase such as rain, cloud waters, seawater and aerosols, the detailed formation mechanisms are not well understood. To better understand the mechanisms of Fe(II) formation, we attempted to determine the molar absorptivity and the quantum yield of Fe(II) photoformation for individual Fe(III)-dicarboxylate species. The concentrations of Fe(II) and total dissolved Fe were measured by a Ferrozine-HPLC method. The Visual MINTEQ computer program was used to calculate the equilibrium concentrations of chemical species in the solutions of Fe(III)-dicarboxylate complexes. The molar absorptivity and the product of the quantum yield and the molar absorptivity of Fe(III)- dicarboxylate complex can be analysed by UV-VIS spectrophotometer and photochemical experiments, and these experimental data were combined with the calculated equilibrium Fe(III) speciation to determine individual molar absorptivity and quantum yield of Fe(II) photoformation for a specific Fe(III)-dicarboxylate complex. Preliminary results, using an oxalate whose quantum yield has been previously reported, indicate that this approach gives lower quantum yield values in air saturated solutions than previously reported.

  6. Degradation of bisphenol A in water by Fe(III)/UVA and Fe(III)/polycarboxylate/UVA photocatalysis.

    Science.gov (United States)

    Alvarez, P M; Rodríguez, E M; Fernández, G; Beltrán, F J

    2010-01-01

    The photodegradation of the endocrine disrupting chemical Bisphenol A (BPA) under UVA irradiation in the presence of Fe(III) or Fe(III)-polycarboxylate systems was studied. The effect of Fe(III) concentration, aqueous pH and the presence of four carboxylic acids (oxalic, malic, tartaric and citric) were investigated. The Fe(III)/UVA system was able to effectively degrade BPA at pH 3 but failed at pH > 4. At any rate, no mineralization of BPA was achieved with the Fe(III)/UVA system. The presence of carboxylic acids greatly enhanced the BPA degradation rate because of the formation of photoactive Fe(III)-polycarboxylate complexes. Aqueous pH in the 3-7 range exerted a negative effect on the BPA degradation rate and TOC conversion in the presence of oxalic, malic and tartaric acids. Only slight effect of pH was observed in the presence of citric acid, being the BPA degradation rate significant even at pH 7.

  7. Preparation of Nd-Fe-B by nitrate-citrate auto-combustion followed by the reduction-diffusion process.

    Science.gov (United States)

    Ma, Hao Xuan; Kim, Chang Woo; Kim, Dong Soo; Jeong, Ji Hun; Kim, In Ho; Kang, Young Soo

    2015-05-07

    The Nd2Fe14B alloy has been successfully synthesized by nitrate-citrate auto-combustion followed by the reduction and diffusion process with low energy consumption. H3BO3, Fe(NO3)3·9H2O, and Nd(NO3)3·6H2O were used as precursors and citric acid was used as the chelating ligand of metal ions. Ammonia water was used to adjust pH to 7. CaH2 was used as a reducing agent for the reduction and diffusion process. NdFeO3 and Fe2O3 were produced during auto-combustion of gel. The combustion process of the gel was investigated by TGA/DTA curve measurements. The phase compositions were studied by XRD measurements. The differences of the overall morphology and magnetic properties were measured by SEM, TEM and vibrating sample magnetometry (VSM) at 300 K. The comparison of the magnetic properties of the reduced samples between the pellet type and the random powder type was done with VSM and it showed better magnetic properties of the pellet type Nd2Fe14B. Making a compact pellet type sample for reduction is more efficient for solid reduction and phase transition for higher coercivity.

  8. Mechanisms for chelator stimulation of microbial Fe(III) -oxide reduction

    Science.gov (United States)

    Lovley, D.R.; Woodward, J.C.

    1996-01-01

    The mechanisms by which nitrilotriacetic acid (NTA) stimulated Fe(III) reduction in sediments from a petroleum-contaminated aquifer were investigated in order to gain insight into how added Fe(III) chelators stimulate the activity of hydrocarbon-degrading, Fe(III)-reducing microorganisms in these sediments, and how naturally occurring Fe(III) chelators might promote Fe(III) reduction in aquatic sediments. NTA solubilized Fe(III) from the aquifer sediments. NTA stimulation of microbial Fe(III) reduction did not appear to be the result of making calcium, magnesium, potassium, or trace metals more available to the microorganisms. Stimulation of Fe(III) reduction could not be attributed to NTA serving as a source of carbon or fixed nitrogen for Fe(III)-reducing bacteria as NTA was not degraded in the sediments. Studies with the Fe(III)-reducing microorganism, Geobacter metallireducens, and pure Fe(III)-oxide forms, demonstrated that NTA stimulated the reduction of a variety of Fe(III) forms, including highly crystalline Fe(III)-oxides such as goethite and hematite. The results suggest that NTA solubilization of insoluble Fe(III)-oxide is an important mechanism for the stimulation of Fe(III) reduction by NTA in aquifer sediments.

  9. [Fe(II)LSCo(III)LS]2 ⇔ [Fe(III)LSCo(II)HS]2 photoinduced conversion in a cyanide-bridged heterobimetallic molecular square.

    Science.gov (United States)

    Mercurol, Julie; Li, Yanling; Pardo, Emilio; Risset, Olivia; Seuleiman, Mannan; Rousselière, Hélène; Lescouëzec, Rodrigue; Julve, Miguel

    2010-12-21

    The self-assembly of [Fe(III){B(pz)(4)}(CN)(3)](-) and [Co(II)(bik)(2)(S)(2)](2+) affords the diamagnetic cyanide-bridged [Fe(II)(LS)Co(III)(LS)](2) molecular square which is converted into the corresponding magnetic [Fe(III)(LS)Co(II)(HS)](2) species under light irradiation at relatively low temperatures.

  10. Condutividade da Polianilina e Poliacrilonitrila Dopadas com Fe(II e Fe(III

    Directory of Open Access Journals (Sweden)

    Yonis Fornazier Filho

    2015-01-01

    Full Text Available In this work we report O estudo da interação de íons Fe(II com a polianilina foi feito através da obtenção deste polímero na forma de salthe studies on Polyaniline Emeraldine (PANI-ES and Polyacrilonitrile (PAN doped with salt of Fe (II and Fe(III. We used the techniques of conductivity measurements with aplicação de pressão.application of pressure.  The results showed that conductivity of PANI-ES increase with pressure of range of 1.73 MPa until 20.0 MPa and PAN also increase with maximum of 6.0 mPa except to samples PAN-2-TT-FeIII and PAN-2-TTAA-FeIII.

  11. Online spectrophotometric determination of Fe(II) and Fe(III) by flow injection combined with low pressure ion chromatography

    Science.gov (United States)

    Chen, Shujuan; Li, Nan; Zhang, Xinshen; Yang, Dongjing; Jiang, Heimei

    2015-03-01

    A simple and new low pressure ion chromatography combined with flow injection spectrophotometric procedure for determining Fe(II) and Fe(III) was established. It is based on the selective adsorption of low pressure ion chromatography column to Fe(II) and Fe(III), the online reduction reaction of Fe(III) and the reaction of Fe(II) in sodium acetate with phenanthroline, resulting in an intense orange complex with a suitable absorption at 515 nm. Various chemical (such as the concentration of colour reagent, eluant and reductive agent) and instrumental parameters (reaction coil length, reductive coil length and wavelength) were studied and were optimized. Under the optimum conditions calibration graph of Fe(II)/Fe(III) was linear in the Fe(II)/Fe(III) range of 0.040-1.0 mg/L. The detection limit of Fe(III) and Fe(II) was respectively 3.09 and 1.55 μg/L, the relative standard deviation (n = 10) of Fe(II) and Fe(III) 1.89% and 1.90% for 0.5 mg/L of Fe(II) and Fe(III) respectively. About 2.5 samples in 1 h can be analyzed. The interfering effects of various chemical species were studied. The method was successfully applied in the determination of water samples.

  12. The effect of post annealing treatment on the citrate sol–gel derived nanocrystalline BaFe12O19 powder: structural, morphological, optical and magnetic properties

    Directory of Open Access Journals (Sweden)

    B. C. Brightlin

    2016-05-01

    Full Text Available Abstract The nanocrystalline BaFe12O19 powders were obtained from citrate sol–gel combustion-derived powder upon annealing at 800–1100 °C, and explored their structural, micro-structural, optical and magnetic properties. The thermal decomposition of citrate sol–gel combustion product was verified by means of thermogravimetric and differential thermal analysis. Structural identification of the citrate sol–gel combustion powder and annealed samples were investigated by powder X-ray diffraction. Though the combustion product exhibits cubic spinel phase material, the annealed powder yields good quality nanocrystalline hexagonal BaFe12O19 phase materials. The thin plate-like flakes morphology with random particle sizes of ~100–200 nm with slightly agglomerated particles of BaFe12O19 phase is analyzed by high resolution scanning electron microscopy for the good quality annealed sample. Photoluminescence emission spectrum of BaFe12O19 material reveals broad emission peak at ~360 nm under the excitation wavelength of 270 nm. Interestingly, the near infrared relative reflectivity of the nanocrystalline BaFe12O19 materials obtained by citrate sol-gel synthesis method is higher than the nanocrystalline BaFe12O19 materials obtained by mechano-thermal and co-precipitation method. The present dark brown colored BaFe12O19 materials can be applied as a ceramic color pigment which includes several applications. The room temperature magnetic hysteresis loop of the annealed BaFe12O19 sample exhibits a ferromagnetic saturation magnetization, M s of 55.774 emu/g at 15 kOe.

  13. The effect of post annealing treatment on the citrate sol-gel derived nanocrystalline BaFe12O19 powder: structural, morphological, optical and magnetic properties

    Science.gov (United States)

    Brightlin, B. C.; Balamurugan, S.

    2016-11-01

    The nanocrystalline BaFe12O19 powders were obtained from citrate sol-gel combustion-derived powder upon annealing at 800-1100 °C, and explored their structural, micro-structural, optical and magnetic properties. The thermal decomposition of citrate sol-gel combustion product was verified by means of thermogravimetric and differential thermal analysis. Structural identification of the citrate sol-gel combustion powder and annealed samples were investigated by powder X-ray diffraction. Though the combustion product exhibits cubic spinel phase material, the annealed powder yields good quality nanocrystalline hexagonal BaFe12O19 phase materials. The thin plate-like flakes morphology with random particle sizes of 100-200 nm with slightly agglomerated particles of BaFe12O19 phase is analyzed by high resolution scanning electron microscopy for the good quality annealed sample. Photoluminescence emission spectrum of BaFe12O19 material reveals broad emission peak at 360 nm under the excitation wavelength of 270 nm. Interestingly, the near infrared relative reflectivity of the nanocrystalline BaFe12O19 materials obtained by citrate sol-gel synthesis method is higher than the nanocrystalline BaFe12O19 materials obtained by mechano-thermal and co-precipitation method. The present dark brown colored BaFe12O19 materials can be applied as a ceramic color pigment which includes several applications. The room temperature magnetic hysteresis loop of the annealed BaFe12O19 sample exhibits a ferromagnetic saturation magnetization, M s of 55.774 emu/g at 15 kOe.

  14. Effect of 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

    2005-11-01

    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.

  15. Redox cycling of Fe(II) and Fe(III) in magnetite by Fe-metabolizing bacteria

    Science.gov (United States)

    Byrne, James M.; Klueglein, Nicole; Pearce, Carolyn; Rosso, Kevin M.; Appel, Erwin; Kappler, Andreas

    2015-03-01

    Microorganisms are a primary control on the redox-induced cycling of iron in the environment. Despite the ability of bacteria to grow using both Fe(II) and Fe(III) bound in solid-phase iron minerals, it is currently unknown whether changing environmental conditions enable the sharing of electrons in mixed-valent iron oxides between bacteria with different metabolisms. We show through magnetic and spectroscopic measurements that the phototrophic Fe(II)-oxidizing bacterium Rhodopseudomonas palustris TIE-1 oxidizes magnetite (Fe3O4) nanoparticles using light energy. This process is reversible in co-cultures by the anaerobic Fe(III)-reducing bacterium Geobacter sulfurreducens. These results demonstrate that Fe ions bound in the highly crystalline mineral magnetite are bioavailable as electron sinks and electron sources under varying environmental conditions, effectively rendering magnetite a naturally occurring battery.

  16. A new combined process for efficient removal of Cu(II) organic complexes from wastewater: Fe(III) displacement/UV degradation/alkaline precipitation.

    Science.gov (United States)

    Xu, Zhe; Gao, Guandao; Pan, Bingcai; Zhang, Weiming; Lv, Lu

    2015-12-15

    Efficient removal of heavy metals complexed with organic ligands from water is still an important but challenging task now. Herein, a novel combined process, i.e., Fe(III)-displacement/UV degradation/alkaline precipitation (abbreviated as Fe(III)/UV/OH) was developed to remove copper-organic complexes from synthetic solution and real electroplating effluent, and other processes including alkaline precipitation, Fe(III)/OH, UV/OH were employed for comparison. By using the Fe(III)/UV/OH process, some typical Cu(II) complexes, such as Cu(II)-ethylenediaminetetraacetic acid (EDTA), Cu(II)-nitrilotriacetic acid (NTA), Cu(II)-citrate, Cu(II)-tartrate, and Cu(II)-sorbate, each at 19.2 mg Cu/L initially, were efficiently removed from synthetic solution with the residual Cu below 1 mg/L. Simultaneously, 30-48% of total organic carbon was eliminated with exception of Cu(II)-sorbate. Comparatively, the efficiency of other processes was much lower than the Fe(III)/UV/OH process. With Cu(II)-citrate as the model complex, the optimal conditions for the combined process were obtained as: initial pH for Fe(III) displacement, 1.8-5.4; molar ratio of [Fe]/[Cu], 4:1; UV irradiation, 10 min; precipitation pH, 6.6-13. The mechanism responsible for the process involved the liberation of Cu(II) ions from organic complexes as a result of Fe(III) displacement, decarboxylation of Fe(III)-ligand complexes subjected to UV irradiation, and final coprecipitation of Cu(II) and Fe(II)/Fe(III) ions. Up to 338.1 mg/L of Cu(II) in the electroplating effluent could be efficiently removed by the process with the residual Cu(II) below 1 mg/L and the removal efficiency of ∼99.8%, whereas direct precipitation by using NaOH could only result in total Cu(II) removal of ∼8.6%. In addition, sunlight could take the place of UV to achieve similar removal efficiency with longer irradiation time (90 min).

  17. 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.

  18. Alterations of the [59Fe]ferric citrate biodistribution in hyperferremic mice after the administration of pyrophosphate and desferrioxamine.

    Science.gov (United States)

    Sawas-Dimopoulou, C; Soulpi, C

    1983-02-01

    One of the most efficient anions in enhancing the ability of desferrioxamine (DFO) to remove iron from transferrin in vitro has been shown to be pyrophosphate (PYP). To evaluate the in vivo effect of PYP in hyperferremic mice, the biodistribution of [59Fe]ferric citrate was studied after the i.p. administration of: 1) only saline in the control animals; 2) an aqueous solution of tetrasodium diphosphate (PYP; 40 gm/2 g of b.wt.); 3) desferral (DFO; 12 mg/20 g of b.wt.); and 4) PYP + DFO at the respective dosages shown above. The radioactivity in each organ, blood, urine and feces was measured and referred to as percentage of the injected dose. PYP administered alone acted as a weaker chelator of iron than DFO. The combined administration of DFO and PYP contributed more than DFO or PYP separately, to the increase of urinary excretion of 59Fe and to the significant decrease of the radioiron concentration in liver (.01 less than P less than .05). The above induced changes are not, however, the additive result of the separate effect of DFO and PYP. That observation would suggest that DFO + PYP combined in a unique treatment, interact with iron through a common reaction pathway and that PYP plays in vivo a synergistic role in that interaction. The kind of iron with which DFO + PYP interacts is then suggested to be the transferrin-bound iron located in extracellular spaces of tissues.

  19. Alterations of the (/sup 59/Fe)ferric citrate biodistribution in hyperferremic mice after the administration of pyrophosphate and desferrioxamine

    Energy Technology Data Exchange (ETDEWEB)

    Sawas-Dimopoulou, C.; Soulpi, C.

    1983-02-01

    One of the most efficient anions in enhancing the ability of desferrioxamine (DFO) to remove iron from transferrin in vitro has been shown to be pyrophosphate (PYP). To evaluate the in vivo effect of PYP in hyperferremic mice, the biodistribution of (/sup 59/Fe)ferric citrate was studied after the i.p. administration of: 1) only saline in the control animals; 2) an aqueous solution of tetrasodium diphosphate (PYP; 40 gm/2 g of b.wt.); 3) desferral (DFO; 12 mg/20 g of b.wt.); and 4) PYP + DFO at the respective dosages shown above. The radioactivity in each organ, blood, urine and feces was measured and referred to as percentage of the injected dose. PYP administered alone acted as a weaker chelator of iron than DFO. The combined administration of DFO and PYP contributed more than DFO or PYP separately, to the increase of urinary excretion of /sup 59/Fe and to the significant decrease of the radioiron concentration in liver (.01 less than P less than .05). The above induced changes are not, however, the additive result of the separate effect of DFO and PYP. That observation would suggest that DFO + PYP combined in a unique treatment, interact with iron through a common reaction pathway and that PYP plays in vivo a synergistic role in that interaction. The kind of iron with which DFO + PYP interacts is then suggested to be the transferrin-bound iron located in extracellular spaces of tissues.

  20. Alterations of the (/sup 59/Fe)ferric citrate biodistribution in hyperferremic mice after the administration of pyrophosphate and desferrioxamine

    Energy Technology Data Exchange (ETDEWEB)

    Sawas-Dimopoulou, C.; Soulpi, C.

    1983-02-01

    One of the most efficient anions in enhancing the ability of desferrioxamine (DFO) to remove iron from transferrin in vitro has been shown to be pyrophosphate (PYP). To evaluate the in vivo effect of PYP in hyperferremic mice, the biodistribution of (/sup 59/Fe)ferric citrate was studied after the i.p. administration of: 1) only saline in the control animals; 2) an aqueous solution of tetrasodium diphosphate; 3) desferral; and 4) PYP + DFO. The radioactivity in each organ, blood, urine and feces was measured and referred to as percentage of the injected dose. PYP administered alone acted as a weaker chelator of iron than DFO. The combined administration of DFO and PYP contributed more than DFO or PYP separately, to the increase of urinary excretion of 59Fe and to the significant decrease of the radioiron concentration in liver. The above induced changes are not, however, the additive result of the separate effect of DFO and PYP. That observation would suggest that DFO + PYP combined in a unique treatment, interact with iron through a common reaction pathway and that PYP plays in vivo a synergistic role in that interaction. The kind of iron with which DFO + PYP interacts is then suggested to be the transferrin-bound iron located in extracellular spaces of tissues.

  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

    in the anaerobic microcosms were mixed nitrate and Fe(III) reducing. Nitrate and Fe(III) were apparently the dominant electron accepters at high and low nitrate concentrations, respectively. When biomass growth is taken into account, nitrate and Fe(III) reduction constituted sufficient electron acceptor capacity...

  2. Tetrachloroethene degradation by reducing-agent enhanced Fe(II)/Fe(III) catalyzed percarbonate

    Science.gov (United States)

    Miao, Z.; Brusseau, M. L.; Lu, S.; Gu, X.; Yan, N.; Qiu, Z.; Sui, Q.

    2015-12-01

    This project investigated the effect of reducing agents on the degradation of tetrachloroethene(PCE) by Fe(II)/Fe(III) catalyzed sodium percarbonate (SPC). SPC possesses similar function as liquid H2O2, such that free H2O2 is released into solution when percarbonate is mixed with water. The addition of reducing agents, including hydroxylamine hydrochloride, sodium sulfite, ascorbic acid and sodium ascorbate, accelerated the Fe(III)/Fe(II) redoxcycle, 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 results of chemical probe tests, using nitrobenzene and carbon tetrachloride, demonstrated that HO● was the predominant radical in the system and that O2●-played a minor role. This was further confirmed by the results of electron paramagnetic resonance measurements and salicylic acid hydroxylationanalysis by high performance liquid chromatography(HPLC). PCE degradation decreased significantly with the addition of isopropanol, a strong HO● scavenger, supporting the hypothesis that HO● was primarily responsible for PCE degradation. It should be noted that the release of Cl- was slightly delayed in the first 20 mins, indicating that intermediate products were produced. However, gas chromatography mass spectrometry (GC/MS) analysis did not detect any chlorinated organic compound except PCE, indicating these intermediates were quickly degraded, which resulted in the complete conversion of PCE to CO2. 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. Cyanide- and phenoxo-bridged heterobimetallic Fe(III)-Mn(III) complexes: Synthesis, crystal structures and magnetic properties

    Indian Academy of Sciences (India)

    Daopeng Zhang; Ping Wang; Kexun Chen; Xia Chen

    2014-11-01

    By employing two -tricyanidoiron(III) precursors [Ph4P][FeIII(pcq)(CN)3] and [Ph4P][FeIII (pzq)(CN)3] as building blocks and a salen-tpye Schiff-basemanganese (III) compound as assembling segment, two tetranuclear cyanide- and phenoxo- bridged heterobimetallic Fe(III)-Mn(III) complexes {[Mn(saltmen)] [Fe(pcq)(CN)3]}2·2CH3OH (1) and {[Mn(saltmen)] [Fe(pzq)(CN)3]}2·2CH3OH (2) (pcq = 8-(pyridine-2-carboxamido, pzq = 8-(pyrazine-2-carboxamido, saltmen2− = N,N′-(1,1,2,2-tetramethylethylene)bis(salicylideneaminato) dianion) have been synthesized and characterized by elemental analysis, IR spectroscopy and X-ray structure determination. Single x-ray analysis reveals their isostructural cyanide-bridged Fe(III)-Mn(III) binuclear structure. The binuclear entity is self-complementary through phenoxo oxygen from the neighbouring complex, giving cyanide- and phenoxo- bridged tetranuclear structure. Furthermore, under the help of the intermolecular - interaction, these two complexes can be constructed into 1D infinite chain supramolecular structure. Investigation over magnetic susceptibilities reveals the overall ferromagnetic coupling between the adjacent Fe(III) and Mn(III) ions bridged by cyanide group with = 5.34 cm-1 and 5.55 cm-1 for complexes 1 and 2, respectively.

  4. Conflicting Role of Water in the Activation of H2O2 and the Formation and Reactivity of Non-Heme Fe-III-OOH and Fe-III-O-Fe-III Complexes at Room Temperature

    NARCIS (Netherlands)

    Padamati, Sandeep K.; Draksharapu, Apparao; Unjaroen, Duenpen; Browne, Wesley R.

    2016-01-01

    The formation of an Fe-III-OOH species by reaction of complex 1 ([(MeN3Py)Fe-II(CH3CN)(2)](2+)) with H2O2 at room temperature is reported and is studied by a combination of UV/vis absorption, EPR, and resonance Raman spectroscopies. The formation of the Fe-III-OOH species, and its subsequent

  5. 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

  6. Geobacter soli sp. nov., a dissimilatory Fe(III)-reducing bacterium isolated from forest soil.

    Science.gov (United States)

    Zhou, Shungui; Yang, Guiqin; Lu, Qin; Wu, Min

    2014-11-01

    A novel Fe(III)-reducing bacterium, designated GSS01(T), was isolated from a forest soil sample using a liquid medium containing acetate and ferrihydrite as electron donor and electron acceptor, respectively. Cells of strain GSS01(T) were strictly anaerobic, Gram-stain-negative, motile, non-spore-forming and slightly curved rod-shaped. Growth occurred at 16-40 °C and optimally at 30 °C. The DNA G+C content was 60.9 mol%. The major respiratory quinone was MK-8. The major fatty acids were C(16:0), C(18:0) and C(16:1)ω7c/C(16:1)ω6c. Strain GSS01(T) was able to grow with ferrihydrite, Fe(III) citrate, Mn(IV), sulfur, nitrate or anthraquinone-2,6-disulfonate, but not with fumarate, as sole electron acceptor when acetate was the sole electron donor. The isolate was able to utilize acetate, ethanol, glucose, lactate, butyrate, pyruvate, benzoate, benzaldehyde, m-cresol and phenol but not toluene, p-cresol, propionate, malate or succinate as sole electron donor when ferrihydrite was the sole electron acceptor. Phylogenetic analyses based on 16S rRNA gene sequences revealed that strain GSS01(T) was most closely related to Geobacter sulfurreducens PCA(T) (98.3% sequence similarity) and exhibited low similarities (94.9-91.8%) to the type strains of other species of the genus Geobacter. The DNA-DNA relatedness between strain GSS01(T) and G. sulfurreducens PCA(T) was 41.4 ± 1.1%. On the basis of phylogenetic analysis, phenotypic characterization and physiological tests, strain GSS01(T) is believed to represent a novel species of the genus Geobacter, and the name Geobacter soli sp. nov. is proposed. The type strain is GSS01(T) ( =KCTC 4545(T) =MCCC 1K00269(T)).

  7. Structure of Co(III and Fe(III transition metal ions in aqueous solution

    Directory of Open Access Journals (Sweden)

    Ahmed M. Mohammed

    2006-06-01

    Full Text Available The hydration structures of Co(III and Fe(III ions have been investigated by Metropolis Monte Carlo (MC simulations using only ion-water pair interaction potentials and by including up to three body correction terms. The hydration structures were evaluated in terms of radial distribution functions, coordination numbers and angular distributions. The structural parameters obtained by including three-body correction terms are in good agreement with experimental values proving that many-body effects play a crucial role in the description of the hydration structure of these highly charged ions.

  8. Geobacter sulfurreducens subsp. ethanolicus, subsp. nov., an ethanol-utilizing dissimilatory Fe(III)-reducing bacterium from a lotus field.

    Science.gov (United States)

    Viulu, Samson; Nakamura, Kohei; Kojima, Akihiro; Yoshiyasu, Yuki; Saitou, Sakiko; Takamizawa, Kazuhiro

    2013-01-01

    An ethanol-utilizing Fe(III)-reducing bacterial strain, OSK2A(T), was isolated from a lotus field in Aichi, Japan. Phylogenetic analysis of the 16S rRNA gene sequences of OSK2A(T) and related strains placed it within Geobacter sulfurreducens PCA(T). Strain OSK2A(T) was shown to be a Gram-negative, motile, rod-shaped bacterium, strictly anaerobic, 0.76-1.65 µm long and 0.28-0.45 μm wide. Its growth occurred at 20-40℃, pH 6.0-8.1, and it tolerated up to 1% NaCl. The G+C content of the genomic DNA was 61.2 mol% and DNA-DNA hybridization value with Geobacter sulfurreducens PCA(T) was 60.7%. The major respiratory quinone was MK-8. The major fatty acids were 16:1 ω7c, 16:0, 14:0, 15:0 iso, 16:1 ω5c, and 18:1 ω7c. Strain OSK2A(T) could utilize H2, ethanol, acetate, lactate, pyruvate, and formate as substrates with Fe(III)-citrate as electron acceptor. Amorphous Fe(III) hydroxide, Fe(III)-NTA, fumarate, malate, and elemental sulfur were utilized as electron acceptors with either acetate or ethanol as substrates. Results obtained from physiological, DNA-DNA hybridization, and chemotaxonomic tests support genotypic and phenotypic differentiation of strain OSK2A(T) from its closest relative. The isolate is assigned as a novel subspecies with the name Geobacter sulfurreducens subsp. ethanolicus, subsp. nov. (type strain OSK2A(T)=DSMZ 26126(T)=JCM 18752(T)).

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

    Science.gov (United States)

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

    2014-01-15

    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)3·xH2O whereas in the presence of iron the precipitate is a mixed Fe(1-x)Crx(OH)3 phase. In this study, we report on the synthesis, characterisation and stability of mixed (Fex,Cr1-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)3·3H2O, was crystalline, highly soluble, i.e. unstable, with a tendency to transform into the stable amorphous hydroxide Cr(OH)3(am) phase. Mixed Fe0.75Cr0.25(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 50μg/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 5.7hydroxides studied were of extended stability in the 4.8

  10. Heterogeneous reduction of PuO₂ with Fe(II): importance of the Fe(III) reaction product.

    Science.gov (United States)

    Felmy, Andrew R; Moore, Dean A; Rosso, Kevin M; Qafoku, Odeta; Rai, Dhanpat; Buck, Edgar C; Ilton, Eugene S

    2011-05-01

    Heterogeneous reduction of actinides in higher, more soluble oxidation states to lower, more insoluble oxidation states by reductants such as Fe(II) has been the subject of intensive study for more than two decades. However, Fe(II)-induced reduction of sparingly soluble Pu(IV) to the more soluble lower oxidation state Pu(III) has been much less studied, even though such reactions can potentially increase the mobility of Pu in the subsurface. Thermodynamic calculations are presented that show how differences in the free energy of various possible solid-phase Fe(III) reaction products can greatly influence aqueous Pu(III) concentrations resulting from reduction of PuO₂(am) by Fe(II). We present the first experimental evidence that reduction of PuO₂(am) to Pu(III) by Fe(II) was enhanced when the Fe(III) mineral goethite was spiked into the reaction. The effect of goethite on reduction of Pu(IV) was demonstrated by measuring the time dependence of total aqueous Pu concentration, its oxidation state, and system pe/pH. We also re-evaluated established protocols for determining Pu(III) {[Pu(III) + Pu(IV)] - Pu(IV)} by using thenoyltrifluoroacetone (TTA) in toluene extractions; the study showed that it is important to eliminate dissolved oxygen from the TTA solutions for accurate determinations. More broadly, this study highlights the importance of the Fe(III) reaction product in actinide reduction rate and extent by Fe(II).

  11. Proteins involved in electron transfer to Fe(III) and Mn(IV) oxides by Geobacter sulfurreducens and Geobacter uraniireducens.

    Science.gov (United States)

    Aklujkar, M; Coppi, M V; Leang, C; Kim, B C; Chavan, M A; Perpetua, L A; Giloteaux, L; Liu, A; Holmes, D E

    2013-03-01

    Whole-genome microarray analysis of Geobacter sulfurreducens grown on insoluble Fe(III) oxide or Mn(IV) oxide versus soluble Fe(III) citrate revealed significantly different expression patterns. The most upregulated genes, omcS and omcT, encode cell-surface c-type cytochromes, OmcS being required for Fe(III) and Mn(IV) oxide reduction. Other electron transport genes upregulated on both metal oxides included genes encoding putative menaquinol : ferricytochrome c oxidoreductase complexes Cbc4 and Cbc5, periplasmic c-type cytochromes Dhc2 and PccF, outer membrane c-type cytochromes OmcC, OmcG and OmcV, multicopper oxidase OmpB, the structural components of electrically conductive pili, PilA-N and PilA-C, and enzymes that detoxify reactive oxygen/nitrogen species. Genes upregulated on Fe(III) oxide encode putative menaquinol : ferricytochrome c oxidoreductase complexes Cbc3 and Cbc6, periplasmic c-type cytochromes, including PccG and PccJ, and outer membrane c-type cytochromes, including OmcA, OmcE, OmcH, OmcL, OmcN, OmcO and OmcP. Electron transport genes upregulated on Mn(IV) oxide encode periplasmic c-type cytochromes PccR, PgcA, PpcA and PpcD, outer membrane c-type cytochromes OmaB/OmaC, OmcB and OmcZ, multicopper oxidase OmpC and menaquinone-reducing enzymes. Genetic studies indicated that MacA, OmcB, OmcF, OmcG, OmcH, OmcI, OmcJ, OmcM, OmcV and PccH, the putative Cbc5 complex subunit CbcC and the putative Cbc3 complex subunit CbcV are important for reduction of Fe(III) oxide but not essential for Mn(IV) oxide reduction. Gene expression patterns for Geobacter uraniireducens were similar. These results demonstrate that the physiology of Fe(III)-reducing bacteria differs significantly during growth on different insoluble and soluble electron acceptors and emphasize the importance of c-type cytochromes for extracellular electron transfer in G. sulfurreducens.

  12. Reductive dechlorination of alpha-, beta-, delta-, and gamma-hexachlorocyclohexane isomers by hydroxocobalamin in the presence of either dithiothreitol or titanium(III) citrate as reducing agents.

    Science.gov (United States)

    Rodríguez-Garrido, B; Arbestain, M Camps; Monterroso, M C; Macías, F

    2004-10-01

    The effect of the reducing potential on the reductive dehalogenation of the different HCH (hexachlorocyclohexane) isomers has not yet been studied. In the present study, the potential for dehalogenation of (alpha-, beta-, delta-, and gamma-HCH isomers by the dithiothreitol (DTT) and titanium(III) citrate (reducing potential at pH 7, -0.33 and -0.48 V, respectively), with and without the addition of hydroxocobalamin was investigated. In the presence of DTT without catalyst, there was no disappearance of any of the HCH isomers studied after 1 h of treatment. However, disappearance of the gamma- and alpha-HCH isomers was observed during the same time period when titanium(III) citrate was used as the reductant in the absence of catalyst (62.9 and 16.6% disappearance, respectively). Addition of the hydroxocobalamin to the DTT system favored mainly the disappearance of gamma- and alpha-HCH (92.9 and 30.8% disappearance after 1 h, respectively); disappearance of delta-HCH and beta-HCH was small (11.9%) or negligible, respectively. Addition of the hydroxocobalamin to the titanium(III) citrate system favored the degradation of all HCH isomers under study: beta- and alpha-HCH completely disappeared to undetectable levels ( alpha-HCH > delta-HCH > beta-HCH, coincided with a decreasing order of the axially positioned Cl atoms of these isomers (considering their thermodynamically most stable configuration). This study is the first description of the rapid degradation of delta- and beta-HCH under abiotic conditions, and the results demonstrate the effect of the reducing potential on the reductive dehalogenation of HCH isomers.

  13. Kinetics of reduction of Fe(III) complexes by outer membrane cytochromes MtrC and OmcA of Shewanella oneidensis MR-1.

    Science.gov (United States)

    Wang, Zheming; Liu, Chongxuan; Wang, Xuelin; Marshall, Matthew J; Zachara, John M; Rosso, Kevin M; Dupuis, Michel; Fredrickson, James K; Heald, Steve; Shi, Liang

    2008-11-01

    Because of their cell surface locations, the outer membrane c-type cytochromes MtrC and OmcA of Shewanella oneidensis MR-1 have been suggested to be the terminal reductases for a range of redox-reactive metals that form poorly soluble solids or that do not readily cross the outer membrane. In this work, we determined the kinetics of reduction of a series of Fe(III) complexes with citrate, nitrilotriacetic acid (NTA), and EDTA by MtrC and OmcA using a stopped-flow technique in combination with theoretical computation methods. Stopped-flow kinetic data showed that the reaction proceeded in two stages, a fast stage that was completed in less than 1 s, followed by a second, relatively slower stage. For a given complex, electron transfer by MtrC was faster than that by OmcA. For a given cytochrome, the reaction was completed in the order Fe-EDTA > Fe-NTA > Fe-citrate. The kinetic data could be modeled by two parallel second-order bimolecular redox reactions with second-order rate constants ranging from 0.872 microM(-1) s(-1) for the reaction between MtrC and the Fe-EDTA complex to 0.012 microM(-1) s(-1) for the reaction between OmcA and Fe-citrate. The biphasic reaction kinetics was attributed to redox potential differences among the heme groups or redox site heterogeneity within the cytochromes. The results of redox potential and reorganization energy calculations showed that the reaction rate was influenced mostly by the relatively large reorganization energy. The results demonstrate that ligand complexation plays an important role in microbial dissimilatory reduction and mineral transformation of iron, as well as other redox-sensitive metal species in nature.

  14. Kinetics of Reduction of Fe(III) Complexes by Outer Membrane Cytochromes MtrC and OmcA of Shewanella oneidensis MR-1▿

    Science.gov (United States)

    Wang, Zheming; Liu, Chongxuan; Wang, Xuelin; Marshall, Matthew J.; Zachara, John M.; Rosso, Kevin M.; Dupuis, Michel; Fredrickson, James K.; Heald, Steve; Shi, Liang

    2008-01-01

    Because of their cell surface locations, the outer membrane c-type cytochromes MtrC and OmcA of Shewanella oneidensis MR-1 have been suggested to be the terminal reductases for a range of redox-reactive metals that form poorly soluble solids or that do not readily cross the outer membrane. In this work, we determined the kinetics of reduction of a series of Fe(III) complexes with citrate, nitrilotriacetic acid (NTA), and EDTA by MtrC and OmcA using a stopped-flow technique in combination with theoretical computation methods. Stopped-flow kinetic data showed that the reaction proceeded in two stages, a fast stage that was completed in less than 1 s, followed by a second, relatively slower stage. For a given complex, electron transfer by MtrC was faster than that by OmcA. For a given cytochrome, the reaction was completed in the order Fe-EDTA > Fe-NTA > Fe-citrate. The kinetic data could be modeled by two parallel second-order bimolecular redox reactions with second-order rate constants ranging from 0.872 μM−1 s−1 for the reaction between MtrC and the Fe-EDTA complex to 0.012 μM−1 s−1 for the reaction between OmcA and Fe-citrate. The biphasic reaction kinetics was attributed to redox potential differences among the heme groups or redox site heterogeneity within the cytochromes. The results of redox potential and reorganization energy calculations showed that the reaction rate was influenced mostly by the relatively large reorganization energy. The results demonstrate that ligand complexation plays an important role in microbial dissimilatory reduction and mineral transformation of iron, as well as other redox-sensitive metal species in nature. PMID:18791025

  15. 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

  16. New method for the direct determination of dissolved Fe(III) concentration in acid mine waters

    Science.gov (United States)

    To, T.B.; Nordstrom, D.K.; Cunningham, K.M.; Ball, J.W.; McCleskey, R.B.

    1999-01-01

    A new method for direct determination of dissolved Fe(III) in acid mine water has been developed. In most present methods, Fe(III) is determined by computing the difference between total dissolved Fe and dissolved Fe(II). For acid mine waters, frequently Fe(II) >> Fe(III); thus, accuracy and precision are considerably improved by determining Fe(III) concentration directly. The new method utilizes two selective ligands to stabilize Fe(III) and Fe(II), thereby preventing changes in Fe reduction-oxidation distribution. Complexed Fe(II) is cleanly removed using a silica-based, reversed-phase adsorbent, yielding excellent isolation of the Fe(III) complex. Iron(III) concentration is measured colorimetrically or by graphite furnace atomic absorption spectrometry (GFAAS). The method requires inexpensive commercial reagents and simple procedures that can be used in the field. Calcium(II), Ni(II), Pb(II), AI(III), Zn(II), and Cd(II) cause insignificant colorimetric interferences for most acid mine waters. Waters containing >20 mg of Cu/L could cause a colorimetric interference and should be measured by GFAAS. Cobalt(II) and Cr(III) interfere if their molar ratios to Fe(III) exceed 24 and 5, respectively. Iron(II) interferes when its concentration exceeds the capacity of the complexing ligand (14 mg/L). Because of the GFAAS elemental specificity, only Fe(II) is a potential interferent in the GFAAS technique. The method detection limit is 2 ??g/L (40 nM) using GFAAS and 20 ??g/L (0.4 ??M) by colorimetry.A new method for direct determination of dissolved Fe(III) in acid mine water has been developed. In most present methods, Fe(III) is determined by computing the difference between total dissolved Fe and dissolved Fe(II). For acid mine waters, frequently Fe(II)???Fe(III); thus, accuracy and precision are considerably improved by determining Fe(III) concentration directly. The new method utilizes two selective ligands to stabilize Fe(III) and Fe(II), thereby preventing changes

  17. As(III) removal and speciation of Fe (Oxyhydr)oxides during simultaneous oxidation of As(III) and Fe(II).

    Science.gov (United States)

    Han, Xu; Song, Jia; Li, Yi-Liang; Jia, Shao-Yi; Wang, Wen-Hui; Huang, Fu-Gen; Wu, Song-Hai

    2016-03-01

    Abiotic oxidation of Fe(II) is an important pathway in the formation of Fe (oxyhydr)oxides. However, how can As(III) affect the oxidation rate of Fe(II) and the speciation of Fe (oxyhydr)oxides, and what's the extent of the newly formed Fe (oxyhydr)oxides on the removal of aqueous arsenic are still poorly understood. Oxidation of Fe(II) under neutral pH conditions was therefore investigated under different molar ratios of As:Fe. Our results suggest that co-existence of aqueous As(III) significantly slows down the oxidation rate of Fe(II). Speciation of Fe (oxyhydr)oxides is dependent on pH and As:Fe ratios. At pH 6.0, formation of lepidocrocite and goethite is apparently inhibited at low As:Fe ratios, and ferric arsenate is favored at high As:Fe ratios. At pH 7.0, lepidocrocite gradually degenerates with the increasing As:Fe ratios. At pH 8.0, arsenite significantly inhibits the development of magnetite and favors a formation of lepidocrocite. XPS analysis further reveals that more than half of As(III) is oxidized to As(V) at pH 6.0 and 7.0, whereas at pH 8.0, the rapid oxidation of Fe(II) as well as the rapid formation of Fe (oxyhydr)oxides facilitate a rapid removal of dissolved As(III) before its further oxidation to As(V). Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. Reduction of Fe(III) colloids by Shewanella putrefaciens: A kinetic model

    Science.gov (United States)

    Bonneville, Steeve; Behrends, Thilo; van Cappellen, Philippe; Hyacinthe, Christelle; Röling, Wilfred F. M.

    2006-12-01

    A kinetic model for the microbial reduction of Fe(III) oxyhydroxide colloids in the presence of excess electron donor is presented. The model assumes a two-step mechanism: (1) attachment of Fe(III) colloids to the cell surface and (2) reduction of Fe(III) centers at the surface of attached colloids. The validity of the model is tested using Shewanella putrefaciens and nanohematite as model dissimilatory iron reducing bacteria and Fe(III) colloidal particles, respectively. Attachment of nanohematite to the bacteria is formally described by a Langmuir isotherm. Initial iron reduction rates are shown to correlate linearly with the relative coverage of the cell surface by nanohematite particles, hence supporting a direct electron transfer from membrane-bound reductases to mineral particles attached to the cells. Using internally consistent parameter values for the maximum attachment capacity of Fe(III) colloids to the cells, Mmax, the attachment constant, KP, and the first-order Fe(III) reduction rate constant, k, the model reproduces the initial reduction rates of a variety of fine-grained Fe(III) oxyhydroxides by S. putrefaciens. The model explains the observed dependency of the apparent Fe(III) half-saturation constant, Km∗, on the solid to cell ratio, and it predicts that initial iron reduction rates exhibit saturation with respect to both the cell density and the abundance of the Fe(III) oxyhydroxide substrate.

  19. Control of Fe(III) site occupancy on the rate and extent of microbial reduction of Fe(III) in nontronite

    Science.gov (United States)

    Jaisi, D.P.; Kukkadapu, R.K.; Eberl, D.D.; Dong, H.

    2005-01-01

    A quantitative study was performed to understand how Fe(III) site occupancy controls Fe(III) bioreduction in nontronite by Shewanella putrefaciens CN32. NAu-1 and NAu-2 were nontronites and contained Fe(III) in different structural sites with 16 and 23% total iron (w/w), respectively, with almost all iron as Fe(III). Mo??ssbauer spectroscopy showed that Fe(III) was present in the octahedral site in NAu-1 (with a small amount of goethite), but in both the tetrahedral and the octahedral sites in NAu-2. Mo??ssbauer data further showed that the octahedral Fe(III) in NAu-2 existed in at least two environments- trans (M1) and cis (M2) sites. The microbial Fe(III) reduction in NAu-1 and NAu-2 was studied in batch cultures at a nontronite concentration of 5 mg/mL in bicarbonate buffer with lactate as the electron donor. The unreduced and bioreduced nontronites were characterized by X-ray diffraction (XRD), Mo??ssbauer spectroscopy, and transmission electron microscopy (TEM). In the presence of an electron shuttle, anthraquinone-2,6-disulfonate (AQDS), the extent of bioreduction was 11%-16% for NAu-1 but 28%-32% for NAu-2. The extent of reduction in the absence of AQDS was only 5%-7% for NAu-1 but 14%-18% for NAu-2. The control experiments with heat killed cells and without cells did not show any appreciable reduction (crystal size distribution. The decrease in crystal size suggests reductive dissolution of nontronite NAu-2, which was supported by aqueous solution chemistry (i.e., aqueous Si). These data suggest that the more extensive Fe(III) bioreduction in NAu-2 was due to the presence of the tetrahedral and the trans-octahedral Fe(III), which was presumed to be more reducible. The biogenic Fe(II) was not associated with biogenic solids or in the aqueous solution. We infer that it may be either adsorbed onto surfaces of nontronite particles/bacteria or in the structure of nontronite. Furthermore, we have demonstrated that natural nontronite clays were capable of

  20. Degradation of atrazine photoinduced by Fe(III)-pyruvate complexes in the aqueous solution.

    Science.gov (United States)

    Zhang, Changbo; Wang, Lei; Pan, Gang; Wu, Feng; Deng, Nansheng; Mailhot, Gilles; Mestankova, Hana; Bolte, Michele

    2009-09-30

    The composition and photochemical properties of the Fe(III)-Pyr complexes in the aqueous solution was studied in this work. Fe(III) was complexed by Pyr in the ratio of 1:3. The photochemical processes occurred in the Fe(III)-Pyr system was studied in detail. Fe(II) was the main intermediate product. DMPO was used as scavenger to determine the active radicals, such as *OH, CO3*-, CO2*-, H and RCO2* by ESR. Photodegradation of atrazine induced by the photolysis of Fe(III)-Pyr was studied and the reaction kinetics fitted the first order reaction. Parameters such as pH, the initial concentrations of Fe(III), pyruvate (Pyr) and atrazine were all investigated. Photoproducts were detected by the LC-MS and the photodegradation scheme was proposed. *OH radical was the main pathway of atrazine degradation.

  1. Thermodynamics of Fe(II)Fe(III) oxide systems I. Hydrothermal Fe3O4

    Science.gov (United States)

    Bartel, J.J.; Westrum, E.F.; Haas, J.L.

    1976-01-01

    The heat capacity of a hydrothermally-prepared polycrystalline sample of Fe3O4 was measured from 53 to 350 K, primarily to study the thermophysics of the Verwey transitions. Although the bifurcation of the transition was confirmed, the sample was found to contain traces of manganese. The observed transition temperatures of 117.0 and 123.0 K are 3.7 and 4.2 K higher respectively than those found in pure Fe3O4. Ancillary analytical results are consistent and indicate a stoichiometry of Mn0.008Fe2.992O4 for this material. Characteristics in the transition region are ascribed to dopant effects. ?? 1976.

  2. 柠檬酸自燃烧法制备BiFeO3工艺及性能研究%Study on Technique and Properties of BiFeO3 Prepared by Citrate Self-Combustion Method

    Institute of Scientific and Technical Information of China (English)

    王春梅; 刘世江; 郝俊红; 李涛; 赵猛; 陈镇平

    2011-01-01

    BiFeO3 powder with distorted rhombohedral perovskite structures were synthesized by the citrate self - combustion method using citric acid as chelating, nitrate as oxidant. XRD and DTA - TG were employed for the obtained powder. The crystal structure and physical properties of BiFeO3 powder and ceramics were investigated. The results show that precursor prepared by citrate sol - gel has self - combustion characteristics and the structure of BiFeO3 has improved after sintering. All samples show good ferroelectricity. BiFeO3 prepared by citrate sol - gel method possesses larger remanent polarization, because of the highly dispersed state of the precursor during the reaction, which will help the formation of BiFeO3.%以柠檬酸做络合剂,硝酸盐做氧化剂,采用柠檬酸-硝酸盐自燃烧法一步合成了具有扭曲菱方钙钛矿结构的BiFeO3粉体.利用X射线衍射(XRD)、差热-热重(DTA -TG)等技术分析了所得BiFeO3粉体,并研究了粉体烧结后BiFeO3陶瓷的相结构和电性能.结果表明,柠檬酸盐溶胶-凝胶法制备的前驱体具有自燃烧特性,自燃烧后BiFeO3粉体的菱方钙钛矿结构已经形成,经压片烧结后,材料的相结构更趋完善.所有样品均表现出较好的铁电性,柠檬酸盐溶胶-凝胶法制备的BiFeO3,因前驱体在反应过程中处于高度均匀分散状态,利于BiFeO3的成相,样品的剩余极化强度较大.

  3. Functional characterization and Me2+ ion specificity of a Ca2+-citrate transporter from Enterococcus faecalis

    NARCIS (Netherlands)

    Blancato, Victor S.; Magni, Christian; Lolkema, Juke S.

    2006-01-01

    Secondary transporters of the bacterial CitMHS family transport citrate in complex with a metal ion. Different members of the family are specific for the metal ion in the complex and have been shown to transport Mg2+-citrate, Ca2+-citrate or Fe3+-citrate. The Fe3+-citrate transporter of Streptococcu

  4. Extraction and separation of Nd(III), Sm(III), Dy(III), Fe(III), Ni(II), and Cs(I) from concentrated chloride solutions with N,N,N',N'-tetra(2-ethylhexyl) diglycolamide as new extractant

    Institute of Scientific and Technical Information of China (English)

    E.A. Mowafy; D. Mohamed

    2015-01-01

    The feasibility of using N,N,N',N'-tetra(2-ethylhexyl)diglycolamide (TEHDGA) in 75 vol.% n-dodecane-25 vol.% n-octanol as agents for the extraction and separation of Nd(III), Sm(III), Dy(III), Fe(III), Ni(II), and Cs(I) from concentrated chlo-ride solution was investigated. Different extraction behaviors were obtained towards rare earth elements (REE) studied and Fe(III), Ni(II) and Cs(I). Efficient separation of Nd(III), Sm(III) and Dy(III) from Fe(III), Ni(II), and Cs(I) was achieved by TEHDGA, depending on the HCl, HNO3 or H2SO4 concentration. A systematic investigation was carried out on the detailed extraction prop-erties of Nd(III), Sm(III), and Dy(III) with TEHDGA from chloride media. The IR spectra of the extracted species were investi-gated.

  5. 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...

  6. Novel mesoporous FeAl bimetal oxides for As(III) removal: Performance and mechanism.

    Science.gov (United States)

    Ding, Zecong; Fu, Fenglian; Cheng, Zihang; Lu, Jianwei; Tang, Bing

    2017-02-01

    In this study, novel mesoporous FeAl bimetal oxides were successfully synthesized, characterized, and employed for As(III) removal. Batch experiments were conducted to investigate the effects of Fe/Al molar ratio, dosage, and initial solution pH values on As(III) removal. The results showed that the FeAl bimetal oxide with Fe/Al molar ratio 4:1 (shorten as FeAl-4) can quickly remove As(III) from aqueous solution in a wide pH range. The FeAl-4 before and after reaction with As(III) was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM) and selected area electron diffraction (SAED), Brunauer-Emmett-Teller (BET) surface area measurement, and X-ray photoelectron spectroscopy (XPS). The BET results showed that the original FeAl-4 with a high surface area of 223.9 m(2)/g was a mesoporous material. XPS analysis indicated that the surface of FeAl-4 possessed a high concentration of M-OH (where M represents Fe and Al), which was beneficial to the immobility of As(III). The excellent performance of FeAl-4 makes it a potentially attractive material for As(III) removal from aqueous solution. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Spectroelectrochemistry of Fe(III)- and Co(III)-mimochrome VI artificial enzymes immobilized on mesoporous ITO electrodes.

    Science.gov (United States)

    Vitale, R; Lista, L; Lau-Truong, S; Tucker, R T; Brett, M J; Limoges, B; Pavone, V; Lombardi, A; Balland, V

    2014-02-21

    UV-visible absorption spectroelectrochemistry elucidated the different redox behaviours of Fe(III)- and Co(III)-mimochrome VI artificial enzymes, adsorbed on mesoporous conductive films of ITO. The reduction of the ferric complex was rapid and reversible, while the cobaltic complex exhibited irreversible processes probably related to multiple coordination states.

  8. Fe(III)EDTA and Fe(II)EDTA-NO reduction by a sulfate reducing bacterium in NO and SO₂ scrubbing liquor.

    Science.gov (United States)

    Chen, Mingxiang; Zhou, Jiti; Zhang, Yu; Wang, Xiaojun; Shi, Zhuang; Wang, Xiaowei

    2015-03-01

    A viable process concept, based on NO and SO2 absorption into an alkaline Fe(II)EDTA (EDTA: ethylenediaminetetraacetic acid) solution in a scrubber combined with biological reduction of the absorbed SO2 utilizing sulfate reducing bacteria (SRB) and regeneration of the scrubbing liquor in a single bioreactor, was developed. The SRB, Desulfovibrio sp. CMX, was used and its sulfate reduction performances in FeEDTA solutions and Fe(II)EDTA-NO had been investigated. In this study, the detailed regeneration process of Fe(II)EDTA solution, which contained Fe(III)EDTA and Fe(II)EDTA-NO reduction processes in presence of D. sp. CMX and sulfate, was evaluated. Fe(III)EDTA and Fe(II)EDTA-NO reduction processes were primarily biological, even if Fe(III)EDTA and Fe(II)EDTA-NO could also be chemically convert to Fe(II)EDTA by biogenic sulfide. Regardless presence or absence of sulfate, more than 87 % Fe(III)EDTA and 98 % Fe(II)EDTA-NO were reduced in 46 h, respectively. Sulfate and Fe(III)EDTA had no affection on Fe(II)EDTA-NO reduction. Sulfate enhanced final Fe(III)EDTA reduction. Effect of Fe(III)EDTA on Fe(II)EDTA-NO reduction rate was more obvious than effect of sulfate on Fe(II)EDTA-NO reduction rate before 8 h. To overcome toxicity of Fe(II)EDTA-NO on SRB, Fe(II)EDTA-NO was reduced first and the reduction of Fe(III)EDTA and sulfate occurred after 2 h. First-order Fe(II)EDTA-NO reduction rate and zero-order Fe(III)EDTA reduction rate were detected respectively before 8 h.

  9. Structural characterization of a family of cytochromes c(7) involved in Fe(III) respiration by Geobacter sulfurreducens.

    Science.gov (United States)

    Pokkuluri, P R; Londer, Y Y; Yang, X; Duke, N E C; Erickson, J; Orshonsky, V; Johnson, G; Schiffer, M

    2010-02-01

    Periplasmic cytochromes c(7) are important in electron transfer pathway(s) in Fe(III) respiration by Geobacter sulfurreducens. The genome of G. sulfurreducens encodes a family of five 10-kDa, three-heme cytochromes c(7). The sequence identity between the five proteins (designated PpcA, PpcB, PpcC, PpcD, and PpcE) varies between 45% and 77%. Here, we report the high-resolution structures of PpcC, PpcD, and PpcE determined by X-ray diffraction. This new information made it possible to compare the sequences and structures of the entire family. The triheme cores are largely conserved but are not identical. We observed changes, due to different crystal packing, in the relative positions of the hemes between two molecules in the crystal. The overall protein fold of the cytochromes is similar. The structure of PpcD differs most from that of the other homologs, which is not obvious from the sequence comparisons of the family. Interestingly, PpcD is the only cytochrome c(7) within the family that has higher abundance when G. sulfurreducens is grown on insoluble Fe(III) oxide compared to ferric citrate. The structures have the highest degree of conservation around "heme IV"; the protein surface around this heme is positively charged in all of the proteins, and therefore all cytochromes c(7) could interact with similar molecules involving this region. The structures and surface characteristics of the proteins near the other two hemes, "heme I" and "heme III", differ within the family. The above observations suggest that each of the five cytochromes c(7) could interact with its own redox partner via an interface involving the regions of heme I and/or heme III; this provides a possible rationalization for the existence of five similar proteins in G. sulfurreducens. 2009 Elsevier B.V. All rights reserved.

  10. Influence of synthesis conditions on microstructure and phase transformations of annealed Sr2FeMoO6-x nanopowders formed by the citrate-gel method.

    Science.gov (United States)

    Yarmolich, Marta; Kalanda, Nikolai; Demyanov, Sergey; Terryn, Herman; Ustarroz, Jon; Silibin, Maksim; Gorokh, Gennadii

    2016-01-01

    The sequence of phase transformations during Sr2FeMoO6-x crystallization by the citrate-gel method was studied for powders synthesized with initial reagent solutions with pH values of 4, 6 and 9. Scanning electron microscopy revealed that the as-produced and annealed powders had the largest Sr2FeMoO6-x agglomerates with diameters in the range of 0.7-1.2 µm. The average grain size of the powders in the dispersion grows from 250 to 550 nm with increasing pH value. The X-ray diffraction analysis of the powders annealed at different temperatures between 770 and 1270 K showed that the composition of the initially formed Sr2FeMoO6-x changes and the molybdenum content increases with further heating. This leads to a change in the Sr2FeMoO6-x crystal lattice parameters and a contraction of the cell volume. An optimized synthesis procedure based on an initial solution of pH 4 allowed a single-phase Sr2FeMoO6-x compound to be obtained with a grain size in the range of 50-120 nm and a superstructural ordering of iron and molybdenum cations of 88%.

  11. Heterogeneous Reduction of PuO2 with Fe(II): Importance of the Fe(III) Reaction Product

    Energy Technology Data Exchange (ETDEWEB)

    Felmy, Andrew R.; Moore, Dean A.; Rosso, Kevin M.; Qafoku, Odeta; Rai, Dhanpat; Buck, Edgar C.; Ilton, Eugene S.

    2011-05-01

    Abstract Heterogeneous reduction of actinides in higher and more soluble oxidation states to lower more insoluble oxidation states by reductants such as Fe(II) has been the subject of intensive study for more than two decades. However, Fe(II)-induced reduction of sparingly soluble Pu(IV) to the more soluble lower oxidation state Pu(III) has been much less studied even though such reactions can potentially increase the mobility of Pu in the subsurface. Thermodynamic calculations are presented that show how differences in the free energy of various possible solid-phase Fe(III) reaction products can greatly influence aqueous Pu(III) concentrations resulting from reduction of PuO2(am) by Fe(II). We present the first experimental evidence that reduction of PuO2(am) to Pu(III) by Fe(II) was enhanced when the Fe(III) mineral goethite was spiked into the reaction. The effect of goethite on reduction of Pu(IV) was demonstrated by measuring the time-dependence of total aqueous Pu concentration, its oxidation state, and system pe/pH. We also re-evaluated established protocols for determining Pu(III) [(Pu(III) + Pu(IV)) - Pu(IV)] by using thenoyltrifluoroacetone (TTA) in toluene extractions; the study showed that it is important to eliminate dissolved oxygen from the TTA solutions for accurate determinations. More broadly, this study highlights the importance of the Fe(III) reaction product in actinide reduction rate and extent by Fe(II).

  12. Adsorption characteristics of U(VI) on Fe(III)Cr(III) (oxy)hydroxides synthesized at different temperatures.

    Science.gov (United States)

    Ahn, Hyangsig; Jo, Ho Young; Lee, Young Jae; Kim, Geon-Young

    2016-07-01

    In this study, the adsorption behavior of U(VI) on (oxy)hydroxides synthesized at different temperatures (25 and 75 °C) was investigated. Four (oxy)hydroxides were synthesized by drying slurries of Fe(III) and Fe(III)Cr(III) (oxy)hydroxide in a vacuum desiccator (25 °C) or in an oven (75 °C). Batch adsorption tests were conducted using the (oxy)hydroxides thus synthesized and groundwater containing uranium ions. In general, the U(VI) removal fraction significantly increased with increasing pH from 3 to 5, remained constant with increasing pH from 5 to 9, and decreased at pH greater than 9, regardless of the type of (oxy)hydroxides and solid-to-liquid ratio. The effect of pH on the U(VI) removal fraction was more significant at a low solid-to-liquid ratio. The oven-dried Fe(III) (oxy)hydroxide exhibited a U(VI) removal fraction lower than that of the vacuum-dried one, whereas the oven-dried Fe(III)Cr(III) (oxy)hydroxide exhibited a U(VI) removal fraction higher than that exhibited by the vacuum-dried one. X-ray photoelectron spectroscopy (XPS) analysis results indicated that the difference in the U(VI) removal fraction is attributed to the dissolution and precipitation of the Fe(III) (oxy)hydroxide during oven drying and dehydration of the Fe(III)Cr(III) (oxy)hydroxide during oven drying.

  13. 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

  14. 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 an

  15. Fe(II)EDTA-NO reduction coupled with Fe(II)EDTA oxidation by a nitrate- and Fe(III)-reducing bacterium.

    Science.gov (United States)

    Dong, Xiyang; Zhang, Yu; Zhou, Jiti; Chen, Mingxiang; Wang, Xiaojun; Shi, Zhuang

    2013-06-01

    The nitrate- and Fe(III)-reducing bacterium Paracoccus versutus LYM was characterized in terms of its ability to perform Fe(II)EDTA-NO reduction coupled with Fe(II)EDTA oxidation (NO-dependent Fe(II)EDTA oxidation, NDFO). It experienced a single anaerobic FeEDTA redox cycling through NDFO and dissimilatory Fe(III)EDTA reduction in FeEDTA culture. The increase in the Fe(II)EDTA concentration contributed to the ascending Fe(II)EDTA-NO reduction rate. The amount of glucose controlled the rate and extent of Fe(II) oxidation during NDFO. Without glucose addition, Fe(II)EDTA-NO reduction rate was at a rather slow rate even in presence of relatively sufficient Fe(II)EDTA. Unlike aqueous Fe(2+) and solid-phase Fe(II), Fe(II)EDTA could prevent cells from encrustations. These findings suggested the occurrence of NDFO preferred being beneficial via a mixotrophic physiology in the presence of an organic cosubstrate to being out of consideration for metabolic strategy.

  16. Role of citrate and phosphate anions in the mechanism of iron(III) sequestration by ferric binding protein: kinetic studies of the formation of the holoprotein of wild-type FbpA and its engineered mutants.

    Science.gov (United States)

    Weaver, Katherine D; Gabricević, Mario; Anderson, Damon S; Adhikari, Pratima; Mietzner, Timothy A; Crumbliss, Alvin L

    2010-07-27

    Ferric binding protein A (FbpA) plays a central role in the iron acquisition processes of pathogenic Neisseria gonorrheae, Neisseria meningitidis, and Haemophilus influenzae. FbpA functions as an iron shuttle within the periplasmic space of these Gram-negative human pathogens. Iron is picked up by FbpA at the periplasmic aspect of the outer membrane with concomitant acquisition of a synergistic anion. Here we report the kinetics and mechanisms involved with loading of iron(III) into iron-free FbpA using iron(III) citrate as an iron source in the presence of excess citrate or phosphate (physiologically available anions) at pH 6.5. In the presence of excess phosphate, iron(III) citrate loads into apo-FbpA in three kinetically distinguishable steps, while in the presence of excess citrate, only two steps are discernible. A stable intermediate containing iron(III) citrate-bound FbpA is observed in each case. The observation of an additional kinetic step and moderate increase in apparent rate constants suggests an active role for phosphate in the iron insertion process. To further elucidate a mechanism for iron loading, we report on the sequestration kinetics of iron(III) citrate in the presence of phosphate with binding site mutant apo-FbpAs, H9E, E57D, E57Q, Q58A, Y195F, and Y196H. Tyrosine mutations drastically alter the kinetics and hamper iron sequestration ability. H9E, E57D, and E57Q have near native iron sequestration behavior; however, iron binding rates are altered, enabling assignment of sequential side chain interactions. Additionally, this investigation elaborates on the function of FbpA as a carrier for iron chelates as well as "naked" or free iron as originally proposed.

  17. Molar Absorptivity and Concentration-Dependent Quantum Yield of Fe(II) Photo-Formation for the Aqueous Solutions of Fe(III)-Dicarboxylate Complexes

    Science.gov (United States)

    Hitomi, Y.; Arakaki, T.

    2009-12-01

    Redox cycles of iron in the aquatic environment affect formation of reactive oxygen species such as hydrogen peroxide and hydroxyl radicals, which in turn determines lifetimes of many organic compounds. Although aqueous Fe(III)-dicarboxylate complexes are considered to be important sources of photo-formed Fe(II), molar absorptivity and quantum yield of Fe(II) formation for individual species are not well understood. We initiated a study to characterize Fe(II) photo-formation from Fe(III)-dicarboxylates with the concentration ranges that are relevant to the natural aquatic environment. The Visual MINTEQ computer program was used to calculate the equilibrium concentrations of individual Fe(III)-dicarboxylate species. The molar absorptivity of Fe(III)-dicarboxylate species was obtained by UV-VIS spectrophotometer, and the product of the quantum yield and the molar absorptivity of Fe(III)-dicarboxylate species were obtained from photochemical experiments. These experimental data were combined with the calculated equilibrium Fe(III)-dicarboxylate concentrations to determine individual molar absorptivity and quantum yield of Fe(II) photo-formation for a specific Fe(III)-dicarboxylate species. We used initial concentrations of less than 10 micromolar Fe(III) to study the photochemical formation of Fe(II). Dicarboxylate compounds studied include oxalate, malonate, succinate, malate, and phthalate. We report molar absorptivity and concentration-dependent quantum yields of Fe(II) photo-formation of individual Fe(III)-dicarboxylates.

  18. Selection of Chelated Fe (III)/Fe (II) Catalytic Oxidation Agents for Desulfurization Based on Iron Complexation Method

    Institute of Scientific and Technical Information of China (English)

    Luo Ying; Liu Youzhi; Qi Guisheng; Guo Huidong; Zhu Zhengfeng

    2014-01-01

    Optimization of factors inlfuencing the experiments on reactions involving 8 different chelating agents and sol-uble Fe (III)/Fe (II) salts was carried out to yield chelated iron complexes. A combination of optimized inlfuencing factors has resulted in a Fe chelating capacity of the iron-based desulfurization solution to be equal to 6.83-13.56 g/L at a redox potential of 0.185-0.3. The desulfurization performance of Fe (III)/Fe (II) chelating agents was investigated on a simulated sulfur-containing industrial gas composed of H2S and N2 in a cross-lfow rotating packed bed. Test results have revealed that the proposed iron-based desulfurization solution showed a sulfur removal efifciency of over 99%along with a Fe chelating capacity exceeding 1.35 g/L. This desulfurization technology which has practical application prospect is currently in the phase of commercial scale-up study.

  19. Contrasting effects of Al substitution on microbial reduction of Fe(III) (hydr)oxides

    Science.gov (United States)

    Ekstrom, Eileen B.; Learman, Deric R.; Madden, Andrew S.; Hansel, Colleen M.

    2010-12-01

    Aluminum, one of the most abundant elements in soils and sediments, is commonly found co-precipitated with Fe in natural Fe(III) (hydr)oxides; yet, little is known about how Al substitution impacts bacterial Fe(III) reduction. Accordingly, we investigated the reduction of Al substituted (0-13 mol% Al) goethite, lepidocrocite, and ferrihydrite by the model dissimilatory Fe(III)-reducing bacterium (DIRB), Shewanella putrefaciens CN32. Here we reveal that the impact of Al on microbial reduction varies with Fe(III) (hydr)oxide type. No significant difference in Fe(III) reduction was observed for either goethite or lepidocrocite as a function of Al substitution. In contrast, Fe(III) reduction rates significantly decreased with increasing Al substitution of ferrihydrite, with reduction rates of 13% Al-ferrihydrite more than 50% lower than pure ferrihydrite. Although Al substitution changed the minerals' surface area, particle size, structural disorder, and abiotic dissolution rates, we did not observe a direct correlation between any of these physiochemical properties and the trends in bacterial Fe(III) reduction. Based on projected Al-dependent Fe(III) reduction rates, reduction rates of ferrihydrite fall below those of lepidocrocite and goethite at substitution levels equal to or greater than 18 mol% Al. Given the prevalence of Al substitution in natural Fe(III) (hydr)oxides, our results bring into question the conventional assumptions about Fe (hydr)oxide bioavailability and suggest a more prominent role of natural lepidocrocite and goethite phases in impacting DIRB activity in soils and sediments.

  20. Bioavailability of Fe(III) in natural soils and the impact on mobility of inorganic contaminants

    Energy Technology Data Exchange (ETDEWEB)

    Kosson, David S.; Cowan, Robert M.; Young, Lily Y.; Hacherl, Eric L.; Scala, David J.

    2002-10-03

    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.

  1. Tuning through-bond Fe(III)/Fe(II) coupling by solvent manipulation of a central ruthenium redox couple.

    Science.gov (United States)

    Lin, Yu-Chen; Chen, Wei-Tin; Tai, Joe; Su, Denny; Huang, Sheng-Yi; Lin, Ingrid; Lin, Ju-Ling; Lee, Mandy M; Chiou, Mong Feng; Liu, Yen-Hsiang; Kwan, Ken-Shin; Chen, Yuan-Jang; Chen, Hsing-Yin

    2009-03-02

    The relationships between the intervalence energy (E(IT)) and the free energy difference (DeltaG) that exists between the minima of redox isomers (Fe(II)-Ru(III)/Fe(III)-Ru(II)) for various heterobimetallic complexes [(R-Fcpy)Ru(NH(3))(5)](2+/3+) (R = H, ethyl, Br, actyl; Fcpy = (4-pyridyl)ferrocenyl; Ru(NH(3))(5) = pentaam(m)ineruthenium) were examined. The changes in DeltaG for the complexes in various solvents were due to the effects of both solvent donicity and the substituents. The intervalence energy versus DeltaG, DeltaG approximately FDeltaE(1/2) (DeltaE(1/2) = E(1/2)(Fe(III/II)) - E(1/2)(Ru(III/II))), plots for the complexes in various solvents suggest a nuclear reorganization energy (lambda) of approximately 6000 cm(-1) (Chen et al. Inorg. Chem. 2000, 39, 189). For [(R-Fcpy)Ru(NH(3))(5)](2+) and [(et-Fcpy)Ru(NH(3))(4)(py)](2+) (Ru(NH(3))(4) = trans-tetraam(m)ineruthenium; py = pyridine) in various solvents, the E(1/2)(Ru(III/II)) of rutheniumam(m)ine typically was less than the E(1/2)(Fe(III/II)) of the ferrocenyl moiety. However, the low-donicity solvents resulted in relatively large values of E(1/2)(Ru(III/II)) for [(et-Fcpy)Ru(NH(3))(4)(py)](2+/3+/4+). Under our unique solvent conditions, a dramatic end-to-end interaction was observed for the trimetal cation, [(et-Fcpy)(2)Ru(NH(3))(4)](4+), in which the [(et-Fcpy)(2)Ru(NH(3))(4)](4+) included a central trans-tetraam(m)ineruthenium(III) and a terminal Fe(II)/Fe(III) pair. In general, results of electrochemical studies of [(et-Fcpy)(2)Ru(NH(3))(4)](2+) indicated both solvent-tunable E(1/2)(Ru(III/II)) (1 e(-)) and solvent-insensitive E(1/2)(Fe(III/II)) (2 e(-)) redox centers. However, in nitriles, two E(1/2)(Fe(III/II)) peaks were found with DeltaE(1/2)(Fe(III/II) - Fe(III/II)) ranging between 83 and 108 mV at a terminal metal-to-metal distance of up to 15.6 A. Furthermore, the bridging dpi orbital of the ruthenium center mediated efficient end-to-end interaction between the combinations of the terminal

  2. Synthesis of Imine-Naphthol Tripodal Ligand and Study of Its Coordination Behaviour towards Fe(III, Al(III, and Cr(III Metal Ions

    Directory of Open Access Journals (Sweden)

    Kirandeep Kaur

    2014-01-01

    Full Text Available A hexadentate Schiff base tripodal ligand is synthesized by the condensation of tris (2-aminoethyl amine with 2-hydroxy-1-naphthaldehyde and characterized by various spectroscopic techniques like UV-VIS, IR, NMR, MASS, and elemental analysis. The solution studies by potentiometric and spectrophotometric methods are done at 25 ± 1°C, µ=0.1 M KCl, to calculate the protonation constants of the ligand and formation constants of metal complexes formed by the ligand with Fe(III, Al(III, and Cr(III metal ions. The affinity of the ligand towards Fe(III is compared with deferiprone (a drug applied for iron intoxication and transferrin (the main Fe(III binding protein in plasma. Structural analysis of the ligand and the metal complexes was done using semiempirical PM6 method. Electronic and IR spectra are calculated by semiempirical methods and compared with experimental one.

  3. Synthesis of Imine-Naphthol Tripodal Ligand and Study of Its Coordination Behaviour towards Fe(III), Al(III), and Cr(III) Metal Ions.

    Science.gov (United States)

    Kaur, Kirandeep; Baral, Minati

    2014-01-01

    A hexadentate Schiff base tripodal ligand is synthesized by the condensation of tris (2-aminoethyl) amine with 2-hydroxy-1-naphthaldehyde and characterized by various spectroscopic techniques like UV-VIS, IR, NMR, MASS, and elemental analysis. The solution studies by potentiometric and spectrophotometric methods are done at 25 ± 1°C, µ = 0.1 M KCl, to calculate the protonation constants of the ligand and formation constants of metal complexes formed by the ligand with Fe(III), Al(III), and Cr(III) metal ions. The affinity of the ligand towards Fe(III) is compared with deferiprone (a drug applied for iron intoxication) and transferrin (the main Fe(III) binding protein in plasma). Structural analysis of the ligand and the metal complexes was done using semiempirical PM6 method. Electronic and IR spectra are calculated by semiempirical methods and compared with experimental one.

  4. Transamidation of carboxamides catalyzed by Fe(III) and water.

    Science.gov (United States)

    Becerra-Figueroa, Liliana; Ojeda-Porras, Andrea; Gamba-Sánchez, Diego

    2014-05-16

    The highly efficient transamidation of several primary, secondary, and tertiary amides with aliphatic and aromatic amines (primary and secondary) is described. The reaction is performed in the presence of a 5 mol % concentration of different hydrated salts of Fe(III), and the results show that the presence of water is crucial. The methodology was also applied to urea and phthalimide to demonstrate its versatility and wide substrate scope. An example of its use is an intramolecular application in the synthesis of 2,3-dihydro-5H-benzo[b]-1,4-thiazepin-4-one, which is the bicyclic core of diltiazem and structurally related drugs (Budriesi, R.; Cosimelli, B.; Ioan, P.; Carosati, E.; Ugenti, M. P.; Spisani, R. Curr. Med. Chem. 2007, 14, 279-287). A plausible mechanism that explains the role of water is proposed on the basis of experimental observations and previous mechanistic suggestions for transamidation reactions catalyzed by transition metals such as copper and aluminum. This methodology represents a significant improvement over other existing methods; it can be performed in air and with wet or technical grade solvents.

  5. Role of Natural Organic Matter in Regulating the Partitioning of Fe(II, III) in Seawater

    Science.gov (United States)

    Guo, L.; Chen, M.; Roberts, K.; Santschi, P. H.

    2008-12-01

    Iron (Fe) is an essential micronutrient and plays an important role in controlling ocean productivity and carbon cycling. Fe has been shown to be mostly complexed with dissolved organic matter in seawater. However, the interaction of Fe with natural organic matter and how the quality and quantity of organic matter affect the chemical speciation of Fe in seawater remain poorly understood. Controlled laboratory experiments have been conducted to examine the partitioning of Fe(II, III) between dissolved, colloidal and particulate phases using radiotracers, model organic compounds, and ultrafiltration. In natural seawater, Fe is mostly partitioned in the colloidal and particulate phases, resulting in a logKd value of 7.3 and a logKc of 6.1, respectively. On average, about 25% of dissolved Fe-55 was found in the complexation of Fe with DOM could depress the bioavailability of Fe in seawater, the resultant Fe reduction may significantly enhance its solubility and bioavailability to marine organisms.

  6. Oxygen isotope indicators of selenate reaction with Fe(II) and Fe(III) hydroxides.

    Science.gov (United States)

    Schellenger, Alexandra E P; Larese-Casanova, Philip

    2013-06-18

    Selenate (SeO(4)(2-)) reduction to elemental selenium is an important Se immobilization process in subsurface environments that could be mediated by Fe(II)-rich minerals or selenate-respiring microorganisms. We report the kinetic isotope effects for (18)O within selenate during abiotic reactions with iron-bearing hydroxides within laboratory experiments. Selenate was reduced to Se(0) by a green rust (chloride interlayer type) and ferrous hydroxide, the two known environmentally relevant mineral reductants for selenate. Reaction kinetics are described by a rapid, low-fractionating uptake step caused by diffusive exchange between selenate and chloride followed by a slower, high-fractionating reduction step caused by electron transfer from structural Fe(II). The dual-phase kinetics cannot be described with the traditional Rayleigh fractionation model; however, well after the initial uptake step, the extent of selenate reaction is well correlated with δ(18)O values in accordance with the Rayleigh model. Selenate-(18)O enrichment (εO) was nearly identical for reaction with chloride green rust (22.7 ± 2.2‰) and ferrous hydroxide (22.1 ± 1.1‰) which suggests a common reduction mechanism by structural Fe(II). The minor enrichment due to anion exchange alone (1.4 ± 0.2‰) was confirmed using iowaite, a nonredox active Mg(II)-Fe(III) layered double hydroxide. Our εO results may contribute to Se isotope forensics to identify selenate reduction within field sites and to possibly distinguish between abiotic and biotic reduction processes.

  7. Anaerobic mineralization of vinyl chloride in Fe(III)-reducing, aquifer sediments

    Science.gov (United States)

    Bradley, P.M.; Chapelle, F.H.

    1996-01-01

    Within anaerobic aquifer systems, reductive dehalogenation of polychlorinated ethenes commonly results in the accumulation of vinyl chloride, which is highly toxic and carcinogenic to humans. Anaerobic reduction of vinyl chloride is considered to be slow and incomplete. Here, we provide the first evidence for anaerobic oxidation of vinyl chloride under Fe(III)reducing conditions. Addition of chelated Fe(III) (as Fe-EDTA) to anaerobic aquifer microcosms resulted in mineralization of up to 34% of [1,2- 14C]vinyl chloride within 84 h. The results indicate that vinyl chloride can be mineralized under anaerobic, Fe(III)-reducing conditions and that the bioavailability of Fe(III) is an important factor affecting the rates of mineralization.

  8. 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.

  9. Kinetics of Microbial Fe(III) Reduction: From the Laboratory to the Field

    Science.gov (United States)

    Bonneville, S.; van Cappellen, P.; Behrends, T.; Hyacinthe, C.

    2005-12-01

    A kinetic model for the direct microbial reduction of Fe(III)solids in the presence of excess electron donor is presented. The model assumes a two-step mechanism: (i) mutual attachment of Fe(III) solids and cells, and (ii) reduction of Fe(III) centers at the surface of attached mineral particles. The validity of the model is tested using Shewanella putrefaciens and nanohematite as model dissimilatory iron reducing bacteria and Fe(III) solid, respectively. The results demonstrate that the iron reduction rates correlate linearly with the relative coverage of the cell surface by nanohematite, hence supporting a direct electron transfer from membrane-bound reductases to the mineral surface. The model is extended to the reduction by S. putrefaciens of other Fe(III) oxyhydroxides, as well as Fe(III)-rich natural sediments. The maximum reduction rates per cell of Fe(III)oxyhydroxides are shown to correlate with the solubility of the solid phases, while the half-saturation constants depend on the solid to cell ratio. The implications of the laboratory-based kinetics for including microbial iron reduction in reactive transport models of natural porous media are discussed.

  10. Redox cycling of Fe(II) and Fe(III) in magnetite by Fe-metabolizing bacteria

    Energy Technology Data Exchange (ETDEWEB)

    Byrne, James; Klueglein, Nicole; Pearce, Carolyn I.; Rosso, Kevin M.; Appel, Erwin; Kappler, Andreas

    2015-03-26

    Despite the regular occurrence of both magnetite and iron-metabolizing bacteria in the same environments, it is currently unknown whether the iron(II) and iron(III) in magnetite can be cycled between different bacteria and whether or how magnetic properties are affected by this metabolic activity. We show through magnetic and spectroscopic measurements that the phototrophic Fe(II)-oxidizer Rhodopseudomonas palustris TIE-1 can oxidize solid-phase magnetite nanoparticles using light energy, leading to a decrease in the measured magnetic susceptibility (MS). This process likely occurs at the surface and is reversible in the dark by the Fe(III)-reducer Geobacter sulfurreducens resulting in an increase in MS. These results show that iron ions bound in highly crystalline mineral magnetite are bioavailable as electron stores and electron sinks under varying environmental conditions, making magnetite a potential “biogeobattery” during day/night cycles. These findings are relevant for environmental studies and reinforce the impact of microbial redox processes on the global iron cycle.

  11. Going wireless: Fe(III) oxide reduction without pili by Geobacter sulfurreducens strain JS-1.

    Science.gov (United States)

    Smith, Jessica A; Tremblay, Pier-Luc; Shrestha, Pravin Malla; Snoeyenbos-West, Oona L; Franks, Ashley E; Nevin, Kelly P; Lovley, Derek R

    2014-07-01

    Previous studies have suggested that the conductive pili of Geobacter sulfurreducens are essential for extracellular electron transfer to Fe(III) oxides and for optimal long-range electron transport through current-producing biofilms. The KN400 strain of G. sulfurreducens reduces poorly crystalline Fe(III) oxide more rapidly than the more extensively studied DL-1 strain. Deletion of the gene encoding PilA, the structural pilin protein, in strain KN400 inhibited Fe(III) oxide reduction. However, low rates of Fe(III) reduction were detected after extended incubation (>30 days) in the presence of Fe(III) oxide. After seven consecutive transfers, the PilA-deficient strain adapted to reduce Fe(III) oxide as fast as the wild type. Microarray, whole-genome resequencing, proteomic, and gene deletion studies indicated that this adaptation was associated with the production of larger amounts of the c-type cytochrome PgcA, which was released into the culture medium. It is proposed that the extracellular cytochrome acts as an electron shuttle, promoting electron transfer from the outer cell surface to Fe(III) oxides. The adapted PilA-deficient strain competed well with the wild-type strain when both were grown together on Fe(III) oxide. However, when 50% of the culture medium was replaced with fresh medium every 3 days, the wild-type strain outcompeted the adapted strain. A possible explanation for this is that the necessity to produce additional PgcA, to replace the PgcA being continually removed, put the adapted strain at a competitive disadvantage, similar to the apparent selection against electron shuttle-producing Fe(III) reducers in many anaerobic soils and sediments. Despite increased extracellular cytochrome production, the adapted PilA-deficient strain produced low levels of current, consistent with the concept that long-range electron transport through G. sulfurreducens biofilms is more effective via pili.

  12. Adsorption of As(III) from Aqueous Solutions by Novel Fe-Mg Type Hydrotalcite.

    Science.gov (United States)

    Ogata, Fumihiko; Kawasaki, Naohito

    2015-01-01

    Morphological and chemical evaluation of Fe-Mg hydrotalcite (Fe-HT) was performed using scanning electron microscopy, X-ray diffraction analysis, and electron microanalysis for application as an adsorbent for water treatment. The adsorption of arsenic III (As(III)) on Fe-HT was evaluated via examination of the effect of the contact time and analysis of the adsorption isotherm. The amount of As(III) adsorbed increased slightly with increasing temperature. The results of the adsorption isotherm studies suggested that As(III) adsorption can be well described by both the Freundlich and Langmuir equations. The adsorption of As(III) on Fe-HT reached equilibrium within 24 h, and the adsorption kinetic data fit the pseudo-second-order kinetic model better than the pseudo-first-order model. The amount of As(III) present on the surface of Fe-HT increased after As(III) adsorption, and the crystalline structure of Fe-HT was maintained after adsorption of As(III). The (003) and (006) peaks in the X-ray diffraction patterns were attributed to basal reflections, and these peaks shifted from respective 2θ values of 10.86 and 21.94° to 11.12 and 22.52°, indicating exchange of As(III) with chloride ions in Fe-HT with consequent narrowing of the inter-layer spacing. Collectively, these results suggest that Fe-HT is prospectively useful for the adsorption of As(III) from aqueous solutions.

  13. Fe(III) solar light induced degradation of diethyl phthalate (DEP) in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Mailhot, G.; Caceres, J.; Malato, S.; Bolte, M.

    2003-07-01

    The degradation of diethyl phthalate (DEP) photoinduced by Fe(III) in aqueous solution has been investigated under solar irradiation in the CPC reactor at Plataforma Solar de Almeria. Hydroxyl radicals OH, responsible of the degradation, are formed via an intramolecular photo redox process in excited Fe(III) aqua complexes. 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. (Author) 28 refs.

  14. Role of Menaquinones in Fe(III) Reduction by Membrane Fractions of Shewanella putrefaciens

    Science.gov (United States)

    Saffarini, Daad A.; Blumerman, Seth L.; Mansoorabadi, Karen J.

    2002-01-01

    Two Tn5-generated mutants of Shewanella putrefaciens with insertions in menD and menB were isolated and analyzed. Both mutants were deficient in the use of several terminal electron acceptors, including Fe(III). This deficiency was overcome by the addition of menaquinone (vitamin K2). Isolated membrane fractions from both mutants were unable to reduce Fe(III) in the absence of added menaquinone when formate was used as the electron donor. These results indicate that menaquinones are essential components for the reduction of Fe(III) by both whole cells and purified membrane fractions when formate or lactate is used as the electron donor. PMID:11790756

  15. Fe(II) sorption on pyrophyllite: Effect of structural Fe(III) (impurity) in pyrophyllite on nature of layered double hydroxide (LDH) secondary mineral formation

    Energy Technology Data Exchange (ETDEWEB)

    Starcher, Autumn N.; Li, Wei; Kukkadapu, Ravi K.; Elzinga, Evert J.; Sparks, Donald L.

    2016-11-01

    Fe(II)-Al(III)-LDH (layered double hydroxide) phases have been shown to form from reactions of aqueous Fe(II) with Fe-free Al-bearing minerals (phyllosilicate/clays and Al-oxides). To our knowledge, the effect of small amounts of structural Fe(III) impurities in “neutral” clays on such reactions, however, were not studied. In this study to understand the role of structural Fe(III) impurity in clays, laboratory batch studies with pyrophyllite (10 g/L), an Al-bearing phyllosilicate, containing small amounts of structural Fe(III) impurities and 0.8 mM and 3 mM Fe(II) (both natural and enriched in 57Fe) were carried out at pH 7.5 under anaerobic conditions (4% H2 – 96% N2 atmosphere). Samples were taken up to 4 weeks for analysis by Fe-X-ray absorption spectroscopy and 57Fe Mössbauer spectroscopy. In addition to the precipitation of Fe(II)-Al(III)-LDH phases as observed in earlier studies with pure minerals (no Fe(III) impurities in the minerals), the analyses indicated formation of small amounts of Fe(III) containing solid(s), most probably hybrid a Fe(II)-Al(III)/Fe(III)-LDH phase. The mechanism of Fe(II) oxidation was not apparent but most likely was due to interfacial electron transfer from the sorbed Fe(II) to the structural Fe(III) and/or surface-sorption-induced electron-transfer from the sorbed Fe(II) to the clay lattice. Increase in the Fe(II)/Al ratio of the LDH with reaction time further indicated the complex nature of the samples. This research provides evidence for the formation of both Fe(II)-Al(III)-LDH and Fe(II)-Fe(III)/Al(III)-LDH-like phases during reactions of Fe(II) in systems that mimic the natural environments. Better understanding Fe phase formation in complex laboratory studies will improve models of natural redox systems.

  16. Spectroscopic evidence for Fe(II)-Fe(III) electron transfer at clay mineral edge and basal sites.

    Science.gov (United States)

    Neumann, Anke; Olson, Tyler L; Scherer, Michelle M

    2013-07-02

    Despite the importance of Fe redox cycling in clay minerals, the mechanism and location of electron transfer remain unclear. More specifically, there is some controversy whether electron transfer can occur through both basal and edge surfaces. Here we used Mössbauer spectroscopy combined with selective chemical extractions to study electron transfer from Fe(II) sorbed to basal planes and edge OH-groups of clay mineral NAu-1. Fe(II) sorbed predominantly to basal planes at pH values below 6.0 and to edge OH-groups at pH value 7.5. Significant electron transfer occurred from edge OH-group bound Fe(II) at pH 7.5, whereas electron transfer from basal plane-sorbed Fe(II) to structural Fe(III) in clay mineral NAu-1 at pH 4.0 and 6.0 occurred but to a much lower extent than from edge-bound Fe(II). Mössbauer hyperfine parameters for Fe(II)-reacted NAu-1 at pH 7.5 were consistent with structural Fe(II), whereas values found at pH 4.0 and 6.0 were indicative of binding environments similar to basal plane-sorbed Fe(II). Reference experiments with Fe-free synthetic montmorillonite SYn-1 provided supporting evidence for the assignment of the hyperfine parameters to Fe(II) bound to basal planes and edge OH-groups. Our findings demonstrate that electron transfer to structural Fe in clay minerals can occur from Fe(II) sorbed to both basal planes and edge OH-groups. These findings require us to reassess the mechanisms of abiotic and microbial Fe reduction in clay minerals as well as the importance of Fe-bearing clay minerals as a renewable source of redox equivalents in subsurface environments.

  17. Structure, Morphology and Chemical Synthesis of Mg1-xZnxFe2O4 Nano-Ferrites Prepared by Citrate-Gel Auto Combustion Method

    Directory of Open Access Journals (Sweden)

    D.Ravikumar

    2014-04-01

    Full Text Available Mg-Zn Nano ferrites having chemical formula Mg1-xZnxFe2O4(where x=0.0, 0.2, 0.4, 0.6, 0.8, 1.0 were synthesized by the citrate-gel auto combustion method. Synthesized powders were sintered at 500oC for four hours in air and characterized by XRD, SEM and EDS.XRD analysis shows that cubic spinal structure of the ferrites and the crystalline sizes (D were found in the range 25-35 nm. The values of the lattice parameter (a increases and X-ray density (dx increases with doping of Zn content. Scanning Electron Microscopy (SEM studies revealed Nano nature of the samples. An elemental composition of the samples was studied by using Energy Dispersive Spectroscopy (EDS. The observed results can be explained on the basis of composition and crystallite size.

  18. Evidence for the aquatic binding of arsenate by natural organic matter-suspended Fe(III)

    Science.gov (United States)

    Ritter, K.; Aiken, G.R.; Ranville, J.F.; Bauer, M. E.; Macalady, D.L.

    2006-01-01

    Dialysis experiments with arsenate and three different NOM samples amended with Fe(III) showed evidence confirming the formation of aquatic arsenate-Fe(III)-NOM associations. A linear relationship was observed between the amount of complexed arsenate and the Fe(III) content of the NOM. The dialysis results were consistent with complex formation through ferric iron cations acting as bridges between the negatively charged arsenate and NOM functional groups and/or a more colloidal association, in which the arsenate is bound by suspended Fe(III)-NOM colloids. Sequential filtration experiments confirmed that a significant proportion of the iron present at all Fe/C ratios used in the dialysis experiments was colloidal in nature. These colloids may include larger NOM species that are coagulated by the presence of chelated Fe(III) and/or NOM-stabilized ferric (oxy)hydroxide colloids, and thus, the solution-phase arsenate-Fe(III)-NOM associations are at least partially colloidal in nature. ?? 2006 American Chemical Society.

  19. Intercalation of Coordinatively Unsaturated Fe(III) Ion within Interpenetrated Metal-Organic Framework MOF-5.

    Science.gov (United States)

    Holmberg, Rebecca J; Burns, Thomas; Greer, Samuel M; Kobera, Libor; Stoian, Sebastian A; Korobkov, Ilia; Hill, Stephen; Bryce, David L; Woo, Tom K; Murugesu, Muralee

    2016-06-01

    Coordinatively unsaturated Fe(III) metal sites were successfully incorporated into the iconic MOF-5 framework. This new structure, Fe(III) -iMOF-5, is the first example of an interpenetrated MOF linked through intercalated metal ions. Structural characterization was performed with single-crystal and powder XRD, followed by extensive analysis by spectroscopic methods and solid-state NMR, which reveals the paramagnetic ion through its interaction with the framework. EPR and Mössbauer spectroscopy confirmed that the intercalated ions were indeed Fe(III) , whereas DFT calculations were employed to ascertain the unique pentacoordinate architecture around the Fe(III) ion. Interestingly, this is also the first crystallographic evidence of pentacoordinate Zn(II) within the MOF-5 SBU. This new MOF structure displays the potential for metal-site addition as a framework connector, thus creating further opportunity for the innovative development of new MOF materials.

  20. Release of 226Ra from uranium mill tailings by microbial Fe(III) reduction

    Science.gov (United States)

    Landa, E.R.; Phillips, E.J.P.; Lovley, D.R.

    1991-01-01

    Uranium mill tailings were anaerobically incubated in the presence of H2 with Alteromonas putrefaciens, a bacterium known to couple the oxidation of H2 and organic compounds to the reduction of Fe(III) oxides. There was a direct correlation between the extent of Fe(III) reduction and the accumulation of dissolved 226Ra. In sterile tailings in which Fe(III) was not reduced, there was negligible leaching of 226Ra. The behavior of Ba was similar to that of Ra in inoculated and sterile systems. These results demonstrate that under anaerobic conditions, microbial reduction of Fe(III) may result in the release of dissolved 226Ra from uranium mill tailings. ?? 1991.

  1. Properties of a complex of Fe(III)-soybean lipoxygenase-1 and 4-nitrocatechol.

    Science.gov (United States)

    Spaapen, L J; Verhagen, J; Veldink, G A; Vliegenthart, J F

    1980-01-18

    Fe(III)-soybean lipoxygenase-1 yields with 4-nitrocatechol a green coloured 1 : 1 complex, which shows at pH 7.0 absorption maxima at 385 nm and 650 nm. The formation of this complex is reversible. The circular dichroism spectrum of the complex of Fe(III)-lipoxygenase-1 and 4-nitrocatechol has a positive band at around 380 nm and a negative band at around 450 nm and is significantly different from that of the Fe(III)-enzyme as such. 4-Nitrocatechol can be displaced from the green complex by 13-L-hydroperoxy-cis-9, trans-11-octadecadienoic acid, resulting in the formation of the blue complex between the Fe(III)-enzyme and 13-L-hydroperoxy-cis-9,trans-11-octadecadienoic acid both under aerobic and anaerobic conditions. Also linoleic acid competes with 4-nitrocatechol for the binding site on the Fe(III)-enzyme, as can be demonstrated under anaerobic conditions, ultimately leading to reduction of the Fe(III)-enzyme. The oxygenation of linoleic acid by Fe(III)-lipoxygenase-1 is inhibited by 4-nitrocatechol. From steady-state kinetics a non-competitive inhibition pattern is obtained. Probably it has to be considered as pseudo non-competitive because of the slow establishment of the complex equilibrium. An inhibition constant (K4NC) of 16.3 microM is found. On prolonged incubation of Fe(III)-lipoxygenase-1 and 4-nitrocatechol the green complex converts into a brown species. This conversion is found to be coupled with a change in the nature of the inhibition from reversible to irreversible. A complex between native lipoxygenase-1 and 4-nitrocatechol is found to be unlikely.

  2. 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.

  3. Effect of desferrioxamine B and Suwannee River fulvic acid on Fe(III) release and Cr(III) desorption from goethite

    Science.gov (United States)

    Stewart, Angela G.; Hudson-Edwards, Karen A.; Dubbin, William E.

    2016-04-01

    Siderophores are biogenic chelating ligands that facilitate the solubilisation of Fe(III) and form stable complexes with a range of contaminant metals and therefore may significantly affect their biogeochemical cycling. Desferrioxamine B (DFOB) is a trihydroxamate siderophore that acts synergistically with fulvic acid and low molecular weight organic ligands to release Fe from Fe(III) oxides. We report the results of batch dissolution experiments in which we determine the rates of Cr(III) desorption and Fe(III) release from Cr(III)-treated synthetic goethite as influenced by DFOB, by fulvic acid, and by the two compounds in combination. We observed that adsorbed Cr(III) at 3% surface coverage significantly reduced Fe(III) release from goethite for all combinations of DFOB and fulvic acid. When DFOB (270 μM) was the only ligand present, dissolved Fe(III) and Cr(III) increased approximately 1000-fold and 16-fold, respectively, as compared to the ligand-free system, a difference we attribute to the slow rate of water exchange of Cr(III). Suwannee River fulvic acid (SRFA) acts synergistically with DFOB by (i) reducing the goethite surface charge leading to increased HDFOB+ surface excess and by (ii) forming aqueous Fe(III)-SRFA species whose Fe(III) is subsequently removed by DFOB to yield aqueous Fe(III)-DFOB complexes. These observations shed new light on the synergistic relationship between DFOB and fulvic acid and reveal the mechanisms of Fe(III) acquisition available to plants and micro-organisms in Cr(III) contaminated environments.

  4. 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 o

  5. High-temperature spin crossover behavior in a nitrogen-rich Fe(III)-based system.

    Science.gov (United States)

    Cook, Cyril; Habib, Fatemah; Aharen, Tomoko; Clérac, Rodolphe; Hu, Anguang; Murugesu, Muralee

    2013-02-18

    A nitrogen-rich ligand bis(1H-tetrazol-5-yl)amine (H(3)bta) was employed to isolate a new Fe(III) complex, Na(2)NH(4)[Fe(III)(Hbta)(3)]·3DMF·2H(2)O (1). Single crystal X-ray diffraction revealed that complex 1 consists of Fe(III) ions in an octahedral environment where each metal ion is coordinated by three Hbta(2-) ligands forming the [Fe(III)(Hbta)(3)](3-) core. Each unit is linked to two one-dimensional (1-D) Na(+)/solvent chains creating a two-dimensional (2-D) network. In addition, the presence of multiple hydrogen bonds in all directions between ammonium cation and ligands of different [Fe(III)(Hbta)(3)](3-) units generates a three-dimensional (3-D) network. Magnetic measurements confirmed that the Fe(III) center undergoes a Spin Crossover (SCO) at high temperature (T(1/2) = 460(10) K).

  6. 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

  7. 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

  8. 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 un

  9. 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 unde

  10. 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.

  11. Subsurface Uranium Fate and Transport: Integrated Experiments and Modeling of Coupled Biogeochemical Mechanisms of Nanocrystalline Uraninite Oxidation by Fe(III)-(hydr)oxides - Project Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Peyton, Brent M. [Montana State Univ., Bozeman, MT (United States); Timothy, Ginn R. [Univ. of California, Davis, CA (United States); Sani, Rajesh K. [South Dakota School of Mines and Technology, Rapid City, SD (United States)

    2013-08-14

    Subsurface bacteria including sulfate reducing bacteria (SRB) reduce soluble U(VI) to insoluble U(IV) with subsequent precipitation of UO2. We have shown that SRB reduce U(VI) to nanometer-sized UO2 particles (1-5 nm) which are both intra- and extracellular, with UO2 inside the cell likely physically shielded from subsequent oxidation processes. We evaluated the UO2 nanoparticles produced by Desulfovibrio desulfuricans G20 under growth and non-growth conditions in the presence of lactate or pyruvate and sulfate, thiosulfate, or fumarate, using ultrafiltration and HR-TEM. Results showed that a significant mass fraction of bioreduced U (35-60%) existed as a mobile phase when the initial concentration of U(VI) was 160 µM. Further experiments with different initial U(VI) concentrations (25 - 900 M) in MTM with PIPES or bicarbonate buffers indicated that aggregation of uraninite depended on the initial concentrations of U(VI) and type of buffer. It is known that under some conditions SRB-mediated UO2 nanocrystals can be reoxidized (and thus remobilized) by Fe(III)-(hydr)oxides, common constituents of soils and sediments. To elucidate the mechanism of UO2 reoxidation by Fe(III) (hydr)oxides, we studied the impact of Fe and U chelating compounds (citrate, NTA, and EDTA) on reoxidation rates. Experiments were conducted in anaerobic batch systems in PIPES buffer. Results showed EDTA significantly accelerated UO2 reoxidation with an initial rate of 9.5 M day-1 for ferrihydrite. In all cases, bicarbonate increased the rate and extent of UO2 reoxidation with ferrihydrite. The highest rate of UO2 reoxidation occurred when the chelator promoted UO2 and Fe(III) (hydr)oxide dissolution as demonstrated with EDTA. When UO2 dissolution did not occur, UO2 reoxidation likely proceeded through an aqueous Fe(III) intermediate as observed for both NTA and

  12. 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.

  13. Microbial Reduction of Al-Substituted Fe(III) (Hydr)oxides: Redefining the Reducing Capacity of Fe Phases in Natural Soils

    Science.gov (United States)

    Ekstrom, E. B.; Hansel, C. M.

    2008-12-01

    Aluminum, one of the most abundant elements in soils and sediments, is also commonly found co- precipitated with Fe in natural Fe (III) (hydr)oxides. Although significant progress has been made elucidating the rates and solid-phase products of Fe(III) reduction by dissimilatory iron-reducing bacteria (DIRB) grown on pure, synthetic iron (hydr)oxides, relatively little is known about the impact of Al co-precipitation within Fe(III) (hydr)oxides on growth and bacterial Fe reduction by DIRB. Two previous studies investigating bacterial Fe reduction of Al-containing goethite minerals found contrasting results. To better understand the role of Al-substitution in controlling the rate, extent, and products of bacterial Fe(III) reduction, we have performed Fe(III) reduction experiments with the model DIRB, Shewanella putrefaciens CN32 grown on synthetic ferrihydrite, lepidocrocite, and goethite containing between 0 and 13 mole % Al. These experiments reveal that the impact of Al varies among Fe(III) (hydr)oxide minerals. Increasing Al-substitution in ferrihydrite results in a decrease of bacterial growth and Fe(III) reduction, while increasing Al content within lepidocrocite causes increased bacterial growth and Fe(III) reduction. For goethite, no change in Fe(III) reduction or growth is observed when growth on goethite containing increasing Al-substitution. Given the prevalence of Al-substitution in natural Fe(III) (hydr)oxides, our results bring into question the conventional assumptions about Fe(III) oxide bioavailability and suggest a more prominent role of natural lepidocrocite phases in impacting DIRB activity in soils and sediments.

  14. 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 structure of the dinuclear complex [{( Hbpbp) Fe(mu-OH)}(2)](ClO4)(4) center dot 2C(3)H(6)O ( 1 center dot 2C(3)H(6)O) shows that only one of the metal-binding cavities of each ligand is occupied by an iron( III) atom and two [Fe(Hbpbp)](3+) units are linked together by two hydroxo bridging groups to form...... bond lengths of the two different octahedral iron sites: Fe -mu-OH, 1.953( 5), 2.013( 5) angstrom and Fe-mu-O, 1.803( 5), 1.802( 5) angstrom. The difference in ligand environment is too small for allowing Mossbauer spectroscopy to distinguish between the two crystallographically independent Fe sites...

  15. Direct Adherence of Fe(III Particles onto Sheaths of Leptothrix sp. Strain OUMS1 in Culture

    Directory of Open Access Journals (Sweden)

    Tatsuki Kunoh

    2016-01-01

    Full Text Available Leptothrix species, one of the Fe/Mn-oxidizing bacteria, oxidize Fe(II and produce extracellular, microtubuar, Fe-encrusted sheaths. Since protein(s involved in Fe(II oxidation is excreted from Leptothrix cells, the oxidation from Fe(II to Fe(III and subsequent Fe(III deposition to sheaths have been thought to occur in the vicinity or within the sheaths. Previously, Fe(III particles generated in MSVP medium amended with Fe(II salts by abiotic oxidation were directly recruited onto cell-encasing and/or -free sheaths of L. cholodnii SP-6. In this study, whether this direct Fe(III adherence to sheaths also occurs in silicon-glucose-peptone (SGP medium amended with Fe(0 (SGP + Fe was investigated using another strain of Leptothrix sp., OUMS1. Preparation of SGP + Fe with Fe powder caused turbidity within a few hours due to abiotic generation of Fe(III particles via Fe(II, and the medium remained turbid until day 8. When OUMS1 was added to SGP + Fe, the turbidity of the medium cleared within 35 h as Fe(III particles adhered to sheaths. When primitive sheaths, cell-killed, cell-free, or lysozyme/EDTA/SDS- and proteinase K-treated sheath remnants were mixed with Fe(III particles, the particles immediately adhered to each. Thus, vital activity of cells was not required for the direct Fe(III particle deposition onto sheaths regardless of Leptothrix strains.

  16. Fe(III) oxides accelerate microbial nitrate reduction and electricity generation by Klebsiella pneumoniae L17.

    Science.gov (United States)

    Liu, Tongxu; Li, Xiaomin; Zhang, Wei; Hu, Min; Li, Fangbai

    2014-06-01

    Klebsiella pneumoniae L17 is a fermentative bacterium that can reduce iron oxide and generate electricity under anoxic conditions, as previously reported. This study reveals that K. pneumoniae L17 is also capable of dissimilatory nitrate reduction, producing NO2(-), NH4(+), NO and N2O under anoxic conditions. The presence of Fe(III) oxides (i.e., α-FeOOH, γ-FeOOH, α-Fe2O3 and γ-Fe2O3) significantly accelerates the reduction of nitrate and generation of electricity by K. pneumoniae L17, which is similar to a previous report regarding another fermentative bacterium, Bacillus. No significant nitrate reduction was observed upon treatment with Fe(2+) or α-FeOOH+Fe(2+), but a slight facilitation of nitrate reduction and electricity generation was observed upon treatment with L17+Fe(2+). This result suggests that aqueous Fe(II) or mineral-adsorbed Fe(II) cannot reduce nitrate abiotically but that L17 can catalyze the reduction of nitrate and generation of electricity in the presence of Fe(II) (which might exist as cell surface-bound Fe(II)). To rule out the potential effect of Fe(II) produced by L17 during microbial iron reduction, treatments with the addition of TiO2 or Al2O3 instead of Fe(III) oxides also exhibited accelerated microbial nitrate reduction and electricity generation, indicating that cell-mineral sorption did account for the acceleration effect. However, the acceleration caused by Fe(III) oxides is only partially attributed to the cell surface-bound Fe(II) and cell-mineral sorption but may be driven by the iron oxide conduction band-mediated electron transfer from L17 to nitrate or an electrode, as proposed previously. The current study extends the diversity of bacteria of which nitrate reduction and electricity generation can be facilitated by the presence of iron oxides and confirms the positive role of Fe(III) oxides on microbial nitrate reduction and electricity generation by particular fermentative bacteria in anoxic environments. Copyright

  17. Development of fluorescent FeIII sensor based on chalcone

    Energy Technology Data Exchange (ETDEWEB)

    Wei Yanli, E-mail: weiyanli@sxu.edu.cn [Research Center of Environmental Science and Engineering, Shanxi University, Taiyuan 030006 (China); Qin Guojie [Institute of Horticulture, Shanxi Academy of Agriculture Science, Taiyuan 030031 (China); Wang Wenyan; Bian Wei; Shuang Shaomin [Research Center of Environmental Science and Engineering, Shanxi University, Taiyuan 030006 (China); Dong Chuan, E-mail: dc@sxu.edu.cn [Research Center of Environmental Science and Engineering, Shanxi University, Taiyuan 030006 (China)

    2011-08-15

    In this paper, 4-dimethylamino 2,5-dihydroxy chalcone (DMADHC), which exhibits excited state intramolecular charge transfer (ICT) characteristics, was synthesized and characterized. A sensitive optochemical sensor for Fe{sup 3+} ion was developed using DMADHC as fluorescence receptor. The fluorescence of DMADHC was gradually quenched with the addition of Fe{sup 3+} ion, which attributed to the formation of 1:1 complex between DMADHC and Fe{sup 3+} ion. The sensor exhibited excellent selectivity for Fe{sup 3+} ion over a large number of cation ions such as alkali, alkaline earth and transitional metal ions with a linear range of 3.984x10{sup -7}-1.135x10{sup -5} and a limit of detection of 8.223x10{sup -8} mol/L. On this basis, the sensor was preliminary applied to the determination of the content of iron ions in multi-vitamin tablet with satisfied results and the recoveries were in the 95-100% interval, and precision (n=5) was better than 5%. - Highlights: > A fluorescence receptor, 4-dimethylamino 2,5-dihydroxy chalcone was synthesis by one-step reaction. > Its intramolecular charge transfer fluorescence characteristics could be blocked by Fe{sup 3+} ion. > Based on this, an optochemical sensor for Fe{sup 3+} ion was developed. > Importantly, our proposed method is particularly useful for determination of Fe{sup 3+} ion in real sample.

  18. Microbial Fe(III) oxide reduction potential in Chocolate Pots hot spring, Yellowstone National Park.

    Science.gov (United States)

    Fortney, N W; He, S; Converse, B J; Beard, B L; Johnson, C M; Boyd, E S; Roden, E E

    2016-05-01

    Chocolate Pots hot springs (CP) is a unique, circumneutral pH, iron-rich, geothermal feature in Yellowstone National Park. Prior research at CP has focused on photosynthetically driven Fe(II) oxidation as a model for mineralization of microbial mats and deposition of Archean banded iron formations. However, geochemical and stable Fe isotopic data have suggested that dissimilatory microbial iron reduction (DIR) may be active within CP deposits. In this study, the potential for microbial reduction of native CP Fe(III) oxides was investigated, using a combination of cultivation dependent and independent approaches, to assess the potential involvement of DIR in Fe redox cycling and associated stable Fe isotope fractionation in the CP hot springs. Endogenous microbial communities were able to reduce native CP Fe(III) oxides, as documented by most probable number enumerations and enrichment culture studies. Enrichment cultures demonstrated sustained DIR driven by oxidation of acetate, lactate, and H2 . Inhibitor studies and molecular analyses indicate that sulfate reduction did not contribute to observed rates of DIR in the enrichment cultures through abiotic reaction pathways. Enrichment cultures produced isotopically light Fe(II) during DIR relative to the bulk solid-phase Fe(III) oxides. Pyrosequencing of 16S rRNA genes from enrichment cultures showed dominant sequences closely affiliated with Geobacter metallireducens, a mesophilic Fe(III) oxide reducer. Shotgun metagenomic analysis of enrichment cultures confirmed the presence of a dominant G. metallireducens-like population and other less dominant populations from the phylum Ignavibacteriae, which appear to be capable of DIR. Gene (protein) searches revealed the presence of heat-shock proteins that may be involved in increased thermotolerance in the organisms present in the enrichments as well as porin-cytochrome complexes previously shown to be involved in extracellular electron transport. This analysis offers

  19. Perfluorooctanoic acid degradation in the presence of Fe(III) under natural sunlight

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Dandan [Beijing Key Laboratory of Water Resource and Environmental Engineering, China University of Geosciences, Beijing 100083 (China); Xiu, Zongming [Department of Civil and Environmental Engineering, Rice University, Houston, TX 77005 (United States); Liu, Fei [Beijing Key Laboratory of Water Resource and Environmental Engineering, China University of Geosciences, Beijing 100083 (China); Wu, Gang [Division of Hematology, Department of Internal Medicine, University of Texas-Medical School at Houston, Houston, TX 77030 (United States); Adamson, Dave; Newell, Charles [GSI Environmental Inc., Houston, TX 77098 (United States); Vikesland, Peter [Department of Civil and Environmental Engineering, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061 (United States); Tsai, Ah-Lim [Division of Hematology, Department of Internal Medicine, University of Texas-Medical School at Houston, Houston, TX 77030 (United States); Alvarez, Pedro J., E-mail: alvarez@rice.edu [Department of Civil and Environmental Engineering, Rice University, Houston, TX 77005 (United States)

    2013-11-15

    Highlights: • PFOA was photo-chemically decomposed in the presence of Fe(III) and natural sunlight. • An alternative reaction pathway involves hydroxyl radical as confirmed by EPR. • Common oxidant-persulfate increased PFOA defluorination extent. -- Abstract: Due to the high bond dissociation energy (BDE) of C-F bonds (116 kcal/mol), perfluorooctanoic acid (PFOA) is a highly recalcitrant pollutant. Herein, we demonstrate a novel method to decompose PFOA in the presence of sunlight and ferric iron (Fe(III)). Under such conditions, 97.8 ± 1.7% of 50 μM PFOA decomposed within 28 days into shorter-chain intermediates and fluoride (F{sup −}), with an overall defluorination extent of 12.7 ± 0.5%. No PFOA was removed under visible light, indicating that UV radiation is required for PFOA decomposition. Spectroscopic analysis indicates that the decomposition reaction is likely initiated by electron-transfer from PFOA to Fe(III), forming Fe(II) and an unstable organic carboxyl radical. An alternative mechanism for the formation of this organic radical involves hydroxyl radicals, detected by electron paramagnetic resonance (EPR). The observation that PFOA can be degraded by Fe(III) under solar irradiation provides mechanistic insight into a possibly overlooked natural attenuation process. Because Fe(III) is abundant in natural waters and sunlight is essentially free, this work represents a potentially important step toward the development of simple and inexpensive remediation strategies for PFOA-contaminated water.

  20. REGULARITIES OF QUANTITATIVE DISTRIBUTION FOR FE(III-REDUCING BACTERIA IN NATURAL ECOSYSTEMS

    Directory of Open Access Journals (Sweden)

    Govorukha V. M.

    2015-08-01

    Full Text Available The aim of the work was quantitative determination of Fe(III-reducing bacteria in natural ecosystems of the Antarctic, the Arctic, the Dead and the Black Sea, middle latitude (Ukraine, Abkhazia and the equatorial zone (Ecuador. It was used the method of quantitative determination of microorganisms by McCready and the colorimetric method for determination of Fe(II compounds . Results. The systemic study of the number of Fe(III-reducing bacteria of both hemispheres in the ecosystems of six geographic regions was carried out for the first time. High number of Fe(III-reducing bacteria in natural ecosystems was experimentally shown. The number of Fe(III-reducing bacteria ranged from 1.1•102 to 2.8•107 cells/g of absolutely dry sample. Conclusions. The presented data showed that Fe(III-reducing bacteria are an integral part of natural ecosystems and can significantly affect the biogeochemical cycles of iron and carbon compounds transformation.

  1. Shewanella oneidensis MR-1-Induced Fe(III) Reduction Facilitates Roxarsone Transformation

    Science.gov (United States)

    Chen, Guowei; Ke, Zhengchen; Liang, Tengfang; Liu, Li; Wang, Gang

    2016-01-01

    Although microbial activity and associated iron (oxy)hydroxides are known in general to affect the environmental dynamics of 4-hydroxy-3-nitrobenzenearsonic acid (roxarsone), the mechanistic understanding of the underlying biophysico-chemical processes remains unclear due to limited experimental information. We studied how Shewanella oneidensis MR-1 –a widely distributed metal-reducing bacterium, in the presence of dissolved Fe(III), affects roxarsone transformations and biogeochemical cycling in a model aqueous system. The results showed that the MR-1 strain was able to anaerobically use roxarsone as a terminal electron acceptor and to convert it to a single product, 3-amino-4-hydroxybenzene arsonic acid (AHBAA). The presence of Fe(III) stimulated roxarsone transformation via MR-1-induced Fe(III) reduction, whereby the resulting Fe(II) acted as an efficient reductant for roxarsone transformation. In addition, the subsequent secondary Fe(III)/Fe(II) mineralization created conditions for adsorption of organoarsenic compounds to the yielded precipitates and thereby led to arsenic immobilization. The study provided direct evidence of Shewanella oneidensis MR-1-induced direct and Fe(II)-associated roxarsone transformation. Quantitative estimations revealed a candidate mechanism for the early-stage environmental dynamics of roxarsone in nature, which is essential for understanding the environmental dynamics of roxarsone and successful risk assessment. PMID:27100323

  2. Shewanella oneidensis MR-1-Induced Fe(III) Reduction Facilitates Roxarsone Transformation.

    Science.gov (United States)

    Chen, Guowei; Ke, Zhengchen; Liang, Tengfang; Liu, Li; Wang, Gang

    2016-01-01

    Although microbial activity and associated iron (oxy)hydroxides are known in general to affect the environmental dynamics of 4-hydroxy-3-nitrobenzenearsonic acid (roxarsone), the mechanistic understanding of the underlying biophysico-chemical processes remains unclear due to limited experimental information. We studied how Shewanella oneidensis MR-1 -a widely distributed metal-reducing bacterium, in the presence of dissolved Fe(III), affects roxarsone transformations and biogeochemical cycling in a model aqueous system. The results showed that the MR-1 strain was able to anaerobically use roxarsone as a terminal electron acceptor and to convert it to a single product, 3-amino-4-hydroxybenzene arsonic acid (AHBAA). The presence of Fe(III) stimulated roxarsone transformation via MR-1-induced Fe(III) reduction, whereby the resulting Fe(II) acted as an efficient reductant for roxarsone transformation. In addition, the subsequent secondary Fe(III)/Fe(II) mineralization created conditions for adsorption of organoarsenic compounds to the yielded precipitates and thereby led to arsenic immobilization. The study provided direct evidence of Shewanella oneidensis MR-1-induced direct and Fe(II)-associated roxarsone transformation. Quantitative estimations revealed a candidate mechanism for the early-stage environmental dynamics of roxarsone in nature, which is essential for understanding the environmental dynamics of roxarsone and successful risk assessment.

  3. Molar Absorptivity and Quantum Yield of Fe(II) Photo-formation for the Aqueous Solutions of Fe(III)-Dicarboxylate Comlexes

    Science.gov (United States)

    Hitomi, Y.; Arakaki, T.

    2009-04-01

    Fe(III)/Fe(II) cycle in the environment affects formation of active oxygen species such as hydrogen peroxide and hydroxyl radicals, which in turn determines lifetimes of many organic compounds. Although aqueous Fe(III)-dicarboxylate complexes are considered to be an important source of photo-chemically formed Fe(II), molar absorptivity and quantum yield of Fe(II) formation for individual species are not well understood. The Visual MINTEQ computer program was used to calculate the equilibrium concentrations of individual Fe(III)-dicarboxylate species in the aqueous solutions of Fe(III)-dicarboxylate complexes. The molar absorptivity and the product of the quantum yield and the molar absorptivity of Fe(III)-dicarboxylate species were obtained by UV-VIS spectrophotometer and photochemical experiments, and these experimental data were combined with the calculated equilibrium Fe(III)-dicarboxylate concentrations to determine individual molar absorptivity and quantum yield of Fe(II) photo-formation for a specific Fe(III)-dicarboxylate species. Dicarboxylate compounds studied were oxalate, malonate, succinate, malate, and phthalate.

  4. Trineodymium(III pentairon(III dodecaoxide, Nd3Fe5O12

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    Takashi Komori

    2009-10-01

    Full Text Available The title compound, Nd3Fe5O12 (NdIG, has an iron garnet structure. One of the Fe atoms is coordinated by six O atoms in a slightly distorted octahedral geometry and has overline{3} site symmetry. The other Fe atom is coordinated by four O atoms in a slightly distorted tetrahedral geometry and has overline{4} site symmetry. The FeO6 octahedron and FeO4 tetrahedron are linked together by corners. The Nd atom is coordinated by eight O atoms in a distorted dodecahedral geometry and has 222 site symmetry. The O atoms occupy general positions.

  5. Interaction of human serum albumin with Fe(III)–deferasirox studied by multispectroscopic methods

    Energy Technology Data Exchange (ETDEWEB)

    Dehghan, Gholamreza, E-mail: dehghan2001d@yahoo.com [Department of Biology, Faculty of Natural Science, University of Tabriz, Tabriz (Iran, Islamic Republic of); Shaghaghi, Masoomeh [Department of Chemistry, Payame Noor University, PO Box 19395-3697 Tehran, I.R. of Iran (Iran, Islamic Republic of); Sattari, Safura [Islamic Azad University, Science and Research Branch, Tehran (Iran, Islamic Republic of); Jouyban, Abolghasem [Drug Applied Research Center and Faculty of Pharmacy, Tabriz University of Medical Sciences, Tabriz 51664 (Iran, Islamic Republic of)

    2014-05-01

    The interaction between the iron complex of deferasirox (Fe(III)–DFX) and human serum albumin (HSA) was studied by fluorescence, UV–vis absorption and circular dichroism (CD) spectroscopy. Binding constants, number of binding sites and binding distance (r) were calculated. Fluorescence data at different temperatures revealed that the fluorescence intensity of HSA is decreased in the presence of Fe(III)–DFX complex, and the fluorescence quenching was the result of the formation of the Fe(III)–DFX–HSA complex, therefore the quenching mechanism was static. The binding constant (K{sub a}) for the interaction was 10{sup 4}, and the number of binding site was obtained ∼1. The thermodynamic parameters including enthalpy (∆H), entropy (∆S) and Gibb's free energy (∆G) changes were calculated according to the van't Hoff equation. These data suggested that hydrophobic interaction was the dominant intermolecular force in stabilizing the complex and the association process was spontaneous. The interaction of HSA with Fe(III)–DFX was also confirmed by UV–vis absorption spectra. The quantitative analysis data of CD spectra showed significant alterations of HSA secondary structure in the presence of Fe(III)–DFX complex in aqueous solution with reduction of α-helices content and increase of β-turn structure. - Highlights: • The interaction between Fe(III)–DFX and (HSA) was studied by multispectroscopic methods. • Fluorescence intensity of HSA is decreased in the presence of Fe(III)–DFX complex through a static quenching procedure. • Thermodynamic data suggested that hydrophobic interaction was the dominant intermolecular force and the association process was spontaneous. • The CD spectra showed significant alterations of HSA secondary structure with reduction of α-helices content and increase of β-turn structure.

  6. Structural and electrical properties of Ni{sub 1-x}Mg{sub x}Fe{sub 2}O{sub 4} synthesized by citrate gel process

    Energy Technology Data Exchange (ETDEWEB)

    John Berchmans, L.; Kalai Selvan, R.; Selva Kumar, P.N.; Augustin, C.O. E-mail: caugustin@rediffmail.com

    2004-08-01

    The structural and electrical properties of magnesium-substituted nickel ferrite having the general formula of Ni{sub 1-x}Mg{sub x}Fe{sub 2}O{sub 4} (x=0, 0.3, 0.6, 0.9) has been studied as a function of magnesium ion concentration. The materials have been prepared by citrate gel process using metal nitrate salts as a cation precursors and citric acid as gelating agent. The powder X-ray diffraction pattern confirms fcc structure for the synthesized compound. The variation of lattice parameter and the tetrahedral radius increases with increase in Mg{sup 2+} ion concentration. The AC electrical parameters such as dielectric constant ({epsilon}') and loss tangent (tan {delta}) for all the systems have been studied as a function of frequency in the range 50 Hz to 10 kHz at room temperature. A maximum DC electrical conductivity of 3.3 S cm{sup -1} was obtained at a temperature of 1000 deg. C and a AC electrical conductivity of 10.94x10{sup -6}at 10 kHz was observed in the composition x=0.6 i.e. for Ni{sub 0.4}Mg{sub 0.6}Fe{sub 2}O{sub 4} compound which may be due to the maximum Fe{sup 2+} concentration in the octahedral sites. The dielectric constant follows the Maxwell's-Wagner interfacial polarization and the relaxation peaks were observed in the dielectric loss properties. The FTIR spectra show the characteristic peaks of ferrite sample. The morphological features were studied using scanning electron microscope.

  7. Effect of Iron Fe (II and Fe (III in a Binary System Evaluated Bioluminescent Method

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    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.

  8. Selection of Chelated Fe (III)/Fe (II) Catalytic Oxidation Agents for Desulfurization Based on Iron Complexation Method

    Institute of Scientific and Technical Information of China (English)

    Luo Ying; Liu Youzhi; Qi Guisheng; Guo Huidong; Zhu Zhengfeng

    2014-01-01

    Optimization of factors inlfuencing the experiments on reactions involving 8 different chelating agents and sol-uble Fe (III)/Fe (II) salts was carried out to yield chelated iron complexes. A combination of optimized inlfuencing factors has resulted in a Fe chelating capacity of the iron-based desulfurization solution to be equal to 6.83—13.56 g/L at a redox potential of 0.185—0.3. The desulfurization performance of Fe (III)/Fe (II) chelating agents was investigated on a simulated sulfur-containing industrial gas composed of H2S and N2 in a cross-lfow rotating packed bed. Test results have revealed that the proposed iron-based desulfurization solution showed a sulfur removal efifciency of over 99%along with a Fe chelating capacity exceeding 1.35 g/L. This desulfurization technology which has practical application prospect is currently in the phase of commercial scale-up study.

  9. Peptide-based FeS4 complexes: the zinc ribbon fold is unsurpassed to stabilize both the FeII and FeIII states.

    Science.gov (United States)

    Jacques, Aurélie; Latour, Jean-Marc; Sénèque, Olivier

    2014-03-14

    Whereas Zn(Cys)4 zinc fingers exist with different protein folds, only the zinc ribbon fold is found in rubredoxin Fe(Cys)4 sites. To assess the significance of this observation, we have investigated the binding and stability of Fe(2+) and Fe(3+) ions by a set of four peptides designed to model Zn(Cys)4 zinc fingers with various folds, i.e. zinc ribbon, treble clef and a loosened zinc ribbon fold. All peptides were shown by means of UV-Vis and CD spectroscopies to form stable 1 : 1 Fe(II)/peptide complexes with binding constants higher than 10(7) M(-1) at pH 7. Their oxidation into Fe(III) complexes and the stability of the latter were compared. The UV-Vis absorption and CD spectroscopic properties of the Fe(II) and Fe(III) complexes were analysed with respect to the structures of the zinc analogues in order to get insight into the local arrangement of the Fe(Cys)4 core around the metal ion. The chemical stability of these complexes was rationalized according to the shielding from the solvent provided by the various peptide folds to the FeS4 core. In addition, we showed that whereas UV-visible spectra inform only on the FeS4, the information derived from the corresponding CD spectra extend to the Cβ orientation and the peptide fold. The results presented here demonstrate that while the zinc ribbon fold is not strictly required to obtain a Fe(Cys)4 site, it affords a drastically superior protection of the site toward external redox agents. This finding brings new clues to engineer stable and redox-active Fe(Cys)4 sites in de novo proteins.

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

    Science.gov (United States)

    Du, Gaoxiang; Li, Zhaohui; Liao, Libing; Hanson, Renee; Leick, Samantha; Hoeppner, Nicole; Jiang, Wei-Teh

    2012-06-30

    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 1.4-2.4mm 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 82mg/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 3mg/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. Copyright © 2012 Elsevier B.V. All rights reserved.

  11. Synthesis and Structural Studies of Cr(III, Mn(II and Fe(III Complexes of N(2-Benzimidazolylacetylacetohydrazone

    Directory of Open Access Journals (Sweden)

    G. H. Anuradha

    2011-01-01

    Full Text Available The ligand N(2-benzimidazolylacetylacetohydrazone (BAAH have been synthesized and characterized. Coordination complexes of Cr(III, Mn(II and Fe(III have been synthesized with the ligand BAAH. These complexes were characterized on the basis of analytical, conductance, thermal, magnetic data and infrared and electronic spectral data. The ligand BAAH is behaving as a neutral tridentate NNO donar employing two azomethine nitrogens (ring and side chain and carbonyl oxygen. The ligand and it's metal complexes were tested for anti microbial activity on the gram positive S. Aureus, E. coli and Proteus.

  12. Reactive iron(III) in sediments: Chemical versus microbial extractions

    Science.gov (United States)

    Hyacinthe, C.; Bonneville, S.; Van Cappellen, P.

    2006-08-01

    The availability of particulate Fe(III) to iron reducing microbial communities in sediments and soils is generally inferred indirectly by performing chemical extractions. In this study, the bioavailability of mineral-bound Fe(III) in intertidal sediments of a eutrophic estuary is assessed directly by measuring the kinetics and extent of Fe(III) utilization by the iron reducing microorganism Shewanella putrefaciens, in the presence of excess electron donor. Microbial Fe(III) reduction is compared to chemical dissolution of iron from the same sediments in buffered ascorbate-citrate solution (pH 7.5), ascorbic acid (pH 2), and 1 M HCl. The results confirm that ascorbate at near-neutral pH selectively reduces the reactive Fe(III) pool, while the acid extractants mobilize additional Fe(II) and less reactive Fe(III) mineral phases. Furthermore, the maximum concentrations of Fe(III) reducible by S. putrefaciens correlate linearly with the iron concentrations extracted by buffered ascorbate-citrate solution, but not with those of the acid extractions. However, on average, only 65% of the Fe(III) reduced in buffered ascorbate-citrate solution can be utilized by S. putrefaciens, probably due to physical inaccessibility of the remaining fraction of reactive Fe(III) to the cells. While the microbial and abiotic reaction kinetics further indicate that reduction by ascorbate at near-neutral pH most closely resembles microbial reduction of the sediment Fe(III) pool by S. putrefaciens, the results also highlight fundamental differences between chemical reductive dissolution and microbial utilization of mineral-bound ferric iron.

  13. Studies on Synthetic and Natural Melanin and Its Affinity for Fe(III Ion

    Directory of Open Access Journals (Sweden)

    T. G. Costa

    2012-01-01

    Full Text Available In this work, we measured the metal-binding sites of natural and synthetic dihydroxyindole (DHI melanins and their respective interactions with Fe(III ions. Besides the two acid groups detected for the DHI system: catechol (Cat and quinone-imine (QI, acetate groups were detected in the natural oligomer by potentiometric titrations. At acidic pH values, Fe(III complexation with synthetic melanin was detected in an Fe(OH(CatH2Cat interaction. With an increase of pH, three new interactions occurred: dihydroxide diprotonated catechol, Fe(OH2(CatH2Cat−, dihydroxide monoprotonated catechol, [Fe(OH2(CatHCat]2−, and an interaction resulting from the association of one quinone-imine and a catechol group, [Fe(OH2(Qi−(CatHCat]3−. In the natural melanin system, we detected the same interactions involving catechol and quinone-imine groups but also the metal interacts with acetate group at pH values lower than 4.0. Furthermore, interactions in the synthetic system were also characterized by infrared spectroscopy by using the characteristic vibrations of catechol and quinone-imine groups. Finally, scanning electronic microscopy (SEM and energy-dispersive X-ray (EDS analysis were used to examine the differences in morphology of these two systems in the absence and presence of Fe(III ions. The mole ratio of metal and donor atoms was obtained by the EDS analysis.

  14. Study on the process of Fe (III) oxide fluorination

    Science.gov (United States)

    Sophronov, V. L.; Kalaev, M. E.; Makaseev, Yu N.; Sachkov, V. I.; Verkhoturova, V. V.

    2016-02-01

    The article deals with a fundamentally new fluoride technology for obtaining fluoride materials, provides data on the kinetics of the process of fluorination of Fe oxide with fluorine, fluoride and ammonium bifluoride. The physical and chemical properties of obtained fluorides are shown: a study of the elemental composition, grain-size composition using the method of scanning electron microscopy and laser diffraction.

  15. Acid-tolerant microaerophilic Fe(II)-oxidizing bacteria promote Fe(III)-accumulation in a fen.

    Science.gov (United States)

    Lüdecke, Claudia; Reiche, Marco; Eusterhues, Karin; Nietzsche, Sandor; Küsel, Kirsten

    2010-10-01

    The ecological importance of Fe(II)-oxidizing bacteria (FeOB) at circumneutral pH is often masked in the presence of O(2) where rapid chemical oxidation of Fe(II) predominates. This study addresses the abundance, diversity and activity of microaerophilic FeOB in an acidic fen (pH ∼ 5) located in northern Bavaria, Germany. Mean O(2) penetration depth reached 16 cm where the highest dissolved Fe(II) concentrations (up to 140 µM) were present in soil water. Acid-tolerant FeOB cultivated in gradient tubes were most abundant (10(6) cells g(-1) peat) at the 10-20 cm depth interval. A stable enrichment culture was active at up to 29% O(2) saturation and Fe(III) accumulated 1.6 times faster than in abiotic controls. An acid-tolerant, microaerophilic isolate (strain CL21) was obtained which was closely related to the neutrophilic, lithoautotrophic FeOB Sideroxydans lithotrophicus strain LD-1. CL21 oxidized Fe(II) between pH 4 and 6.0, and produced nanoscale-goethites with a clearly lower mean coherence length (7 nm) perpendicular to the (110) plane than those formed abiotically (10 nm). Our results suggest that an acid-tolerant population of FeOB is thriving at redox interfaces formed by diffusion-limited O(2) transport in acidic peatlands. Furthermore, this well-adapted population is successfully competing with chemical oxidation and thereby playing an important role in the microbial iron cycle.

  16. 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.

  17. 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.

  18. 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.

  19. Stimulated anoxic biodegradation of aromatic hydrocarbons using Fe(III) ligands

    Science.gov (United States)

    Lovley, D.R.; Woodward, J.C.; Chapelle, F.H.

    1994-01-01

    Contamination of ground waters with water-soluble aromatic hydrocarbons, common components of petroleum pollution, often produces anoxic conditions under which microbial degradation of the aromatics is slow. Oxygen is often added to contaminated ground water to stimulate biodegradation, but this can be technically difficult and expensive. Insoluble Fe(III) oxides, which are generally abundant in shallow aquifers, are alternative potential oxidants, but are difficult for microorganisms to access. Here we report that adding organic ligands that bind to Fe(III) dramatically increases its bioavailability, and that in the presence of these ligands, rates of degradation of aromatic hydrocarbons in anoxic aquifer sediments are comparable to those in oxic sediments. We find that even benzene, which is notoriously refractory in the absence of oxygen, can be rapidly degraded. Our results suggest that increasing the bioavailability of Fe(III) by adding suitable ligands provides a potential alternative to oxygen addition for the bioremediation of petroleum-contaminated aquifers.Contamination of ground waters with water-soluble aromatic hydrocarbons, common components of petroleum pollution, often produces anoxic conditions under which microbial degradation of the aromatics is slow. Oxygen is often added to contaminated ground water to stimulate biodegradation, but this can be technically difficult and expensive. Insoluble Fe(III) oxides, which are generally abundant in shallow aquifers, are alternative potential oxidants, but are difficult for microorganisms to access. Here we report that adding organic ligands that bind to Fe(III) dramatically increases its bioavailability, and that in the presence of these ligands, rates of degradation of aromatic hydrocarbons in anoxic aquifer sediments are comparable to those in oxic sediments. We find that even benzene, which is notoriously refractory in the absence of oxygen, can be rapidly degraded. Our results suggest that increasing

  20. 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.

  1. Enhanced reduction of Fe(III) oxides and methyl orange by Klebsiella oxytoca in presence of anthraquinone-2-disulfonate.

    Science.gov (United States)

    Yu, Lei; Wang, Shi; Tang, Qing-Wen; Cao, Ming-Yue; Li, Jia; Yuan, Kun; Wang, Ping; Li, Wen-Wei

    2016-05-01

    Klebsiella oxytoca GS-4-08 is capable of azo dye reduction, but its quinone respiration and Fe(III) reduction abilities have not been reported so far. In this study, the abilities of this strain were reported in detail for the first time. As the biotic reduction of Fe(III) plays an important role in the biogeochemical cycles, two amorphous Fe(III) oxides were tested as the sole electron acceptor during the anaerobic respiration of strain GS-4-08. For the reduction of goethite and hematite, the biogenic Fe(II) concentrations reached 0.06 and 0.15 mM, respectively. Humic acid analog anthraquinone-2-disulfonate (AQS) was found to serve as an electron shuttle to increase the reduction of both methyl orange (MO) and amorphous Fe(III) oxides, and improve the dye tolerance of the strain. However, the formation of Fe(II) was not accelerated by biologically reduced AQS (B-AH2QS) because of the high bioavailability of soluble Fe(III). For the K. oxytoca strain, high soluble Fe(III) concentrations (above 1 mM) limit its growth and decolorization ability, while lower soluble Fe(III) concentrations produce an electron competition with MO initially, and then stimulate the decolorization after the electron couples of Fe(III)/Fe(II) are formed. With the ability to respire both soluble Fe(III) and insoluble Fe(III) oxides, this formerly known azo-reducer may be used as a promising model organism for the study of the interaction of these potentially competing processes in contaminated environments.

  2. Geochemical control of microbial Fe(III) reduction potential in wetlands: Comparison of the rhizosphere to non-rhizosphere soil

    Science.gov (United States)

    Weiss, J.V.; Emerson, D.; Megonigal, J.P.

    2004-01-01

    We compared the reactivity and microbial reduction potential of Fe(III) minerals in the rhizosphere and non-rhizosphere soil to test the hypothesis that rapid Fe(III) reduction rates in wetland soils are explained by rhizosphere processes. The rhizosphere was defined as the area immediately adjacent to a root encrusted with Fe(III)-oxides or Fe plaque, and non-rhizosphere soil was 0.5 cm from the root surface. The rhizosphere had a significantly higher percentage of poorly crystalline Fe (66??7%) than non-rhizosphere soil (23??7%); conversely, non-rhizosphere soil had a significantly higher proportion of crystalline Fe (50??7%) than the rhizosphere (18??7%, Psoil Fe(III)-oxide pool. Similarly, microbial reduction consumed 75-80% of the rhizosphere pool in 10 days compared to 30-40% of the non-rhizosphere soil pool. Differences between the two pools persisted when samples were amended with an electron-shuttling compound (AQDS), an Fe(III)-reducing bacterium (Geobacter metallireducens), and organic carbon. Thus, Fe(III)-oxide mineralogy contributed strongly to differences in the Fe(III) reduction potential of the two pools. Higher amounts of poorly crystalline Fe(III) and possibly humic substances, and a higher Fe(III) reduction potential in the rhizosphere compared to the non-rhizosphere soil, suggested the rhizosphere is a site of unusually active microbial Fe cycling. The results were consistent with previous speculation that rapid Fe cycling in wetlands is due to the activity of wetland plant roots. ?? 2004 Federation of European Microbiological Societies. Published by Elsevier B.V. All rights reserved.

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

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    Ramazan GÜRKAN

    2013-12-01

    Full Text Available 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-1 was 0.06 μg L-1. The relative standard deviation was 2.7 % (20 μg L-1, N: 5, recoveries for Fe(II were in range of 99.0-102.0% 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.

  4. 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.

  5. Molecular Underpinnings of Fe(III) Oxide Reduction by Shewanella Oneidensis MR-1

    Science.gov (United States)

    Shi, Liang; Rosso, Kevin M.; Clarke, Tomas A.; Richardson, David J.; Zachara, John M.; Fredrickson, James K.

    2012-01-01

    In the absence of O2 and other electron acceptors, the Gram-negative bacterium Shewanella oneidensis MR-1 can use ferric [Fe(III)] (oxy)(hydr)oxide 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 and related strains of metal-reducing Shewanella have evolved machinery (i.e., metal-reducing or Mtr pathway) for transferring electrons from the inner-membrane, through the periplasm and across the outer-membrane 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 belongs to the NapC/NrfH family of quinol dehydrogenases. It is proposed that CymA oxidizes the quinol in the inner-membrane and transfers the released electrons to MtrA either directly or indirectly through other periplasmic proteins. 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 through the outer-membrane to the MtrC and OmcA on the outmost bacterial surface. MtrC and OmcA are the outer-membrane decaheme c-Cyts that are translocated across the outer-membrane by the bacterial type II secretion system. Functioning as terminal reductases, MtrC and OmcA can bind the surface of Fe(III) oxides and transfer electrons directly to these minerals via their solvent-exposed hemes. 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. Because of their extracellular location and broad redox potentials, MtrC and OmcA can also serve as the terminal reductases for soluble forms of Fe(III). In addition to Fe(III) oxides, Mtr pathway is also involved in reduction of

  6. Heterogeneous photo-Fenton degradation of polyacrylamide in aqueous solution over Fe(III)-SiO(2) catalyst.

    Science.gov (United States)

    Liu, Ting; You, Hong; Chen, Qiwei

    2009-03-15

    This article presents preparation, characterization and evaluation of heterogeneous Fe(III)-SiO(2) catalysts for the photo-Fenton degradation of polyacrylamide (PAM) in aqueous solution. Fe(III)-SiO(2) catalysts are prepared by impregnation method with two iron salts as precursors, namely Fe(NO(3))(3) and FeSO(4), and are characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) methods. The irradiated Fe(III)-SiO(2) is complexed with 1,10-phenanthroline, then is measured by UV-vis-diffuse reflectance spectroscopy (UV-vis-DRS) and XPS to confirm the oxidation state of Fe in solid state. By investigating the photo-Fenton degradation of PAM in aqueous solution, the results indicate that Fe(III)-SiO(2) catalysts exhibit an excellent photocatalytic activity in the degradation of PAM. Moreover, the precursor species and the OH(-)/Fe mole ratio affect the photocatalytic activity of Fe(III)-SiO(2) catalysts to a certain extent. Finally, the amount of Fe ions leaching from the Fe(III)-SiO(2) catalysts is much low.

  7. Heterogeneous photo-Fenton degradation of polyacrylamide in aqueous solution over Fe(III)-SiO{sub 2} catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Liu Ting [Department of Environmental Science and Engineering, Harbin Institute of Technology, P.O. Box 2606, 202 Haihe Road, Harbin 150090 (China); You Hong [Department of Environmental Science and Engineering, Harbin Institute of Technology, P.O. Box 2606, 202 Haihe Road, Harbin 150090 (China)], E-mail: youhong@hit.edu.cn; Chen Qiwei [Department of Environmental Science and Engineering, Harbin Institute of Technology, P.O. Box 2606, 202 Haihe Road, Harbin 150090 (China)

    2009-03-15

    This article presents preparation, characterization and evaluation of heterogeneous Fe(III)-SiO{sub 2} catalysts for the photo-Fenton degradation of polyacrylamide (PAM) in aqueous solution. Fe(III)-SiO{sub 2} catalysts are prepared by impregnation method with two iron salts as precursors, namely Fe(NO{sub 3}){sub 3} and FeSO{sub 4}, and are characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) methods. The irradiated Fe(III)-SiO{sub 2} is complexed with 1,10-phenanthroline, then is measured by UV-vis-diffuse reflectance spectroscopy (UV-vis-DRS) and XPS to confirm the oxidation state of Fe in solid state. By investigating the photo-Fenton degradation of PAM in aqueous solution, the results indicate that Fe(III)-SiO{sub 2} catalysts exhibit an excellent photocatalytic activity in the degradation of PAM. Moreover, the precursor species and the OH{sup -}/Fe mole ratio affect the photocatalytic activity of Fe(III)-SiO{sub 2} catalysts to a certain extent. Finally, the amount of Fe ions leaching from the Fe(III)-SiO{sub 2} catalysts is much low.

  8. 21 CFR 184.1296 - Ferric ammonium citrate.

    Science.gov (United States)

    2010-04-01

    ... citrate (iron (III) ammonium citrate) is prepared by the reaction of ferric hydroxide with citric acid, followed by treatment with ammonium hydroxide, evaporating, and drying. The resulting product occurs in two forms depending on the stoichiometry of the initial reactants. (1) Ferric ammonium citrate (iron...

  9. Bioavailability of Fe(III) in Loess Sediments: An Important Source of Electron Acceptors

    Energy Technology Data Exchange (ETDEWEB)

    Bishop, Michael E.; Jaisi, Deb P.; Dong, Hailiang; Kukkadapu, Ravi K.; Ji, Junfeng

    2010-08-01

    A quantitative study was conducted to understand if Fe (III) in loess sediments is available for microbial respiration by using a common metal reducing bacterium, Shewanella putrefaciens, CN32. The loess samples were collected from three different sites: St. Louis (Peoria), Missouri, USA; Huanxia (HX) and Yanchang (YCH), Shanxi Province of China. Wet chemical analyses indicated that the total Fe concentration for the three samples was 1.69%, 2.76%, and 3.29%, respectively, of which 0.48%, 0.67%, and 1.27% was Fe(III). All unreduced loess sediments contained iron oxides and phyllosilicates (smectite, illite, chlorite, vermiculite), in addition to common minerals such as quartz, feldspar, plagioclase, calcite, and dolomite. Bioreduction experiments were performed at a loess concentration of 20 mg/mL using lactate as the sole electron donor, Fe(III) in loess as the sole electron acceptor in the presence and absence of anthraquinone-2, 6-disulfonate (AQDS) as an electron shuttle. Experiments were performed in non-growth (bicarbonate buffer) and growth (M1) media with a cell concentration of ~2.8 x 107 and 2.1 x 107 cells/mL, respectively. The unreduced and bioreduced solids were analyzed by X-ray diffraction (XRD), Mössbauer spectroscopy, diffuse reflection spectroscopy (DRS), and scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) methods. Despite many similarities among the three loess samples, the extent and rate of Fe (III) reduction varied significantly. For example, in presence of AQDS the extent of reduction in the non-growth experiment was 25% in HX, 34% in Peoria, and 38% in YCH. The extent of reduction in the growth experiment was 72% in HX, 94% in Peoria, and 56% in YCH. The extent of bioreduction was lower in absence of AQDS. Overall, AQDS and the M1 growth medium significantly enhanced the rate and extent of bioreduction. Fe(III) in iron oxides and Fe(III)-containing phyllosilicates was bioreduced. Biogenic illite, siderite, and

  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. Comparative Effects of Electron Transfer Mediators on the Bioreduction of Fe(III) Oxide

    Science.gov (United States)

    O'Loughlin, E. J.

    2007-12-01

    The transfer of electrons from microbes to sparingly-soluble, extracellular electron acceptors such as Fe(III) oxides can occur via direct contact with the mineral surface, by dissolution of the mineral facilitated by exogenous or endogenous ligands and subsequent reduction of the dissolved Fe(III) ligand complex, and by facilitated electron transfer involving endogenous or exogenous electron transfer mediators (ETMs, also commonly referred to as electron shuttles) that are reduced by the microbes and then subsequently diffuse away from the cell and transfer electrons to the Fe(III) mineral surface, regenerating the oxidized form of the ETM. This study examines the effects of a series of compounds representing major classes of natural and synthetic organic ETMs (including low molecular-mass quinones, humic substances, phenazines, phenoxazines, phenothiazines, and indigo derivatives) on the bioreduction of lepidocrocite (γ-FeOOH) by the dissimilatory Fe(III)-reducing bacterium Shewanella putrefaciens CN32. S. putrefaciens CN32 was able to reduce lepidocrocite in the absence of exogenous ETMs; however, relative to the control, all of the synthetic ETMs examined in this study enhanced the bioreduction of lepidocrocite. The extent of the enhanced bioreduction increased with decreasing reduction potential of the given ETM redox couple. However, the addition of Suwannee River fulvic acid, humic acid, or unfractionated NOM (10 mg organic C L-1) resulted in, at best, a minimal enhancement of lepidocrocite bioreduction relative to the control that did not contain any added exdogenous ETM. These results suggest that the relative contribution of humic substances to microbially mediated Fe(III) reduction may be minimal in low-carbon environments such as oligotrophic lakes and typical groundwaters.

  12. Nanosheets of Two-Dimensional Magnetic and Conducting Fe(II)/Fe(III) Mixed-Valence Metal-Organic Frameworks.

    Science.gov (United States)

    Benmansour, Samia; Abhervé, Alexandre; Gómez-Claramunt, Patricia; Vallés-García, Cristina; Gómez-García, Carlos J

    2017-08-09

    We report the synthesis, magnetic properties, electrical conductivity, and delamination into thin nanosheets of two anilato-based Fe(II)/Fe(III) mixed-valence two-dimensional metal-organic frameworks (MOFs). Compounds [(H3O)(H2O)(phenazine)3][Fe(II)Fe(III)(C6O4X2)3]·12H2O [X = Cl (1) and Br (2)] present a honeycomb layered structure with an eclipsed packing that generates hexagonal channels containing the water molecules. Both compounds show ferrimagnetic ordering at ca. 2 K coexisting with electrical conductivity (with room temperature conductivities of 0.03 and 0.003 S/cm). Changing the X group from Cl to Br leads to a decrease in the ordering temperature and room temperature conductivity that is correlated with the decrease of the electronegativity of X. Despite the ionic charge of the anilato-based layers, these MOFs can be easily delaminated in thin nanosheets with the thickness of a few monolayers.

  13. Rapid electron exchange between surface-exposed bacterial cytochromes and Fe(III) minerals

    Science.gov (United States)

    White, Gaye F.; Shi, Zhi; Shi, Liang; Wang, Zheming; Dohnalkova, Alice C.; Marshall, Matthew J.; Fredrickson, James K.; Zachara, John M.; Butt, Julea N.; Richardson, David J.; Clarke, Thomas A.

    2013-04-01

    The mineral-respiring bacterium Shewanella oneidensis uses a protein complex, MtrCAB, composed of two decaheme cytochromes, MtrC and MtrA, brought together inside a transmembrane porin, MtrB, to transport electrons across the outer membrane to a variety of mineral-based electron acceptors. A proteoliposome system containing a pool of internalized electron carriers was used to investigate how the topology of the MtrCAB complex relates to its ability to transport electrons across a lipid bilayer to externally located Fe(III) oxides. With MtrA facing the interior and MtrC exposed on the outer surface of the phospholipid bilayer, the established in vivo orientation, electron transfer from the interior electron carrier pool through MtrCAB to solid-phase Fe(III) oxides was demonstrated. The rates were 103 times higher than those reported for reduction of goethite, hematite, and lepidocrocite by S. oneidensis, and the order of the reaction rates was consistent with those observed in S. oneidensis cultures. In contrast, established rates for single turnover reactions between purified MtrC and Fe(III) oxides were 103 times lower. By providing a continuous flow of electrons, the proteoliposome experiments demonstrate that conduction through MtrCAB directly to Fe(III) oxides is sufficient to support in vivo, anaerobic, solid-phase iron respiration.

  14. 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.

  15. The life cycle of iron Fe(III) oxide: impact of fungi and bacteria

    Science.gov (United States)

    Bonneville, Steeve

    2014-05-01

    Iron oxides are ubiquitous reactive constituents of soils, sediments and aquifers. They exhibit vast surface areas which bind a large array of trace metals, nutrients and organic molecules hence controlling their mobility/reactivity in the subsurface. In this context, understanding the "life cycle" of iron oxide in soils is paramount to many biogeochemical processes. Soils environments are notorious for their extreme heterogeneity and variability of chemical, physical conditions and biological agents at play. Here, we present studies investigating the role of two biological agents driving iron oxide dynamics in soils, root-associated fungi (mycorrhiza) and bacteria. Mycorrhiza filaments (hypha) grow preferentially around, and on the surface of nutrient-rich minerals, making mineral-fungi contact zones, hot-spots of chemical alteration in soils. However, because of the microscopic nature of hyphae (only ~ 5 µm wide for up to 1 mm long) and their tendency to strongly adhere to mineral surface, in situ observations of this interfacial micro-environment are scarce. In a microcosm, ectomycorrhiza (Paxillus involutus) was grown symbiotically with a pine tree (Pinus sylvestris) in the presence of freshly-cleaved biotite under humid, yet undersaturated, conditions typical of soils. Using spatially-resolved ion milling technique (FIB), transmission electron microscopy and spectroscopy (TEM/STEM-EDS), synchrotron based X-ray microscopy (STXM), we were able to quantify the speciation of Fe at the biotite-hypha interface. The results shows that substantial oxidation of biotite structural-Fe(II) into Fe(III) subdomains occurs at the contact zone between mycorrhiza and biotite. Once formed, iron(III) oxides can reductively dissolve under suboxic conditions via several abiotic and microbial pathways. In particular, they serve as terminal electron acceptors for the oxidation of organic matter by iron reducing bacteria. We aimed here to understand the role of Fe(III) mineral

  16. Preparation and surface photoelectric properties of Fe(II/III) complexes

    Science.gov (United States)

    Jin, Jing; Xu, Xiao-Ting; Li, Dan; Han, Xiao; Li, Lei; Chi, Yu-Xian; Niu, Shu-Yun; Zhang, Guang-Ning

    2013-05-01

    Four Fe(II/III) supramolecules, {[Fe(Hpdc)2(H2O)2]·2H2O} (1), [Fe(HImbc)2(H2O)2] (2), [Fe(phen)2(CN)2]·CH3CH2OH·2H2O (3), K[Fe(tp)2]·SO4 (4) (H2pdc = 2,5-Pyridinedicarboxylic acid, H2Imbc = 4,5-Imidazoledicarboxylic acid, phen = 1,10-phenanthroline, tp- = poly(pyrazolyl)borate), were synthesized by hydrothermal and room temperature stirring methods. They were characterized by single crystal X-ray diffraction, surface photovoltage spectroscopy (SPS), field-induced surface photovoltage spectroscopy (FISPS), electron paramagnetic resonance (EPR), UV-Vis absorption spectra (UV-Vis), infrared spectra (IR) and element analysis. The structural analyses indicate that complex (1) is a supramolecule with 2D structure connected by hydrogen bonds. Complex (2) is a supramolecule with hydrogen-bonded 3D structure. Complexes (3) and (4) are both 1D supramolecules connected by hydrogen bonds. The electronic state of central metal Fe(II) ions in complexes (1) and (2) is d6 with FeN2O4 coordination mode, lying in weaker distorted octahedral field. The electronic state of Fe(II) ion in complex (3) is d6 with Fe(CN)2N4 mode in the strong distorted octahedral field. The electronic state of Fe(III) ion in complex (4) is d5 with FeN6 mode, lying in the strong octahedral field. The micro-environment of Fe(II/III) ions in the four complexes is further investigated by EPR. The SPS of four complexes all exhibit photovoltage responses in the range of 300-700 nm. This indicates that they all possess certain photoelectric conversion capability. The effects of component, structure, type of ligands of the complexes, valence state and coordination micro-environment of the central metal ions on the SPS were discussed. Furthermore, the SPS and UV-Vis absorption spectra were interrelated.

  17. Nontronite (NAu-1) Structure Associated with Microbial Fe(III) Reduction in Various Redox Conditions

    Science.gov (United States)

    Koo, T.; Kim, S.; Kim, J.

    2011-12-01

    Shewanella oneidensis MR-1 respires the structural Fe(III) of smectite and promotes illite formation in O2-free environment (Kostka et al., 1996, Kim et al., 2004). Since S. oneidensis is a facultative iron reducing bacterium, it is crucial to understand the structural changes induced by bio-reduction of structural Fe(III) in various redox conditions. Furthermore, the changes in cation exchange capacity (CEC) of bio-reduced nontronite upon the modification of mineral structure has not been extensively studied in terms of Fe-cycling. In this present study, we reported the evolution of nontronite structure at various time points in various redox conditions and corresponding CEC upon reduction and re-oxidation. S. oneidensis MR-1 was incubated in M1 medium with Na-lactate as the electron donor and Fe in nontronite (NAu-1) as the sole electron acceptor at pH 7 in anaerobic chamber for 3 hrs, 12 hrs, 1 day, 2 days, 4 days, 7 days, 14 days, and 21 days. O2 gas bubbling was then applied to the sample at each time point for 24 hours for re-oxidation. The triplet samples at each time point for both reduction and re-oxidation experiments were prepared. The extent of Fe(III) reduction measured by 1,10-phenanthroline method (Stucki and Anderson, 1981) indicated that the structural Fe(III) was reduced up to 8.8% of total Fe(III) within 21 days. XRD data with various treatments such as air dried, glycolated and lithium-saturated showed that K-nontronite may be formed because no discrete 10-Å illite peak was observed in Li-saturated sample upon glycolation. The CEC increased from 747 meg/kg to 1145 meg/kg during Fe(III) reduction and decreased to 954 meg/kg upon re-oxidation, supporting the possible formation of K-nontronite. The direct observation by electron microscopy verified the structural changes in nontonite in various redox conditions. The long-term experiment for 6 months, is in progress in anaerobic chamber, and results will be discussed. Kim, J. W., Dong, H., Seabaugh

  18. Spin relaxation in antiferromagnetic Fe–Fe dimers slowed down by anisotropic DyIII ions

    Directory of Open Access Journals (Sweden)

    Valeriu Mereacre

    2013-11-01

    Full Text Available By using Mössbauer spectroscopy in combination with susceptibility measurements it was possible to identify the supertransferred hyperfine field through the oxygen bridges between DyIII and FeIII in a {Fe4Dy2} coordination cluster. The presence of the dysprosium ions provides enough magnetic anisotropy to “block” the hyperfine field that is experienced by the iron nuclei. This has resulted in magnetic spectra with internal hyperfine fields of the iron nuclei of about 23 T. The set of data permitted us to conclude that the direction of the anisotropy in lanthanide nanosize molecular clusters is associated with the single ion and crystal field contributions and 57Fe Mössbauer spectroscopy may be informative with regard to the the anisotropy not only of the studied isotope, but also of elements interacting with this isotope.

  19. Moessbauer study of peroxynitrito complex formation with Fe{sup III}-chelates

    Energy Technology Data Exchange (ETDEWEB)

    Homonnay, Zoltan, E-mail: homonnay@ludens.elte.hu; Buszlai, Peter; Nador, Judit [Eoetvoes University, Institute of Chemistry (Hungary); Sharma, Virender K. [Florida Institute of Technology (United States); Kuzmann, Erno; Vertes, Attila [Eoetvoes University, Institute of Chemistry (Hungary)

    2012-03-15

    The reaction of the {mu}-oxo-diiron(III)-L complex (L = EDTA, ethylene diamine tetraacetate, HEDTA, hydroxyethyl ethylene diamine triacetate, and CyDTA, cyclohexane diamine tetraacetate) with peroxynitrite in alkaline solution was studied by Moessbauer spectroscopy using rapid-freezing technique. These complexes yield an (L)Fe{sup III}({eta}{sup 2}-O{sub 2}){sup 3-} complex ion when they react with hydrogen peroxide and the formation of the peroxide adduct results in a deep purple coloration of the solution. The same color appears when the reaction occurs with peroxinitrite. Although spectrophotometry indicated some difference between the molar extinction coefficients of the peroxo and the peroxinitrito adducts, the Moessbauer parameters proved to be the same within experimental error. It is concluded that the peroxynitrite ion decomposes when reacting with Fe{sup III}(L) and the peroxo adduct forms.

  20. Effect of phosphate, silicate, and Ca on the morphology, structure and elemental composition of Fe(III)-precipitates formed in aerated Fe(II) and As(III) containing water

    Science.gov (United States)

    Kaegi, Ralf; Voegelin, Andreas; Folini, Doris; Hug, Stephan J.

    2010-10-01

    We investigated Fe(III)-precipitates formed from Fe(II) oxidation in water at pH 7 as a function of dissolved Fe(II), As(III), phosphate, and silicate in the absence and presence of Ca. We used transmission electron microscopy (TEM), including selected area electron diffraction (SAED) and energy dispersive X-ray spectroscopy (EDX) to characterize the morphology, structure and elemental composition of the precipitates. Results from our companion X-ray absorption spectroscopy (XAS) study suggested that the oxidation of Fe(II) leads to the sequential formation of distinct polymeric units in the following order: Fe(III)-phosphate oligomers in the presence of phosphate, silicate-rich hydrous ferric oxide (HFO-Si) at high Si/Fe (>0.5) or 2-line ferrihydrite (2L-Fh) at lower Si/Fe (˜0.1-0.5), and lepidocrocite (Lp) in the absence of phosphate at low Si/Fe (arrangement of the different polymeric units within Fe(III)-precipitates. The resulting structural and compositional heterogeneity of short-range-ordered Fe(III)-precipitates likely affects their colloidal stability and their chemical reactivity and needs to be considered when addressing the fate of co-transformed trace elements such as arsenic.

  1. Formation of Fe(III)-containing mackinawite from hydroxysulphate green rust by sulphate reducing bacteria

    Energy Technology Data Exchange (ETDEWEB)

    Langumier, M. [Laboratoire d' Etude des Materiaux en Milieux Agressifs, EA3167, Universite de La Rochelle, Batiment Marie Curie, Avenue Michel Crepeau, F-17042 La Rochelle cedex 01 (France); Littoral, Environnement et Societes, UMR 6250, CNRS-Universite de La Rochelle, 2 rue Olympe de Gouges, F-17000 La Rochelle (France); Federation de Recherche en Environnement et Developpement Durable, FR CNRS 3097 (France); Sabot, R. [Laboratoire d' Etude des Materiaux en Milieux Agressifs, EA3167, Universite de La Rochelle, Batiment Marie Curie, Avenue Michel Crepeau, F-17042 La Rochelle cedex 01 (France); Federation de Recherche en Environnement et Developpement Durable, FR CNRS 3097 (France); Obame-Ndong, R. [Laboratoire d' Etude des Materiaux en Milieux Agressifs, EA3167, Universite de La Rochelle, Batiment Marie Curie, Avenue Michel Crepeau, F-17042 La Rochelle cedex 01 (France); Littoral, Environnement et Societes, UMR 6250, CNRS-Universite de La Rochelle, 2 rue Olympe de Gouges, F-17000 La Rochelle (France); Federation de Recherche en Environnement et Developpement Durable, FR CNRS 3097 (France); Jeannin, M. [Laboratoire d' Etude des Materiaux en Milieux Agressifs, EA3167, Universite de La Rochelle, Batiment Marie Curie, Avenue Michel Crepeau, F-17042 La Rochelle cedex 01 (France); Federation de Recherche en Environnement et Developpement Durable, FR CNRS 3097 (France); Sable, S. [Littoral, Environnement et Societes, UMR 6250, CNRS-Universite de La Rochelle, 2 rue Olympe de Gouges, F-17000 La Rochelle (France); Federation de Recherche en Environnement et Developpement Durable, FR CNRS 3097 (France); Refait, Ph. [Laboratoire d' Etude des Materiaux en Milieux Agressifs, EA3167, Universite de La Rochelle, Batiment Marie Curie, Avenue Michel Crepeau, F-17042 La Rochelle cedex 01 (France); Federation de Recherche en Environnement et Developpement Durable, FR CNRS 3097 (France)], E-mail: prefait@univ-lr.fr

    2009-11-15

    The interactions between Fe(II-III) hydroxysulphate GR(SO{sub 4}{sup 2-}) and sulphate reducing bacteria (SRB) were studied. The considered SRB, Desulfovibrio desulfuricans subsp. aestuarii ATCC 29578, were added with GR(SO{sub 4}{sup 2-}) to culture media. Different conditions were envisioned, corresponding to various concentrations of bacteria, various sources of sulphate (dissolved SO{sub 4}{sup 2-} + GR(SO{sub 4}{sup 2-}) or GR(SO{sub 4}{sup 2-}) alone) and various atmospheres (N{sub 2}:H{sub 2} or N{sub 2}:CO{sub 2}:H{sub 2}). In the first part of the study, CO{sub 2} was deliberately omitted so as to avoid the formation of carbonated compounds, and GR(SO{sub 4}{sup 2-}) was the only source of sulphate. Cell concentration increases from {approx}4 x 10{sup 7} to {approx}7 x 10{sup 8} cells/mL in 2 weeks. The evolution with time of the iron compounds, monitored by Raman spectroscopy and X-ray diffraction, showed the progressive formation of a FeS compound, the Fe(III)-containing mackinawite. This result is consistent with the association GR(SO{sub 4}{sup 2-})/SRB/FeS observed in rust layers formed on steel in seawater. In the presence of CO{sub 2} and additional dissolved sulphate species, a rapid growth of the bacteria could be observed, leading to the total transformation of GR(SO{sub 4}{sup 2-}) into mackinawite, found in three physico-chemical states (nanocrystalline, crystalline stoichiometric FeS and Fe(III)-containing), and siderite FeCO{sub 3}.

  2. Synthesis of Ionic Imprinted Polymer Particles for Selective Membrane Transport ofFe(III using Polyeugenol as the Functional Polymer

    Directory of Open Access Journals (Sweden)

    Muhammad Cholid Djunaidi

    2016-03-01

    Full Text Available The preparation of Ionic Imprinted Polymer (IIP particles for selective membrane transport of Fe (III had been done using polyeugenol as functional polymer and PVA (polyvinyl alcohol (Mr 125,000 solution in 1-Methyl-2-pyrrolidone (NMP solvent as membrane base. The membrane was then cut and Fe(III was removed by acid to produce IIP particles membrane. Analysis of the membrane and its constituent was done by IR, SEM and also TOC analysis. Experimental results showed the transport of Fe(III was faster with the decrease of membrane thickness and the higher concentration of template. However, the transport of Fe(III was slower for higher concentration of PVA (Polyvinyl Alcohol in the membrane. The selectivity of all IIP particles membrane was confirmed as they were all unable to transport Cr (III, while NIP (Non-imprinted Polymer membrane was able transport Cr (III.

  3. Study of the reaction between ammonium thiocyanate and Fe (II or Fe (III using infrared spectroscopy: an experiment of prebiotic chemistry

    Directory of Open Access Journals (Sweden)

    Dimas Augusto Morozin Zaia

    2010-09-01

    Full Text Available The prebiotic chemistry studies the reactions that could be played an important role on origins of life on Earth. However, these reactions should be carried out under conditions that existed on the prebiotic Earth. The laboratory experiments of heating substances in solid state could be corresponding to the following prebiotic environments: cooling lava from volcanoes on the ground and impact of meteorites or comets on the earth. The present study examined the reaction in solid state between ammonium thiocyanate and Fe (II or Fe (III. The samples were heated at 220 ºC in several different times (6 hours, 24 hours, 7 days. The most important finding of this work is that a reaction of oxidation-reduction is occurring between Fe (II and ammonium thiocyanate, the infrared spectrum of the reaction product ammonium thiocyanate/Fe (II showed a band that it is characteristic of ferricyanate. The infrared spectra also showed bands that they are characteristics of guanidine thiocyanate. Thus, the heating of ammonium thiocyanate with Fe (II in solid state is synthesizing guanidine thiocyanate and at the same time oxidizing Fe (II to Fe (III. The product of reaction between Fe (III and ammonium thiocyanate is guanidine thiocyanate. Fe (II and Fe (III are reacting with ammonium thiocyanate in different way.

  4. Influence of geochemical properties and land-use types on the microbial reduction of Fe(III) in subtropical soils.

    Science.gov (United States)

    Liu, Chengshuai; Wang, Yongkui; Li, Fangbai; Chen, Manjia; Zhai, Guangshu; Tao, Liang; Liu, Chuanping

    2014-08-01

    Microbial Fe(III) reduction significantly impacts the geochemical processes and the composition of most subsurface soils. However, up to now, the factors influencing the efficiency of Fe(III) reduction in soils have not been fully described. In this study, soil Fe(III) reduction processes related to geochemical properties and land-use types were systematically investigated using iron-rich soils. The results showed that microbial Fe(III) reduction processes were efficient and their rates varied significantly in different types of soils. Fe(III) reduction rates were 1.1-5.6 times as much in soils with glucose added as in those without glucose. Furthermore, Fe(III) reduction rates were similar in soils from the same parent materials, while they were highest in soils developed from sediments, with a mean rate of 1.87 mM per day when supplemented with glucose. In addition, the Fe(III) reduction rates, reaching 0.99 and 0.59 mM per day on average with and without glucose added, respectively, were higher in the paddy soils affected heavily by human activities than those in the forest soils (average rates of 0.38 and 0.15 mM per day when with and without glucose, respectively). All the soil weathering indices correlated linearly with Fe(III) reduction rates, even though the reduction of iron in soils with higher weathering degrees was partly inhibited by a higher soil protonation trend and fewer available iron reduction sites in the soils, which gives lower reduction rates. These results clearly illustrate that soil Fe(III) reduction rates are greatly dependent on soil geochemical properties and land-use types and help define which soil types exhibit similar degrees of Fe(III) reduction under field conditions.

  5. Redox activation of Fe(III)-thiosemicarbazones and Fe(III)-bleomycin by thioredoxin reductase: specificity of enzymatic redox centers and analysis of reactive species formation by ESR spin trapping.

    Science.gov (United States)

    Myers, Judith M; Cheng, Qing; Antholine, William E; Kalyanaraman, Balaraman; Filipovska, Aleksandra; Arnér, Elias S J; Myers, Charles R

    2013-07-01

    Thiosemicarbazones such as Triapine (Tp) and Dp44mT are tridentate iron (Fe) chelators that have well-documented antineoplastic activity. Although Fe-thiosemicarbazones can undergo redox cycling to generate reactive species that may have important roles in their cytotoxicity, there is only limited insight into specific cellular agents that can rapidly reduce Fe(III)-thiosemicarbazones and thereby promote their redox activity. Here we report that thioredoxin reductase-1 (TrxR1) and glutathione reductase (GR) have this activity and that there is considerable specificity to the interactions between specific redox centers in these enzymes and various Fe(III) complexes. Site-directed variants of TrxR1 demonstrate that the selenocysteine (Sec) of the enzyme is not required, whereas the C59 residue and the flavin have important roles. Although TrxR1 and GR have analogous C59/flavin motifs, TrxR is considerably faster than GR. For both enzymes, Fe(III)(Tp)2 is reduced faster than Fe(III)(Dp44mT)2. This reduction promotes redox cycling and the generation of hydroxyl radical (HO) in a peroxide-dependent manner, even with low-micromolar levels of Fe(Tp)2. TrxR also reduces Fe(III)-bleomycin and this activity is Sec-dependent. TrxR cannot reduce Fe(III)-EDTA at significant rates. Our findings are the first to demonstrate pro-oxidant reductive activation of Fe(III)-based antitumor thiosemicarbazones by interactions with specific enzyme species. The marked elevation of TrxR1 in many tumors could contribute to the selective tumor toxicity of these drugs by enhancing the redox activation of Fe(III)-thiosemicarbazones and the generation of reactive oxygen species such as HO.

  6. 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

  7. 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.

  8. 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.

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

    Science.gov (United States)

    Kleinert, Susanne; Muehe, Eva M; Posth, Nicole R; Dippon, Urs; Daus, Birgit; Kappler, Andreas

    2011-09-01

    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 whether Fe(II)-oxidizing bacteria influenced filter efficiency. We found up to 10(7) Fe(II)-oxidizing bacteria/g dry-weight in GEH-filters and determined the performance of filter material in the presence and absence of Fe(II)-oxidizing bacteria. GEH-material sorbed 1.7 mmol As(V)/g Fe and was ~8 times more efficient than biogenic Fe(III) minerals that sorbed only 208.3 μmol As(V)/g Fe. This was also ~5 times more efficient than a 10:1-mixture of GEH-material and biogenic Fe(III) minerals that bound 322.6 μmol As(V)/g Fe. Coprecipitation of As(V) with biogenic Fe(III) minerals removed 343.0 μmol As(V)/g Fe, while As removal by coprecipitation with biogenic minerals in the presence of GEH-material was slightly less efficient as GEH-material only and yielded 1.5 mmol As(V)/g Fe. The present study thus suggests that the formation of biogenic Fe(III) minerals lowers rather than increases As removal efficiency of the filters probably due to the repulsion of the negatively charged arsenate by the negatively charged biogenic minerals. For this reason we recommend excluding microorganisms from filters (e.g., by activated carbon filters) to maintain their high As removal capacity.

  10. Rapid acceleration of ferrous iron/peroxymonosulfate oxidation of organic pollutants by promoting Fe(III)/Fe(II) cycle with hydroxylamine.

    Science.gov (United States)

    Zou, Jing; Ma, Jun; Chen, Liwei; Li, Xuchun; Guan, Yinghong; Xie, Pengchao; Pan, Chao

    2013-10-15

    The reaction between ferrous iron (Fe(II)) with peroxymonosulfate (PMS) generates reactive oxidants capable of degrading refractory organic contaminants. However, the slow transformation from ferric iron (Fe(III)) back to Fe(II) limits its widespread application. Here, we added hydroxylamine (HA), a common reducing agent, into Fe(II)/PMS process to accelerate the transformation from Fe(III) to Fe(II). With benzoic acid (BA) as probe compound, the addition of HA into Fe(II)/PMS process accelerated the degradation of BA rapidly in the pH range of 2.0-6.0 by accelerating the key reactions, including the redox cycle of Fe(III)/Fe(II) and the generation of reactive oxidants. Both sulfate radicals and hydroxyl radicals were considered as the primary reactive oxidants for the degradation of BA in HA/Fe(II)/PMS process with the experiments of electron spin resonance and alcohols quenching. Moreover, HA was gradually degraded to N2, N2O, NO2 (−), and NO3 (−), while the environmentally friendly gas of N2 was considered as its major end product in the process. The present study might provide a promising idea based on Fe(II)/PMS process for the rapid degradation of refractory organic contaminants in water treatment.

  11. Fenten chemistry of Fe(III)-exchanged zeolitic minerals treated with antioxidants.

    Science.gov (United States)

    Ruda, Toni A; Dutta, Prabir K

    2005-08-15

    Respirable mineral fibers, such as asbestos, are known to cause pleural mesothelioma, pulmonary fibrosis, and bronchial carcinoma, often years after exposure. Erionite and mordenite, two mineral aluminosilicates (zeolites) with different toxicities, can be used as models to help understand asbestos toxicity. Erionite is carcinogenic, while mordenite is relatively benign. No iron is typically present in erionite or mordenite, but because of their ion-exchange properties they can acquire iron after inhalation. The iron is typically in the Fe(III) form and will need to be reduced prior to any Fenton activity. Lung lining fluid contains antioxidants, such as glutathione (GSH) and ascorbic acid (AA), which can reduce Fe(III) to Fe(II). In this study, we have compared the Fenton reactivity of Fe(III)-exchanged erionite and mordenite after treatment with antioxidants. The Fenton assay involved the reaction of hydroxyl radicals with dimethyl sulfoxide. Fenton reactivity was most marked with AA followed by GSH, and hydrogen peroxide also exhibited minor reactivity. Erionite generated an order of magnitude greater hydroxyl radicals than mordenite, normalized to the surface iron content, providing support for the hypothesis that the iron coordination at the mineral surface plays a significant role in bioactivity.

  12. Characterization of microbially Fe(III)-reduced nontronite: Environmental cell-transmission electron microscopy study

    Science.gov (United States)

    Kim, J.-W.; Furukawa, Y.; Daulton, T.L.; Lavoie, D.; Newell, S.W.

    2003-01-01

    Microstructural changes induced by the microbial reduction of Fe(III) in nontronite by Shewanella oneidensis were studied using environmental cell (EC)-transmission electron microscopy (TEM), conventional TEM, and X-ray powder diffraction (XRD). Direct observations of clays by EC-TEM in their hydrated state allowed for the first time an accurate and unambiguous TEM measurement of basal layer spacings and the contraction of layer spacing caused by microbial effects, most likely those of Fe(III) reduction. Non-reduced and Fe(III)-reduced nontronite, observed by EC-TEM, exhibited fringes with mean d001 spacings of 1.50 nm (standard deviation, ?? = 0.08 nm) and 1.26 nm (?? = 0.10 nm), respectively. In comparison, the same samples embedded with Nanoplast resin, sectioned by microtome, and observed using conventional TEM, displayed layer spacings of 1.0-1.1 nm (non-reduced) and 1.0 nm (reduced). The results from Nanoplast-embedded samples are typical of conventional TEM studies, which have measured nearly identical layer spacings regardless of Fe oxidation state. Following Fe(III) reduction, both EC- and conventional TEM showed an increase in the order of nontronite selected area electron diffraction patterns while the images exhibited fewer wavy fringes and fewer layer terminations. An increase in stacking order in reduced nontronite was also suggested by XRD measurements. In particular, the ratio of the valley to peak intensity (v/p) of the 1.7 nm basal 001 peak of ethylene glycolated nontronite was measured at 0.65 (non-reduced) and 0.85 (microbially reduced).

  13. 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.

  14. Adsorption of some transition metal ions (Cu(II), Fe(III), Cr(III) and Au(III)) onto lignite-based activated carbons modified by oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Paunka St. Vassileva; Albena K. Detcheva [Bulgarian Academy of Sciences, Sofia (Bulgaria). Institute of General and Inorganic Chemistry

    2010-03-15

    The main purpose of the present work was to study the adsorption of some transition metal ions from aqueous solution via a novel porous material obtained from Bulgarian lignite (Chukurovo deposit) and its oxidized modifications. The adsorption of Cu(II), Fe(III), Cr(III) and Au(III) ions was investigated using batch methods to study solutions with different concentrations and acidities. It was found that the adsorption process was affected significantly by the pH value of the aqueous solution. Treatment of the equilibrium data using the linear Langmuir, Freundlich and Dubinin-Radushkevich models allowed the maximum adsorption capacities to be calculated. The uptake of Au(III) ions was almost 100% for the three adsorbents investigated, being greater than 300 mg/l and independent of the pH over the pH range studied. The initial activated carbon proved to be the most suitable for the selective adsorption of Au(III) ions from aqueous solutions in the presence of other transition metal ions, while its oxidized modification Ch-P exhibited an enhanced adsorption efficiency towards transition metals.

  15. Adsorption of Some Transition Metal Ions (Cu(II), Fe(III), Cr(III) and Au(III)) onto lignite-based activated carbons modified by oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Vassileva, P.S.; Detcheva, A.K. [Bulgarian Academy of Science, Sofia (Bulgaria)

    2010-07-01

    The main purpose of the present work was to study the adsorption of some transition metal ions from aqueous solution via a novel porous material obtained from Bulgarian lignite (Chukurovo deposit) and its oxidized modifications. The adsorption of Cu(II), Fe(III), Cr(III) and Au(III) ions was investigated using batch methods to study solutions with different concentrations and acidities. It was found that the adsorption process was affected significantly by the pH value of the aqueous solution. Treatment of the equilibrium data using the linear Langmuir, Freundlich and Dubinin-Radushkevich models allowed the maximum adsorption capacities to be calculated. The uptake of Au(III) ions was almost 100% for the three adsorbents investigated, being greater than 300 mg/l and independent of the pH over the pH range studied. The initial activated carbon proved to be the most suitable for the selective adsorption of Au(III) ions from aqueous solutions in the presence of other transition metal ions, while its oxidized modification Ch-P exhibited an enhanced adsorption efficiency towards transition metals.

  16. Outer membrane-associated serine protease involved in adhesion of Shewanella oneidensis to Fe(III) oxides.

    Science.gov (United States)

    Burns, Justin L; Ginn, Brian R; Bates, David J; Dublin, Steven N; Taylor, Jeanette V; Apkarian, Robert P; Amaro-Garcia, Samary; Neal, Andrew L; Dichristina, Thomas J

    2010-01-01

    The facultative anaerobe Shewanella oneidensis MR-1 respires a variety of anaerobic electron acceptors, including insoluble Fe(III) oxides. S. oneidensis employs a number of novel strategies for respiration of insoluble Fe(III) oxides, including localization of respiratory proteins to the cell outer membrane (OM). The molecular mechanism by which S. oneidensis adheres to and respires Fe(III) oxides, however, remains poorly understood. In the present study, whole cell fractionation and MALDI-TOF-MS/MS techniques were combined to identify a serine protease (SO3800) associated with the S. oneidensis OM. SO3800 contained predicted structural motifs similar to cell surface-associated serine proteases that function as bacterial adhesins in other gram-negative bacteria. The gene encoding SO3800 was deleted from the S. oneidensis genome, and the resulting mutant strain (DeltaSO3800) was tested for its ability to adhere to and respire Fe(III) oxides. DeltaSO3800 was severely impaired in its ability to adhere to Fe(III) oxides, yet retained wild-type Fe(III) respiratory capability. Laser Doppler velocimetry and cryoetch high-resolution SEM experiments indicated that DeltaSO3800 displayed a lower cell surface charge and higher amount of surface-associated exopolysaccharides. Results of this study indicate that S. oneidensis may respire insoluble Fe(III) oxides at a distance, negating the requirement for attachment prior to electron transfer.

  17. Spiral Dinuclear Complexes of Tetradentate N(4) Diazine Ligands with Mn(II), Fe(II), Fe(III), Co(III), and Ni(II) Salts.

    Science.gov (United States)

    Xu, Zhiqiang; Thompson, Laurence K.; Miller, David O.; Clase, Howard J.; Howard, Judith A. K.; Goeta, Andrés E.

    1998-07-13

    A series of dinuclear complexes of the tetradentate dipyridyl-diazine ligand PAHAP with Mn(II), Fe(II), Fe(III), Co(III), and Ni(II) salts is reported in which three ligands wrap themselves around the six-coordinate metal centers in a rare spiral-like fashion. A similar Fe(II) complex is found for the dipyrazinyl-diazine ligand PZHPZ. The ligands are severely twisted with dihedral angles between the metal chelate ring mean planes on each ligand in the range 50-70 degrees, values close to the expected twist angle for orthogonality between the bridging nitrogen atom p orbitals. Full structures are reported for the dinuclear complexes [Mn(2)(PAHAP)(3)](ClO(4))(4).5H(2)O (1), [Fe(2)(PAHAP)(3)](NO(3))(4).3H(2)O (2), [Fe(2)(PZHPZ)(3)](NO(3))(4).5H(2)O (5), [Co(2)(PAHAP)(3)](NO(3))(6).5H(2)O (6), and [Ni(2)(PAHAP)(3)][Ni(H(2)O)(6)](NO(3))(6).4.5H(2)O (7). Other derivatives [Fe(2)(PAHAP)(3)](ClO(4))(4).4H(2)O (3), [Fe(2)(PAHAP)(3)](ClO(4))(6).4.5H(2)O (4), [Ni(2)(PAHAP)(3)](ClO(4))(4).5H(2)O (8), and [Fe(PHAAP-H)(H(2)O)(2)(NO(3))](NO(3))(2) (9) are also reported. Complex 1 crystallized in the monoclinic system, space group C2/c, with a = 13.4086(2) Å, b = 32.0249(1) Å, c = 14.3132(2) Å, alpha = 90 degrees, beta = 115.635(1) degrees, gamma = 90 degrees, and Z = 4. Complex 2 crystallized in the cubic system, space group Pa&thremacr;, with a = b = c = 21.0024(1) Å, alpha = beta = gamma = 90 degrees, and Z = 8. Complex 5 crystallized in the monoclinic system, space group P2/n, with a = 14.039(3) Å, b = 11.335(6) Å, c = 14.6517(15) Å, beta = 96.852(11) degrees, and Z = 1. Complex 6 crystallized in the trigonal system, space group R&thremacr;c(h), with a = b = 17.386(2) Å, c = 32.15(2) Å, alpha = beta = 90 degrees, gamma = 120 degrees, and Z = 4. Complex 7 crystallized in the trigonal system, space group R&thremacr;c, with a = b = 17.3737(3) Å, c = 33.235(6) Å, alpha = beta = 90 degrees, gamma = 120 degrees, and Z = 27. Weak ferromagnetic coupling was observed for 1

  18. 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.

  19. 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; Cete, 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, (1)H-(13)C 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(2)O, 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(2)O)(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.

  20. The nature of the intermediates in the reactions of Fe(III)- and Mn(III)-microperoxidase-8 with H(2)O(2): a rapid kinetics study.

    Science.gov (United States)

    Primus, Jean-Louis; Grunenwald, Sylvie; Hagedoorn, Peter-Leon; Albrecht-Gary, Anne-Marie; Mandon, Dominique; Veeger, Cees

    2002-02-20

    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 and metal-hydroperoxo intermediates of M(III)MP-8 upon reaction of H(2)O(2) with Fe(III)MP-8 and Mn(III)MP-8 was investigated by rapid-scan stopped-flow spectroscopy and transient EPR. Two steps (k(obs1) and k(obs2)) were observed and analyzed for the reaction of hydrogen peroxide with both catalysts. The plots of k(obs1) as function of [H(2)O(2)] at pH 8.0 and pH 9.1 for Fe(III)MP-8, and at pH 10.2 and pH 10.9 for Mn(III)MP-8, exhibit saturation kinetics, which reveal the accumulation of an intermediate. Double reciprocal plots of 1/k(obs1) as function of 1/[H(2)O(2)] at different pH values reveal a competitive effect of protons in the oxidation of M(III)MP-8. This effect of protons is confirmed by the linear dependence of 1/k(obs1) on [H(+)] showing that k(obs1) increases with the pH. The UV-visible spectra of the intermediates formed at the end of the first step (k(obs1)) exhibit a spectrum characteristic of a high-valent metal-oxo intermediate for both catalysts. Transient EPR of Mn(III)MP-8 incubated with an excess of H(2)O(2), at pH 11.5, shows the detection of a free radical signal at g approximately equal to 2 and of a resonance at g approximately equal to 4 characteristic of a Mn(IV) (S = 3/2) species. On the basis of these results, the following mechanism is proposed: (i) M(III)MP-8-OH(2) is deprotonated to M(III)MP-8-OH in a rapid preequilibrium step, with a pK(a) = 9.2 +/- 0.9 for Fe(III)MP-8 and a pK(a) = 11.2 +/- 0.3 for Mn(III)MP-8; (ii) M(III)MP-8-OH reacts with H(2)O(2) to form Compound 0, M(III)MP8-OOH, with a second-order rate constant k(1) = (1.3 +/- 0.6) x 10(6) M(-1) x s(-1) for Fe(III)MP-8 and k(1) = (1.6 +/- 0.9) x 10(5) M(-1) x s(-1) for Mn(III

  1. Effects of microbial iron reduction and oxidation on the immobilization and mobilization of copper in synthesized Fe(III) minerals and Fe-rich soils.

    Science.gov (United States)

    Hu, Chaohua; Zhang, Youchi; Zhang, Lei; Luo, Wensui

    2014-04-01

    The effects of microbial iron reduction and oxidation on the immobilization and mobilization of copper were investigated in a high concentration of sulfate with synthesized Fe(III) minerals and red earth soils rich in amorphous Fe (hydr)oxides. Batch microcosm experiments showed that red earth soil inoculated with subsurface sediments had a faster Fe(III) bioreduction rate than pure amorphous Fe(III) minerals and resulted in quicker immobilization of Cu in the aqueous fraction. Coinciding with the decrease of aqueous Cu, SO4(2-) in the inoculated red earth soil decreased acutely after incubation. The shift in the microbial community composite in the inoculated soil was analyzed through denaturing gradient gel electrophoresis. Results revealed the potential cooperative effect of microbial Fe(III) reduction and sulfate reduction on copper immobilization. After exposure to air for 144 h, more than 50% of the immobilized Cu was remobilized from the anaerobic matrices; aqueous sulfate increased significantly. Sequential extraction analysis demonstrated that the organic matter/sulfide-bound Cu increased by 52% after anaerobic incubation relative to the abiotic treatment but decreased by 32% after oxidation, indicating the generation and oxidation of Cu-sulfide coprecipitates in the inoculated red earth soil. These findings suggest that the immobilization of copper could be enhanced by mediating microbial Fe(III) reduction with sulfate reduction under anaerobic conditions. The findings have an important implication for bioremediation in Cucontaminated and Fe-rich soils, especially in acid-mine-drainage-affected sites.

  2. Regulatory Fe(II/III) heme: the reconstruction of a molecule's biography.

    Science.gov (United States)

    Kühl, Toni; Imhof, Diana

    2014-09-22

    More than 20 years of research on heme as a temporary effector molecule of proteins have revealed its widespread impact on virtually all primary functions in the human organism. As our understanding of this influence is still growing, a comprehensive overview of compiled data will give fresh impetus for creativity and developing new strategies in heme-related research. From known data concerning heme-regulated proteins and their involvement in the development of diseases, we provide concise information of Fe(II/III) heme as a regulator and the availability of "regulatory heme". The latter is dependent on the balance between free and bound Fe(II/III) heme, here termed "hemeostasis". Imbalance of this system can lead to the development of diseases that were not always attributed to this small molecule. Diseases such as cancer or Alzheimer's disease highlight the reawakened interest in heme, whose function was previously believed to be completely understood.

  3. Photochemical degradation of environmentally persistent perfluorooctanoic acid (PFOA) in the presence of Fe(III)

    Institute of Scientific and Technical Information of China (English)

    Yuan Wang; Peng Yi Zhang; Gang Pan; Hao Chen

    2008-01-01

    Environmentally persistent and bioaccumulative perfluorooctanic acid (PFOA) was difficult to be decomposed under the irradiation of 254 nm UV light. However, in the presence of 80μmol /L Fe(III), 80% of PFOA with initial concentration of 48μmol/L (20 mg/L) was effectively degraded and 47.8% of fluorine atoms in PFOA molecule were transformed into inorganic fluoride ion after 4 h reaction. Shorter chain perfluorocarboxylic acids bearing C3-C7 and fluoride ion were detected and identified by LC/MS and IC as the degradation products in the aqueous solution. It was proposed that complexes of PFOA with Fe(III) initiated degradation of PFOA irradiated with 254 nm UV light.

  4. OmcB, a c-Type Polyheme Cytochrome, Involved in Fe(III) Reduction in Geobacter sulfurreducens

    OpenAIRE

    2003-01-01

    Microorganisms in the family Geobacteraceae are the predominant Fe(III)-reducing microorganisms in a variety of subsurface environments in which Fe(III) reduction is an important process, but little is known about the mechanisms for electron transport to Fe(III) in these organisms. The Geobacter sulfurreducens genome was found to contain a 10-kb chromosomal duplication consisting of two tandem three-gene clusters. The last genes of the two clusters, designated omcB and omcC, encode putative o...

  5. 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.

  6. Biochar-Facilitated Reduction of Crystalline Fe(III) in Hematite

    Science.gov (United States)

    Xu, S.; Yang, Y.; Roden, E. E.; Tang, Y.; Huang, R.; Adhikari, D.

    2015-12-01

    Pyrogenic organic matter is a significant component of soil organic matter, the transformation of which may play a crucial role in the coupled redox cycles of carbon and iron. However, scant information is available for the role of pyrogenic carbon in the redox cycle of iron. Herein, we studied the influences of wheat straw-derived biochar on the microbial reduction of hematite by Shewanella oneidensis MR-1. In the presence of 10 mg/L biochar, microbial reduction of hematite was substantially accelerated by 41% to 142%. Reduction of hematite was enhanced to similar degrees by aqueous biochar with the concentration of 1-3 mg C/L. Importance of the aqueous biochar was also supported by the response of enhancement of Fe reduction to the dose of biochar particles, closely linked to the change in aqueous biochar concentration rather than the amount of total biochar particles. Microbiologically pre-reduced biochar reduced hematite abiotically, demonstrating the electron shuttling capacity of aqueous biochar for hematite reduction. On the other side, biochar particles sorbed Fe(II) and consequently decreased the accumulation of Fe(II) in solution to facilitate the reduction of hematite further. We reported for the first time the biochar-facilitated microbial reduction of crystalline Fe(III), through electron shuttling processes mediated by aqueous biochar and complexation of Fe(II) by biochar particles. Such impacted redox cycles of Fe would be important for the soil environment with relatively high content of indigenous pyrogenic carbon or substantial application of biochar.

  7. Composition and anion ordering in some Fe II-III hydroxysalt green rusts (carbonate, oxalate, methanoate): The fougerite mineral

    Science.gov (United States)

    Génin, Jean-Marie R.; Ruby, Christian

    2008-03-01

    Main features of Fe II-III hydroxysalts (green rusts) are obtained from XRD. Moreover, Mössbauer spectroscopy revealed that several Fe II sites exist. The structure is classified in green rusts one and two (GR1 and GR2) according to the stacking sequence of Fe(OH) 2 brucite-like layers depending on the shape and type of anions inserted within interlayers. Long range order as determined for hydroxysulphate GR2(SO 42-) is extended to distributions of cations and anions within GR1s even though these are not observed by XRD. Abundances of Fe II and Fe III environments within GR1s that intercalate carbonate, oxalate and methanoate (formate) are found for compositions [Fe 6IIFe 2III(OH) 16] 2+·[CO 32-·5H 2O] 2-, [Fe 4IIFe 2III(OH) 12] 2+·[CO 32-·3H 2O] 2-, [Fe 6IIFe 2III(OH) 16] 2+·[C 2O 42-·4H 2O] 2- and [Fe 5IIFe 2III(OH) 14] 2+·[2HCOO -·3H 2O] 2-, which correspond to orders α, β and γ where the cation distances are (2 × a0), (√3 × a0) or a mixture of both, with a ferric molar ratio x = {[Fe III]/[Fe total]} = 1/4, 1/3 and 2/7, respectively. Anion distributions within interlayers are devised and long range orders in other layered double hydroxides could questionably be extended from these models. The formula [Fe 6II(1- x) Fe 6 xIIIO 12H 2(7-3 x) ] 2+·[CO 32-·3H 2O] 2- for the fougerite mineral, which is the oxyhydroxycarbonate obtained by deprotonation of Fe II-III hydroxycarbonate [Fe 4IIFe 2III(OH) 12] 2+·[CO 32-·3H 2O] 2- where x ∈ [1/3,2/3] is confirmed.

  8. Metal-Assisted Oxo Atom Addition to an Fe(III) Thiolate.

    Science.gov (United States)

    Villar-Acevedo, Gloria; Lugo-Mas, Priscilla; Blakely, Maike N; Rees, Julian A; Ganas, Abbie S; Hanada, Erin M; Kaminsky, Werner; Kovacs, Julie A

    2017-01-11

    Cysteinate oxygenation is intimately tied to the function of both cysteine dioxygenases (CDOs) and nitrile hydratases (NHases), and yet the mechanisms by which sulfurs are oxidized by these enzymes are unknown, in part because intermediates have yet to be observed. Herein, we report a five-coordinate bis-thiolate ligated Fe(III) complex, [Fe(III)(S2(Me2)N3(Pr,Pr))](+) (2), that reacts with oxo atom donors (PhIO, IBX-ester, and H2O2) to afford a rare example of a singly oxygenated sulfenate, [Fe(III)(η(2)-S(Me2)O)(S(Me2))N3(Pr,Pr)](+) (5), resembling both a proposed intermediate in the CDO catalytic cycle and the essential NHase Fe-S(O)(Cys114) proposed to be intimately involved in nitrile hydrolysis. Comparison of the reactivity of 2 with that of a more electron-rich, crystallographically characterized derivative, [Fe(III)S2(Me2)N(Me)N2(amide)(Pr,Pr)](-) (8), shows that oxo atom donor reactivity correlates with the metal ion's ability to bind exogenous ligands. Density functional theory calculations suggest that the mechanism of S-oxygenation does not proceed via direct attack at the thiolate sulfurs; the average spin-density on the thiolate sulfurs is approximately the same for 2 and 8, and Mulliken charges on the sulfurs of 8 are roughly twice those of 2, implying that 8 should be more susceptible to sulfur oxidation. Carboxamide-ligated 8 is shown to be unreactive towards oxo atom donors, in contrast to imine-ligated 2. Azide (N3(-)) is shown to inhibit sulfur oxidation with 2, and a green intermediate is observed, which then slowly converts to sulfenate-ligated 5. This suggests that the mechanism of sulfur oxidation involves initial coordination of the oxo atom donor to the metal ion. Whether the green intermediate is an oxo atom donor adduct, Fe-O═I-Ph, or an Fe(V)═O remains to be determined.

  9. Shewanella oneidensis MR-1-Induced Fe(III) Reduction Facilitates Roxarsone Transformation

    OpenAIRE

    2016-01-01

    Although microbial activity and associated iron (oxy)hydroxides are known in general to affect the environmental dynamics of 4-hydroxy-3-nitrobenzenearsonic acid (roxarsone), the mechanistic understanding of the underlying biophysico-chemical processes remains unclear due to limited experimental information. We studied how Shewanella oneidensis MR-1 –a widely distributed metal-reducing bacterium, in the presence of dissolved Fe(III), affects roxarsone transformations and biogeochemical cyclin...

  10. 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.

  11. 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.

  12. Rapid electron exchange between surface-exposed bacterial cytochromes and Fe(III) minerals

    Energy Technology Data Exchange (ETDEWEB)

    White, Gaye F.; Shi, Zhi; Shi, Liang; Wang, Zheming; Dohnalkova, Alice; Marshall, Matthew J.; Fredrickson, Jim K.; Zachara, John M.; Butt, Julea N.; Richardson, David; Clarke, Thomas A.

    2013-04-16

    The mineral respiring bacterium Shewanella oneidensis uses a protein complex, MtrCAB, composed of two decaheme cytochromes brought together inside a transmembrane porin to transport electrons across the outer membrane to a variety of mineral-based electron acceptors. A proteoliposome system that contains methyl viologen as an internalised electron carrier has been used to investigate how the topology of the MtrCAB complex relates to its ability to transport electrons across a lipid bilayer to externally-located Fe(III) oxides. With MtrA facing the interior and MtrC exposed on the outer surface of the phospholipid bilayer, direct electron transfer from the interior through MtrCAB to solid-phase Fe(III) oxides was demonstrated. The observed rates of conduction through the protein complex were 2 to 3 orders of magnitude higher than that observed in whole cells, demonstrating that direct electron exchange between MtrCAB and Fe(III) oxides is efficient enough to support in-vivo, anaerobic, solid phase iron respiration.

  13. Kinetic studies of nitrate removal from aqueous solution using granular chitosan-Fe(III) complex.

    Science.gov (United States)

    Hu, Qili; Chen, Nan; Feng, Chuanping; Zhang, Jing; Hu, Weiwu; Lv, Long

    2016-01-01

    In the present study, a granular chitosan-Fe(III) complex was prepared as a feasible adsorbent for the removal of nitrate from an aqueous solution. There was no significant change in terms of nitrate removal efficiency over a wide pH range of 3-11. Nitrate adsorption on the chitosan-Fe(III) complex followed the Langmuir-Freundlich isotherm model. In order to more accurately reflect adsorption and desorption behaviors at the solid/solution interface, kinetic model I and kinetic model II were proposed to simulate the interfacial process in a batch system. Nitrate adsorption on the chitosan-Fe(III) complex followed the pseudo-first-order kinetic model and kinetic model I. The proposed half-time could provide useful information for optimizing process design. Adsorption and desorption rate constants obtained from kinetic model I and kinetic model II were beneficial to understanding the interfacial process and the extent of adsorption reaction. Kinetic model I and kinetic model II implied that nitrate uptake exponentially approaches a limiting value.

  14. 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.

  15. Catalytic wet peroxide oxidation of p-nitrophenol by Fe (III) supported on resin.

    Science.gov (United States)

    Liou, Rey-May; Chen, Shih-Hsiung; Huang, Cheng-Hsien; Lai, Cheng-Lee; Shih, C Y; Chang, Jing-Song; Hung, Mu-Ya

    2010-01-01

    Fe(III) supported on resin (Fe(III)-resin) as an effective catalyst for peroxide oxidation was prepared and applied for the degradation of p-nitrophenol (PNP). Catalytic wet peroxide oxidation (CWPO) experiments with hydrogen peroxide as oxidant were performed in a batch rector with p-nitrophenol as the model pollutant. Under given conditions (PNP concentration 500 mg/L, H(2)O(2) 0.1 M, 80°C, resin dosage 0.6% g/mL), p-nitrophenol was almost completely removed, corresponding to an 84% of COD removal. It was found that the reaction temperature, oxidant concentration. and initial pH of solution significantly affected both p-nitrophenol conversion and COD removal by oxidation. It can be inferred from the experiments that Fe(III) supported on resin was an effective catalyst in the mineralization of p-nitrophenol. In an acidic environment of oxidation, the leaching test showed that there was only a slight leaching effect on the activity of catalytic oxidation. It was also confirmed by the aging test of catalysts in the oxidation.

  16. Extraction of Fe(III) and U(VI) with 1-phenyl-3-methyl-4-acyl-pyrazolones-5 from aqueous solutions of different acids and complexing agents. Separation of Fe(III) from U(VI)

    Energy Technology Data Exchange (ETDEWEB)

    Okafor, E.C. (Nigeria Univ., Nsukka (Nigeria). Dept. of Pure and Industrial Chemistry); Uzoukwu, B.A. (Port Harcourt Univ. (Nigeria). Dept. of Pure and Industrial Chemistry)

    1990-01-01

    Solvent extraction behaviour of Fe(III) and U(VI) in aqueous media containing various mineral acids or complexing agents, using 4-butyryl, 4-palmitoyl and 4-trichloroacetyl derivatives of 1-phenyl-3-methyl-pyrazolone-5 in xylene as extraction reagents have been studied. The possible extraction mechanism has been investigated. Solid complexes of Fe(III) and U(VI) with the chelating agents have been isolated and analysed. Separation factors of Fe(III) and U(VI) using these chelating agents are reported and methods suggested for separation of Fe(III) from U(VI) in an aqueous medium containing 0.1 M HCl or 5x10{sup -4} M EDTA. (orig.).

  17. Applying the Fe(III) binding property of a chemical transferrin mimetic to Ti(IV) anticancer drug design.

    Science.gov (United States)

    Parks, Timothy B; Cruz, Yahaira M; Tinoco, Arthur D

    2014-02-03

    As an endogenous serum protein binder of Ti(IV), transferrin (Tf) serves as an excellent vehicle to stabilize the hydrolysis prone metal ion and successfully transport it into cells. This transporting role is thought to be central to Ti(IV)'s anticancer function, but efforts to synthesize Ti(IV) compounds targeting transferrin have not produced a drug. Nonetheless, the Ti(IV) transferrin complex (Ti2Tf) greatly informs on a new Ti(IV)-based anticancer drug design strategy. Ti2Tf interferes with cellular uptake of Fe(III), which is particularly detrimental to cancer cells because of their higher requirement for iron. Ti(IV) compounds of chemical transferrin mimetic (cTfm) ligands were designed to facilitate Ti(IV) activity by attenuating Fe(III) intracellular levels. In having a higher affinity for Fe(III) than Ti(IV), these ligands feature the appropriate balance between stability and lability to effectively transport Ti(IV) into cancer cells, release Ti(IV) via displacement by Fe(III), and deplete the intracellular Fe(III) levels. The cTfm ligand N,N'-di(o-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid (HBED) was selected to explore the feasibility of the design strategy. Kinetic studies on the Fe(III) displacement process revealed that Ti(IV) can be transported and released into cells by HBED on a physiologically relevant time scale. Cell viability studies using A549 cancerous and MRC5 normal human lung cells and testing the cytotoxicity of HBED and its Ti(IV), Fe(III), and Ga(III) compounds demonstrate the importance of Fe(III) depletion in the proposed drug design strategy and the specificity of the strategy for Ti(IV) activity. The readily derivatized cTfm ligands demonstrate great promise for improved Ti(IV) anticancer drugs.

  18. 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

  19. Direct and simultaneous spectrophotometric determination of Fe (III and Ni (II using salicylaldehyde acetoacetic acid hydrazone – Applications

    Directory of Open Access Journals (Sweden)

    V Srilalitha

    2010-12-01

    Full Text Available A rapid, simple and sensitive spectrophotometric method has been developed for determination of Fe (III and Ni (II using salicylaldehyde acetoacetic acid hydrazone (SAAH as a chromophoric reagent. The linear calibration ranges were obtained in each case. The proposed method is applied for the simultaneous determination of Fe (III and Ni (II utilizing their first order spectra. The method is based on the zero crossing measurement of first derivative amplitudes. The first derivative amplitudes at 525 nm and 395 nm obey Beer's law in the concentration range 0.054-0.270 μg/mL and 0.112-0.561 μg/mL for Fe (III and Ni (II respectively. A large number of foreign ions do not interfere in the present method. The method is used for the determination of micro amounts of Fe (III and Ni (II in alloy steels and in synthetic mixtures.

  20. 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

  1. Microbial removal of uranyl by sulfate reducing bacteria in the presence of Fe (III) (hydr)oxides.

    Science.gov (United States)

    Zhengji, Yi

    2010-09-01

    Microbiological reduction of uranyl by sulfate reducing bacteria (SRB) has been proposed as a promising method for removal of radionuclide from groundwater. In this study, we examined the effect of two naturally occurring Fe(III) (hydr)oxides, hematite and goethite, on the bioreduction of U(VI) by a mixed culture of SRB via laboratory batch experiments. The biogenic precipitate from U(VI) bioreduction was determined using X-ray absorption near edge structure (XANES) analysis, showing a typical feature of uraninite (UO(2)). In the presence of either hematite or goethite-containing Fe(III) ranging from 10 to 30 mM, the reduction of U(VI) was retarded by both minerals and the retardatory effect was enhanced with increasing amount of Fe(III) (hydr)oxide. When exposed to a mixture of hematite and goethite with the total Fe(III) kept constant at 20 mM, the retardatory effect on U(VI) reduction by the minerals were directly correlated with the fraction of hematite present. A slow increase in U(VI) concentration was also found in all Fe(III) (hydr)oxide treatments after 10-13 days, accompanied by the release of Fe(II) into the solution. The presence of Fe(III) (hydr)oxide can cause the eventual incomplete bioreduction of U(VI). However, it was not the case for the control without minerals. When mixing biogenic uraninite with hematite or goethite without SRB, Fe(II) was also detected in the solution. These findings suggest that the U(VI) remobilization after 1013 days may be due to reoxidation of the uraninite by the solid-phase Fe(III) (hydr)oxide. Copyright 2010 Elsevier Ltd. All rights reserved.

  2. Study Of Fe(iii)-nta Chelates Stability For Applicability In Photo-fenton At Neutral Ph

    OpenAIRE

    De Luca; Antonella; Dantas; Renato F.; Esplugas; Santiago (Archidiócesis) . Arzobispo (Agustín Antolínez).

    2016-01-01

    The stability of ferric nitrilotriacetate chelates (Fe(III)-NTA) was studied under thermal, oxidative and photochemical stress. The knowledge of chelate stability is fundamental to correctly implement the management system of wastewater treatment plant for application of chelates as catalyst in photo-Fenton process at neutral pH. Fe(III)-NTA solution stability was monitored under different temperature conditions (T=10-30 degrees C), in presence and absence of UV-A irradiation and by adding th...

  3. Adsorption Kinetic Properties of As(III) on Synthetic Nano Fe-Mn Binary Oxides

    Institute of Scientific and Technical Information of China (English)

    Mei Yu; Yanxin Wang; Shuqiong Kong; Evalde Mulindankaka; Yuan Fang; Ya Wu

    2016-01-01

    The adsorptive removal of arsenic by synthetically-prepared nano Fe-Mn binary oxides (FM) was investigated. A novel method using potassium permanganate and ferric chloride as raw materials was used to synthesise FM. The molar ratio of Fe and Mn in the synthetic Fe-Mn binary oxides was 4 : 3. The FM-1 and FM-2 (prepared at different activation temperatures) having high specific surface areas (358.87 and 128.58 m2/g, respectively) were amorphous and of nano particle types. The amount of arsenic adsorbed on FM-1 was higher than that adsorbed on FM-2 particles. After adsorption by FM-1, residual arsenic concentration decreased to less than 10μg/L. The adsorption kinetics data were analyzed using different kinetic models including pseudofirst-order model, pseudo second-order model, Elovich model and in-traparticle diffusion model. Pseudo second-order kinetic model was the most appropriate model to describe the adsorption kinetics. The adsorption percentage of As(III) increased in the pH range of 2–3 while it de-creased with the increase of pH ( 3III) removal using FM-1 and FM-2 were also studied and the order of the effects is as follows: NO3-, Cl-, F-III) for adsorptive sites on the surface of the ad-sorbents.The higher adsorption capacity of FM-1 makes it potentially attractive adsorbent for the removal of As(III) from groundwater.

  4. 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.

  5. 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.

  6. Evaluating enhanced sulfate reduction and optimized volatile fatty acids (VFA) composition in anaerobic reactor by Fe (III) addition.

    Science.gov (United States)

    Liu, Yiwen; Zhang, Yaobin; Ni, Bing-Jie

    2015-02-17

    Anaerobic reactors with ferric iron addition have been experimentally demonstrated to be able to simultaneously improve sulfate reduction and organic matter degradation during sulfate-containing wastewater treatment. In this work, a mathematical model is developed to evaluate the impact of ferric iron addition on sulfate reduction and organic carbon removal as well as the volatile fatty acids (VFA) composition in anaerobic reactor. The model is successfully calibrated and validated using independent long-term experimental data sets from the anaerobic reactor with Fe (III) addition under different operational conditions. The model satisfactorily describes the sulfate reduction, organic carbon removal and VFA production. Results show Fe (III) addition induces the microbial reduction of Fe (III) by iron reducing bacteria (IRB), which significantly enhances sulfate reduction by sulfate reducing bacteria (SRB) and subsequently changes the VFA composition to acetate-dominating effluent. Simultaneously, the produced Fe (II) from IRB can alleviate the inhibition of undissociated H2S on microorganisms through iron sulfide precipitation, resulting in further improvement of the performance. In addition, the enhancement on reactor performance by Fe (III) is found to be more significantly favored at relatively low organic carbon/SO4(2-) ratio (e.g., 1.0) than at high organic carbon/SO4(2-) ratio (e.g., 4.5). The Fe (III)-based process of this work can be easily integrated with a commonly used strategy for phosphorus recovery, with the produced sulfide being recovered and then deposited into conventional chemical phosphorus removal sludge (FePO4) to achieve FeS precipitation for phosphorus recovery while the required Fe (III) being acquired from the waste ferric sludge of drinking water treatment process, to enable maximum resource recovery/reuse while achieving high-rate sulfate removal.

  7. Fe(III) oxides protect fermenter-methanogen syntrophy against interruption by elemental sulfur via stiffening of Fe(II) sulfides produced by sulfur respiration.

    Science.gov (United States)

    Igarashi, Kensuke; Kuwabara, Tomohiko

    2014-03-01

    Thermosipho globiformans (rod-shaped thermophilic fermenter) and Methanocaldococcus jannaschii (coccal hyperthermophilic hydrogenotrophic methanogen) established H2-mediated syntrophy at 68 °C, forming exopolysaccharide-based aggregates. Electron microscopy showed that the syntrophic partners connected to each other directly or via intercellular bridges made from flagella, which facilitated transfer of H2. Elemental sulfur (S(0)) interrupted syntrophy; polysulfides abiotically formed from S(0) intercepted electrons that were otherwise transferred to H(+) to produce H2, resulting in the generation of sulfide (sulfur respiration). However, Fe(III) oxides significantly reduced the interruption by S(0), accompanied by stiffening of Fe(II) sulfides produced by the reduction of Fe(III) oxides with the sulfur respiration-generated sulfide. Sea sand replacing Fe(III) oxides failed to generate stiffening or protect the syntrophy. Several experimental results indicated that the stiffening of Fe(II) sulfides shielded the liquid from S(0), resulting in methane production in the liquid. Field-emission scanning electron microscopy showed that the stiffened Fe(II) sulfides formed a network of spiny structures in which the microorganisms were buried. The individual fermenter rods likely produced Fe(II) sulfides on their surface and became local centers of a core of spiny structures, and the connection of these cores formed the network, which was macroscopically recognized as stiffening.

  8. 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.

  9. Free energy of formation for green rust sodium sulphate (NaFe II6Fe III3(OH) 18(SO 4) 2(s))

    Science.gov (United States)

    Davesne, E.; Dideriksen, K.; Christiansen, B. C.; Sonne, M.; Ayala-Luis, K. B.; Koch, C. Bender; Hansen, H. C. B.; Stipp, S. L. S.

    2010-11-01

    In a recent study, sulphate-bearing green rust (GR) was shown to incorporate Na + in its structure (NaFe II6Fe III3(OH) 18(SO 4) 2(s); GR). The compound was synthesised by aerial oxidation of Fe(OH) 2(s) in the presence of NaOH. This paper reports on its free energy of formation (ΔGf0). Freshly synthesised GR was titrated with 0.5 M H 2SO 4 in an inert atmosphere at 25 °C, producing dissolved Fe 2+ and magnetite or goethite. Solution concentrations, PHREEQC and the MINTEQ database were used to calculate reaction constants for the reactions: 2NaFeII6 FeIII3 (OH)18(SO)+12H+(aq) ⇆9Fe2+(aq) +2Na+(aq) +4SO42-(aq) +3FeFeIII2 O+24HO,K=10 and NaFeII6 FeIII3 (OH)18(SO)+9H(aq)+⇆6Fe2+(aq) +Na+(aq) +2SO42-(aq) +3α-FeOOH+12HO,K=10. From the determined equilibrium constants and published ΔGf0 values for the other compounds, we derived ΔGf0 = -6366 ± 18 kJ/mol for anhydrous GR. The solubility product at 25 °C and atmospheric pressure is K = 10 -210.5±3.2. It is not yet known if the extent of Na + incorporation in GR depends on formation pathway; it cannot be excluded that both Na-free GR and GR exist. If so, uncertainty in ΔGf0 determined from acid titration is such that the EH-pH stability fields of the two phases are statistically indistinguishable for Na + concentrations as low as ˜30 μM (2 SD level; 0.036 M SO 42- concentration). In sea water, where Na + and SO 42- concentrations are high, but soluble Fe 2+ is low, GR is expected to form where local conditions increase concentration gradients, such as for corrosion of metallic iron and steel. Another example of an environment that would provide GR-favourable conditions is a degrading concrete and steel radioactive waste storage facility, where groundwater is saline. Green rust is a well-known sink for redox-active trace components, making it a compound that should be considered in risk assessment modelling of groundwater quality. Phase stability is critical in such simulations.

  10. Synthesis and characterization of dopamine substitue tripodal trinuclear [(salen/salophen/salpropen)M] (Mdbnd Cr(III), Mn(III), Fe(III) ions) capped s-triazine complexes: Investigation of their thermal and magnetic properties

    Science.gov (United States)

    Uysal, Şaban; Koç, Ziya Erdem

    2016-04-01

    In this work, we aimed to synthesize and characterize a novel tridirectional ligand including three catechol groups and its novel tridirectional-trinuclear triazine core complexes. For this purpose, we used melamine (2,4,6-triamino-1,3,5-triazine) (MA) as starting material. 2,4,6-tris(4-carboxybenzimino)-1,3,5-triazine (II) was synthesized by the reaction of an equivalent melamine (I) and three equivalent 4-carboxybenzaldehyde. 4,4‧,4″-((1E,1‧E,1″E)-((1,3,5-triazine-2,4,6-triyl)tris(azanylylidene))tris(methanylylidene))tris(N-(3,4-dihydroxyphenethyl)benzamide) L (IV) was synthesized by the reaction of one equivalent (II) and three equivalent dopamine (3,4-dihydroxyphenethylamine) (DA) by using two different methods. (II, III, IV) and nine novel trinuclear Cr(III), Mn(III) and Fe(III) complexes of (IV) were characterized by means of elemental analyses, 1H NMR, FT-IR spectrometry, LC-MS (ESI+) and thermal analyses. The metal ratios of the prepared complexes were performed using Atomic Absorption Spectrophotometry (AAS). We also synthesized novel tridirectional-trinuclear systems and investigated their effects on magnetic behaviors of [salen, salophen, salpropen Cr(III)/Mn(III)/Fe(III)] capped complexes. The complexes were determined to be low-spin distorted octahedral Mn(III) and Fe(III), and distorted octahedral Cr(III) all bridged by catechol group.

  11. 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

  12. Nanostructured Fe(III) catalysts for water oxidation assembled with the aid of organic acid salt electrolytes

    Science.gov (United States)

    Zhao, Qiang; Li, Dandan; Gao, Guofeng; Yuan, Wen; Hao, Genyan; Li, Jinping

    2016-11-01

    We describe the preparation of three partially ordered iron-based catalyst films (Fe-OAc, Fe-Pro, Fe-But) with nanoporous structure by electrodeposition from organate electrolytes containing Fe2+. The anions of the organic acids assisted the partial ordering of the nanostructured Fe(III) catalysts for water oxidation. A model involving an electrical double layer is invoked to explain the role of the organate electrolyte system in their formation. Analytical results have revealed the main component of the iron-based films to be a β-FeOOH structure. The Fe-But catalyst catalyzed water oxidation in 0.1 m potassium carbonate solution with an average activity of 1.48 mA cm-2 and an overpotential of 433 mV.

  13. Adsorption of Sb(III) and Sb(V) on Freshly Prepared Ferric Hydroxide (FeOxHy).

    Science.gov (United States)

    He, Zan; Liu, Ruiping; Liu, Huijuan; Qu, Jiuhui

    2015-02-01

    This study prepared fresh ferric hydroxide (in-situ FeOxHy) by the enhanced hydrolysis of Fe(3+) ions, and investigates its adsorptive behaviors toward Sb(III) and Sb(V) through laboratory and pilot-scale studies. A contact time of 120-min was enough to achieve adsorption equilibrium for Sb(III) and Sb(V) on the in-situ FeOxHy, and the Elovich model was best to describe the adsorption kinetics of Sb(III) and Sb(V). The Freundlich model was better than Langmuir model to describe the adsorption of Sb(III) and Sb(V) on the in-situ FeOxHy, and the maximum adsorption capacity of Sb(III) and Sb(V) was determined to be 12.77 and 10.21 mmol/g the in-situ FeOxHy as Fe, respectively. Adsorption of Sb(V) decreased whereas that of Sb(III) increased with elevated pH over pH 3-10, owing to the different electrical properties of Sb(III) and Sb(V). Adsorption of Sb(III) and Sb(V) was slightly affected by ionic strength, and thus indicated the formation of inner sphere complexes between Sb and the adsorbent. Sulfate and carbonate showed little effect on the adsorption of Sb(III) and Sb(V). Phosphate significantly inhibited the adsorption of Sb(V), whereas slightly effected that of Sb(III) due to its similar chemical structure to Sb(V). Pilot-scale continuous experiment indicated the feasibility of using in-situ FeOxHy to remove Sb(V), and equilibrium adsorption capacity at the equilibrium Sb(V) concentration of 10 μg/L was determined to be 0.11, 0.07, 0.07, 0.11, and 0.12 mg/g the in-situ FeOxHy as Fe at equilibrium pH of 7.5-7.7, 6.9-7.0, 6.3-6.6, 5.9-6.4, and 5.2-5.9, respectively.

  14. The photochemistry of [Fe(III)N3(cyclam-ac)]PF6 at 266 nm.

    Science.gov (United States)

    Torres-Alacan, Joel; Krahe, Oliver; Filippou, Alexander C; Neese, Frank; Schwarzer, Dirk; Vöhringer, Peter

    2012-03-01

    The photochemistry of iron azido complexes is quite challenging and poorly understood. For example, the photochemical decomposition of [Fe(III)N(3)(cyclam-ac)]PF(6) ([1]PF(6)), where cyclam-ac represents the 1,4,8,11-tetraazacyclotetradecane-1-acetate ligand, has been shown to be wavelength-dependent, leading either to the rare high-valent iron(V) nitrido complex [Fe(V)N(cyclam-ac)]PF(6) ([3]PF(6)) after cleavage of the azide N(α)-N(β) bond, or to a photoreduced Fe(II) species after Fe-N(azide) bond homolysis. The mechanistic details of this intriguing reactivity have never been studied in detail. Here, the photochemistry of 1 in acetonitrile solution at room temperature has been investigated using step-scan and rapid-scan time-resolved Fourier transform infrared (FTIR) spectroscopy following a 266 nm, 10 ns pulsed laser excitation. Using carbon monoxide as a quencher for the primary iron-containing photochemical product, it is shown that 266 nm excitation of 1 results exclusively in the cleavage of the Fe-N(azide) bond, as was suspected from earlier steady-state irradiation studies. In argon-purged solutions of [1]PF(6), the solvent-stabilized complex cation [Fe(II)(CH(3)CN)(cyclam-ac)](+) (2red) together with the azide radical (N(3)(.)) is formed with a relative yield of 80%, as evidenced by the appearance of their characteristic vibrational resonances. Strikingly, step-scan experiments with a higher time resolution reveal the formation of azide anions (N(3)(-)) during the first 500 ns after photolysis, with a yield of 20%. These azide ions can subsequently react thermally with 2red to form [Fe(II)N(3)(cyclam-ac)] (1red) as a secondary product of the photochemical decomposition of 1. Molecular oxygen was further used to quench 1red and 2red to form what seems to be the elusive complex [Fe(O(2))(cyclam-ac)](+) (6).

  15. 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.

  16. Mixed ligand complex formation of FeIII with boric acid and typical N-donor multidentate ligands

    Indian Academy of Sciences (India)

    G N Mukherjee; Ansuman Das

    2002-06-01

    Equilibrium study of the mixed ligand complex formation of FeIII with boric acid in the absence and in the presence of 2,2'-bipyridine, 1,10-phenanthroline, diethylenetriamine and triethylenetetramine (L) in different molar ratios provides evidence of formation of Fe(OH)2+, Fe(OH)$^{+}_{2}$, Fe(L)3+, Fe(H2BO4), Fe(OH)(H2BO4)-, Fe(OH)2(H2BO4)2-, Fe(L)(H2BO4) and Fe2(L)2(BO4)+ complexes. Fe(L)$^{3+}_{2}$, Fe(L)2(H2BO4) and Fe2(L)4(BO4)+ complexes are also indicated with 2,2'-bipyridine and 1,10-phenanthroline. Complex formation equilibria and stability constants of the complexes at 25 ± 0 × 1° C in aqueous solution at a fixed ionic strength, = 0.1 mol -3 (NaNO3) have been determined by potentiometric method.

  17. Crystal structure of K0.75[FeII3.75FeIII1.25(HPO36]·0.5H2O, an open-framework iron phosphite with mixed-valent FeII/FeIII ions

    Directory of Open Access Journals (Sweden)

    Edurne S. Larrea

    2016-01-01

    Full Text Available Single crystals of the title compound, potassium hexaphosphitopentaferrate(II,III hemihydrate, K0.75[FeII3.75FeIII1.25(HPO36]·0.5H2O, were grown under mild hydrothermal conditions. The crystal structure is isotypic with Li1.43[FeII4.43FeIII0.57(HPO36]·1.5H2O and (NH42[FeII5(HPO36] and exhibits a [FeII3.75FeIII1.25(HPO36]0.75− open framework with disordered K+ (occupancy 3/4 as counter-cations. The anionic framework is based on (001 sheets of two [FeO6] octahedra (one with point group symmetry 3.. and one with point group symmetry .2. linked along [001] through [HPO3]2− oxoanions. Each sheet is constructed from 12-membered rings of edge-sharing [FeO6] octahedra, giving rise to channels with a radius of ca 3.1 Å where the K+ cations and likewise disordered water molecules (occupancy 1/4 are located. O...O contacts between the water molecule and framework O atoms of 2.864 (5 Å indicate hydrogen-bonding interactions of medium strength. The infrared spectrum of the compound shows vibrational bands typical for phosphite and water groups. The Mössbauer spectrum is in accordance with the presence of FeII and FeIII ions.

  18. Speciation of Fe(II) and Fe(III) by the modified ferrozine method, FIA-spectrophotometry, and flame AAS after cloud-point extraction

    Energy Technology Data Exchange (ETDEWEB)

    Giokas, Dimosthenis L.; Paleologos, Evangelos K.; Karayannis, Miltiades I. [Laboratory of Analytical Chemistry, Department of Chemistry, University of Ioannina (Greece)

    2002-07-01

    A method has been developed for the simultaneous determination of traces of Fe(III) and Fe(II) in water by on-line coupling of spectrophotometry with flame atomic absorption spectrometry (FAAS). The method involves cloud-point extraction (CPE) of both species with ammonium pyrrolidinecarbodithioate (APDC) under standard conditions, which facilitates the in situ complexation and extraction of both species. Differentiation of the oxidation states of iron is achieved by using mathematical equations to overcome the interference of Fe(III) in the spectrophotometric determination of Fe(II) when they are both present in the same solution. In this manner the time-consuming and labor-intensive steps of preoxidation of Fe(II) or reduction of Fe(III) are eliminated. By preconcentrating a 10-mL sample solution detection limits as low as 7 {mu}g L{sup -1}, were obtained after a single-step extraction procedure. The relative standard deviation (n=4, 30 {mu}g L{sup -1}) was 2.6 % and 1.8 % for spectrophotometry and FAAS, respectively. Recoveries in the range of 96-105 % were obtained by analysis of spiked real samples. The method was further verified by analyzing a certified reference material (IMEP-9); for this the recovery was 98.5 %. (orig.)

  19. DECOLORIZATION OF BROMOCRESOL PURPLE (BCP PHOTOINDUCED BY A Fe (III OXYHYDROXYDE (GOETHITE

    Directory of Open Access Journals (Sweden)

    S BELATTAR

    2014-06-01

    Full Text Available This study focused on the decolorization of bromocresol purple (BCP using Fe (III oxyhydroxide (Goethite as an inducer. The mixture dye- Goethite in dark condition and ambient temperature, shows a reaction between the dye and the Fe (III oxyhydroxide. Indeed, the tracking of the reaction using UV-visible spectrophotometry showed a low decrease in the principal band of the dye. This reveal the existence of an interaction between the substrate and the Goethite whitch is important in acidic medium. The irradiation at 365 nm of mixture Goethite-BCP (1g.L-1- 10-4 M leads to a transformation of substrate. The decrease of the band at 432nm and the presence of an isosbestic point at 508 nm support the transformation of BCP.  The substrate kinetics disappearances are improved in acidic medium. The addition of hydrogen peroxide (5.10-3 mol.L-1 in a suspension of Goethite, accelerate significantly the rate of disappearance of the dye. Natural radiation tests showed that the degradation was faster than artificial one at 365 nm. Studies on mineralization using COD method certify that this method, compatible with the environment, may be considered in the treatment of wastewater.

  20. Synthesis, spectroscopic, thermal and anticancer studies of metal-antibiotic chelations: Ca(II), Fe(III), Pd(II) and Au(III) chloramphenicol complexes

    Science.gov (United States)

    Al-Khodir, Fatima A. I.; Refat, Moamen S.

    2016-09-01

    Four Ca(II), Fe(III), Pd(II) and Au(III) complexes of chloramphenicol drug have been synthesized and well characterized using elemental analyses, (infrared, electronic, and 1H-NMR) spectra, magnetic susceptibility measurement, and thermal analyses. Infrared spectral data show that the chloramphenicol drug coordinated to Ca(II), Pd(II) and Au(III) metal ions through two hydroxyl groups with 1:1 or 1:2 M ratios, but Fe(III) ions chelated towards chloramphenicol drug via the oxygen and nitrogen atoms of amide group with 1:2 ratio based on presence of keto↔enol form. The X-ray powder diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM) techniques were used to identify the nano-size particles of both iron(III) and gold(III) chloramphenicol complexes. The antimicrobial assessments of the chloramphenicol complexes were scanned and collected the results against of some kind of bacteria and fungi. The cytotoxic activity of the gold(III) complex was tested against the human colon carcinoma (HCT-116) and human hepatocellular carcinoma (HepG-2) tumor cell lines.

  1. Carbon dots preparation as a fluorescent sensing platform for highly efficient detection of Fe(III) ions in biological systems.

    Science.gov (United States)

    Hamishehkar, Hamed; Ghasemzadeh, Bahar; Naseri, Abdolhossein; Salehi, Roya; Rasoulzadeh, Farzaneh

    2015-01-01

    Water-soluble carbon dots (CDs) were prepared, using a facile hydrothermal oxidation route of cyclic oligosaccharide α-CD, as carbon sources, and alkali as additives. The successful synthesis of CDs was confirmed by scanning electron microscopy (SEM), dynamic light scattering (DLS), FTIR, UV-visible absorption, and emission fluorescence. The characterizations showed that the prepared CDs are spherical and well-dispersed in water with average diameters of approximately 2 nm. These water-soluble CDs have excellent photo stability towards photo bleaching during 30 days. The obtained CDs showed a strong emission at the wavelength of 450 nm, with an optimum excitation of 360 nm. The fluorescence quenching of CDs in the presence of Fe(III) ions was used as fluorescent probes for quantifying Fe(III) ions in aqueous solution. Under optimum condition, the fluorescence intensity versus Fe(III) concentration gave a linear response, according to Stern-Volmer equation. The linearity range of the calibration curve and the limit of detection were 1.60×10(-5) to 16.6×10(-5) mol L(-1), and 6.05×10(-6) mol L(-1), respectively, which was in the range for serum analysis of Fe(III). It was concluded that the prepared CDs had a great potential as fluorescent probes for applications in analysis of Fe(III) ions in the blood serum samples, which is hardly interfered by other ions.

  2. 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.

  3. A New Insight of Graphene oxide-Fe(III) Complex Photochemical Behaviors under Visible Light Irradiation

    Science.gov (United States)

    Liu, Renlan; Zhu, Xiaoying; Chen, Baoliang

    2017-01-01

    Graphene oxide (GO) contains not only aromatic carbon lattice but also carboxyl groups which enhanced the aqueous solubility of GO. To study the transformation of GO nanosheets in natural environments, GO aqueous dispersion was mixed with Fe3+ ions to form photoactive complex. Under visible light irradiation, Fe(III) of the complex would be reduced to Fe(II) which could subsequently reduce highly toxic Cr(VI) to Cr3+. The electron of the reduction was contributed by the decarboxylation of carboxyl groups on GO and iron was acting as a catalyst during the photoreduction. On the other hand, the consumption of carboxyl groups may convert GO to rGO which are tend to aggregate since the decreased electrostatic repulsion and the increased π-π attraction. The formed Cr3+ may be electrostatically adsorbed by the rGO sheets and simultaneously precipitated with the aggregated rGO sheets, resulting the effective removal of chromium and GO nanosheets from the aqueous environment. This study may shed a light on understanding the environmental transformation of GO and guide the treatment of Cr(VI). PMID:28084446

  4. Energetic Limitations on Microbial Respiration of Organic Compounds using Aqueous Fe(III) Complexes

    Science.gov (United States)

    Naughton, H.; Fendorf, S. E.

    2015-12-01

    Soil organic matter constitutes up to 75% of the terrestrial carbon stock. Microorganisms mediate the breakdown of organic compounds and the return of carbon to the atmosphere, predominantly through respiration. Microbial respiration requires an electron acceptor and an electron donor such as small fatty acids, organic acids, alcohols, sugars, and other molecules that differ in oxidation state of carbon. Carbon redox state affects how much energy is required to oxidize a molecule through respiration. Therefore, different organic compounds should offer a spectrum of energies to respiring microorganisms. However, microbial respiration has traditionally focused on the availability and reduction potential of electron acceptors, ignoring the organic electron donor. We found through incubation experiments that the organic compound serving as electron donor determined how rapidly Shewanella putrefaciens CN32 respires organic substrate and the extent of reduction of the electron acceptor. We simulated a range of energetically favorable to unfavorable electron acceptors using organic chelators bound to Fe(III) with equilibrium stability constants ranging from log(K) of 11.5 to 25.0 for the 1:1 complex, where more stable complexes are less favorable for microbial respiration. Organic substrates varied in nominal oxidation state of carbon from +2 to -2. The most energetically favorable substrate, lactate, promoted up to 30x more rapid increase in percent Fe(II) compared to less favorable substrates such as formate. This increased respiration on lactate was more substantial with less stable Fe(III)-chelate complexes. Intriguingly, this pattern contradicts respiration rate predicted by nominal oxidation state of carbon. Our results suggest that organic substrates will be consumed so long as the energetic toll corresponding to the electron donor half reaction is counterbalanced by the energy available from the electron accepting half reaction. We propose using the chemical

  5. Stability of arsenate-bearing Fe(III)/Al(III) co-precipitates in the presence of sulfide as reducing agent under anoxic conditions.

    Science.gov (United States)

    Doerfelt, Christoph; Feldmann, Thomas; Roy, Ranjan; Demopoulos, George P

    2016-05-01

    Currently, the co-precipitation of arsenate with ferric iron at molar ratios Fe(III)/As(V) ≥ 3 by lime neutralization produces tailings solids that are stable under oxic conditions. However not much is known about the stability of these hazardous co-precipitates under anoxic conditions. These can develop in tailings storage sites by the action of co-discharged reactive sulfides, organic reagent residuals or bacterial activity. The ferric matrix can then undergo reductive dissolution reactions, which could release arsenic into the pore water. Co-ions like aluminum could provide a redox-immune sink to scavenge any mobilized arsenic as a result of reduction of ferric. As such, in this work Fe(III)/As(V) = 4 and aluminum substituted Fe(III)/Al(III)/As(V) = 2/2/1 co-precipitates were produced in a mini continuous co-precipitation process circuit and subjected to excess sulfide addition under inert gas to evaluate their stability. It was found that the ferric-arsenate co-precipitate could retain up to 99% (30 mg/L in solution) of its arsenic content despite the high pH (10.5) and extremely reducing (Eh ferric iron was reduced. Partial aluminum substitution was found to cut the amount of mobilized arsenic by 50% (down to 15 mg/L) hence mixed Fe(III)/Al(III)-arsenate co-precipitates may offer better resistance to reductive destabilization over the long term than all iron co-precipitates. Copyright © 2016 Elsevier Ltd. All rights reserved.

  6. 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...

  7. Tri-μ-ethanethiolato-bis{[η5-1,2,3,4-tetramethyl-5-(trimethylsilylcyclopentadienyl]iron(II,III}(FeII–FeIII

    Directory of Open Access Journals (Sweden)

    Jing Li

    2009-12-01

    Full Text Available The title complex, [Fe2(C2H5S3(C12H21Si2], has an unusual Fe2S3 core. The two 1,2,3,4-tetramethyl-5-(trimethylsilylcyclopentadienyl (Cp′ ligands coordinate to the Fe atoms with their C5 planes perpendicular [dihedral angles = 88.23 (7 and 88.55 (7°] to the Fe—Fe vector, building two Cp′Fe subunits. These two subunits are bridged by three thiolate ligands. There are no significant differences in the coordination geometries between the two Fe atoms. The short Fe—Fe distance of 2.7842 (5 Å is clear evidence of an intermetallic bond. Such a diiron–sulfur structure might act as a model of active sites in some metalloproteins.

  8. Nano-sized magnetic iron oxides as catalysts for heterogeneous Fenton-like reactions-Influence of Fe(II)/Fe(III) ratio on catalytic performance.

    Science.gov (United States)

    Rusevova, Klara; Kopinke, Frank-Dieter; Georgi, Anett

    2012-11-30

    Nano-sized Fe(II, III) oxides with various Fe(II)/Fe(III) ratios were characterized and tested as catalysts for the oxidative degradation of phenol via Fenton-like reactions at neutral pH. Under conditions typically applied for wet peroxide oxidation, Fe(II) in magnetite is oxidized to Fe(III), successively converting the mineral into maghemite. The residual Fe(II) content in the catalyst core is of only minor benefit for the catalytic activity in phenol oxidation, i.e. magnetite is not superior to maghemite. Achievable reaction rates for phenol degradation appeared to be rather low, e.g. phenol half-life of about 12 h when 3 g L(-1) magnetite and 5 g L(-1) H(2)O(2) were applied. Preceding surface-reduction of maghemite by NaBH(4), leading to an over-stoichiometric Fe(II) content compared to magnetite, only enhanced the non-productive decomposition of H(2)O(2) rather than the rate of phenol degradation. Reaction rates were shown to be relatively insensitive to catalyst concentration in the range of 1-10 g L(-1), probably resulting from a scavenging of reactive species by the catalyst surface, whereby particle agglomeration seems to play a key role. Degradation experiments with various structurally distinct compounds were carried out, indicating a similar selectivity of the heterogeneous Fenton-like system to that known for oxidation with ·OH. Copyright © 2012 Elsevier B.V. All rights reserved.

  9. 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.

  10. Study of Stability Constants of Fe (Iii And Mn (Ii with Chloramphenicol by Paper Electrophoretic Technique

    Directory of Open Access Journals (Sweden)

    Arvind Singh

    2014-12-01

    Full Text Available Stabilty constant of binary complexes of Fe(III and Mn(II with medicinally important ligand chloramphenicol antibiotics in solution were determined by paper electrophoretic technique. Stability constant of the complexes were determined at 25°C temperature and 0.1M (HClO4 ionic strength. Our study is based upon the migration of a spot of metal ions on a paper strip at different pH against mobility gives information about the binary complexes and permits to calculate their stability constant. The stability constant data revealed that chloramphenicol may be used as chelating agent in chelation for medical treatment of metal overload or poisoning.

  11. Polymorphism in the spin-crossover ferric complexes [(TPA)Fe(III)(TCC)]PF6.

    Science.gov (United States)

    Collet, Eric; Boillot, Marie Laure; Hebert, Johan; Moisan, Nicolas; Servol, Marina; Lorenc, Maciej; Toupet, Loïc; Buron-Le Cointe, Marylise; Tissot, Antoine; Sainton, Joelle

    2009-08-01

    We have identified two polymorphs of the molecular complex [(TPA)Fe((III))(TCC)]PF(6) [TPA = tris(2-pyridylmethyl)amine and TCC = 3,4,5,6-tetrachlorocatecholate dianion]: one is monoclinic and the other is orthorhombic. By lowering the temperature both undergo a thermal spin-crossover between a high-spin (S = 5/2) and a low-spin (S = 1/2) state, which we detected by magnetic, optical and X-ray diffraction measurements. The thermal crossover is only slightly shifted between the polymorphs. Their crystalline structures consist of similar cation layers alternating with PF(6) anion layers, packed differently in the two polymorphs. The magnetic and optical properties of the polymorphs are presented.

  12. Highly solar active Fe(III) immobilised alumina for the degradation of Acid Violet 7

    Energy Technology Data Exchange (ETDEWEB)

    Muthuvel, Inbasekaran; Swaminathan, Meenakshisundaram [Department of Chemistry, Annamalai University, Annamalainagar 608 002 (India)

    2008-08-15

    The hetero-Fenton catalyst Fe(III)-Al{sub 2}O{sub 3} was prepared and characterised by ICP-AES, FT-IR and SEM-EDX. A detailed investigation of photocatalytic degradation of Acid Violet 7 (AV 7) using this Fenton immobilised Al{sub 2}O{sub 3} catalyst was carried out. The optimal reaction conditions for the photodegradation of AV 7 with this catalyst are reported. Higher efficiency of the catalyst in solar light than in UV light makes this heterophoto-Fenton degradation, a green technological process. The catalyst is found to be stable and reusable. The completion of degradation has also been confirmed by chemical oxygen demand (COD) measurements. (author)

  13. Microbial reduction of Fe(III) in hematite nanoparticles by Geobacter sulfurreducens.

    Science.gov (United States)

    Yan, Beizhan; Wrenn, Brian A; Basak, Soubir; Biswas, Pratim; Giammar, Daniel E

    2008-09-01

    The rates of microbial Fe(III) reduction of three sizes of hematite nanoparticles by Geobacter sulfurreducens were measured under two H2 partial pressures (0.01 and 1 atm) and three pH (7.0, 7.5, and 8.0) conditions. Hematite particles with mean primary particle sizes of 10, 30, and 50 nm were synthesized by a novel aerosol method that allows tight control of the particle size distribution. The mass-normalized reduction rates of the 10 and 30 nm particles were comparable to each other and higher than the rate for the 50 nm particles. However, the surface area-normalized rate was highest for the 30 nm particles. Consistent with a previously published model, the reduction rates are likely to be proportional to the bacteria-hematite contact area and not to the total hematite surface area. Surface area-normalized iron reduction rates were higher than those reported in previous studies, which may be due to the sequestration of Fe(II) through formation of vivianite. Similar initial reduction rates were observed under all pH and H2 conditions studied.

  14. Palladium local structure of La(1-x)Sr(x)Co(1-y)Fe(y-0.03)Pd(0.03)O(3-δ) perovskites synthesized using a one pot citrate method.

    Science.gov (United States)

    Puleo, Fabrizio; Liotta, Leonarda F; La Parola, Valeria; Banerjee, Dipanjan; Martorana, Antonino; Longo, Alessandro

    2014-11-01

    Nanostructured La1-xSrxCo1-yFey-0.03Pd0.03O3-δ (LSCF-Pd) perovskites with fixed La-Sr composition (x = 0.4) and two different Fe contents (y = 0.2 and 0.8) were successfully synthesized using a one pot citrate method starting from nitrates of the metal cations. Pd-free La1-xSrxCo1-yFeyO3-δ (LSCF) systems were prepared for comparison. LSCF powders were calcined at 1300 °C and characterized by XRD and Rietveld refinement, EXAFS, XPS, TPR analyses. Promotion of La0.6Sr0.4Co0.8Fe0.2O3-δ and of La0.6Sr0.4Co0.2Fe0.8O3-δ by incorporation of palladium was evidenced by solving the local environment of Pd using EXAFS spectroscopy. XPS analyses, in agreement with TPR measurements, demonstrated an increase of superficial oxygen vacancies, the variation being much more pronounced in the La0.6Sr0.4Co0.8Fe0.17Pd0.03O3-δ sample. It is argued that this increase is associated with the introduction of Pd in the B site of LSCF. Moreover, ionic Pd(4+) was detected as the only palladium species on the perovskite surface, whereas Pd metal clusters of about 2 nm, not detectable in the surface, are embedded in the matrix and strongly interact with the bulk. This result has strong consequences in the synthesis and in the design of new perovskite materials that can be used as cathodes in fuel cell application at intermediate operating temperatures.

  15. Photocatalytic degradation of phenol in Aqueous Solutions by Fe(III-doped TiO2/UV Process

    Directory of Open Access Journals (Sweden)

    R Nabizadeh Nodehi

    2011-01-01

    Full Text Available "n "nBackgrounds and Objectives: Phenol and phenolic compounds are widely used in industry and daily liFe, and are of high interest due to stability in the environment, dissolution ability in water and health problems. In this regard, phenol removal from water is of high importance. The purpose of this study was to investigate the efficiency of photodegradation process for removal of phenol from aqueous system by use of Fe-doped TiO2 nanoparticles prepared by sol-gel method."nMaterials and Methods: Phenol concentrations of 5, 10, 50 and 100 mg/L were prepared and exposed to UV and Fe-doped TiO2, separately and simultaneously. Also the effect of initial phenol concentration, Fe-doped TiO2 loading and pH were studied. Various doses of photocatalist investigated for Fe- doped TiO2 were 0.25, 0.5 and 1 g/L. pH was studied at three ranges, acidic (pH=3, neutral (pH=7 and alkaline (pH=11."nResults: Maximum degradation was obtained at acidic pH, 0.5 g/L of Fe-doped TiO2 for all of phenol concentrations. With increasing initial concentration of phenol, photocatalytic degradation decreased. In comparison with Fe-doped TiO2/UV process, efficiency of UV radiation alone was low in phenol degradation (% 64.5 at 100 mg/l of phenol concentration. Also the amount of phenol adsorbed on the Fe-doped TiO2 was negligible at dark conditions."nConclusion: Results of this study showed that Fe(III- doped TiO2 nanoparticles had an important effect on photocatalytic degradation of high initial phenol concentration when Fe(III-doped TiO2/ UV process applied.

  16. Iron (III oxide fabrication from natural clay with reference to phase transformation γ- → α-Fe2O3

    Directory of Open Access Journals (Sweden)

    Šaponjić Aleksandra

    2017-01-01

    Full Text Available Amorphous iron (III oxide was obtained from clay, using ammonium hydroxide as a precipitating agent. Influence of freeze drying under vacuum, as a drying method, on particle size, chemical composition, and crystallinity of obtained iron (III oxide powder was investigated. After freeze drying, precipitate was annealed in air at 500°C and 900°C. X-ray diffraction, particle size analysis, scanning electron microscopy, energy dispersive spectrometry, Fourier transform infrared spectroscopy, thermogravimetric and differential thermal analysis were used to characterize obtained iron (III oxide powder. All of three powders obtained by freeze drying and annealing, have low crystallinity and particles with irregular layered shape. Narrow particle size distribution was given by an average diameter value of around 50 μm for all observed powders. Iron-bearing materials like α-Fe2O3 and γ- Fe2O3 are obtained. Differential thermal analysis curve of obtained samples showed endothermic reaction at 620°C which could be ascribed to phase transition from cubic form γ- → α- Fe2O3. Thermal transformations of iron (III oxide, obtained from clay as a natural source, is suitable to explore in the framework of materials chemistry, and opens the possibility to synthesize materials based on Fe2O3 with specific magnetic behavior. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. III-45012, Grant no. OI-172045, Grant no. III-45015, Grant no. OI-176010, Grant no. OI-172056 and Grant no. III-45007

  17. U(VI) Uptake and Reduction by Fe(II)-Bearing Secondary Mineralization Products of the Bioreduction of Fe(III) Oxides by Dissimilatory Fe(III)-Reducing Bacteria

    Science.gov (United States)

    O'Loughlin, E. J.; Kelly, S. D.; Kemner, K. M.

    2008-12-01

    Biogenic Fe(II) phases (magnetite, green rust, siderite, vivianite, etc.) provide a reservoir of reducing capacity in the subsurface that may contribute to the reduction of contaminants such as U(VI). In this study we examined the potential for the uptake and reduction of U(VI) in the presence of biogenic green rust, (BioGR) biogenic magnetite (BioMAG), and biogenic siderite (BioSID) resulting from the reduction of Fe(III) oxides by Shewanella putrefaciens CN32. Suspensions of biogenic Fe(II) phases were pasteurized (70 °C for 1 h) to eliminate the potential for microbial reduction of U(VI) and washed repeatedly to remove any soluble reductants. The suspensions were then spiked with uranyl chloride solution. Within 48 h, the total solution-phase U(VI) concentrations decreased from 500 μM to 1.5 μM in the U-BioGR system, to 392 μM in the U-BioMAG system, and to 472 μM in the U-BioSID system, as determined by ICP- OES. Analysis of the samples by U LIII extended X-ray absorption fine structure spectroscopy (EXAFS) indicated that despite a stoichiometric excess of Fe(II), no more than 6% of U(VI) was reduced in the U- BioSID system, and no more than 22% of U(VI) was reduced in the U-BioMAG system. For comparison, in the U-BioGR system, no less than 80% of U(VI) was reduced to U(IV). Uptake of U(VI) by BioGR and BioMAG was accompanied by the formation of nanoparticulate uraninite. The U EXAFS data from the U-BioSID system was consistent with partial U(VI)/U(IV) substitution for Fe(II) in the surface layer of siderite particles and adsorption of U(IV). Our results clearly demonstrate that there are significant differences in reactivity among biogenic Fe(II) phases with respect to the uptake and reduction of U(VI).

  18. Trisilver(I citrate

    Directory of Open Access Journals (Sweden)

    Andreas Fischer

    2011-02-01

    Full Text Available Trisilver(I citrate, 3Ag+·C6H5O73−, was obtained by evaporation of a saturated aqueous solution of the raw material that had been obtained from sodium dihydrogen citrate and silver nitrate. It features one formula unit in the asymmetric unit. There is an intramolecular O—H...O hydrogen bond between the OH group and one of the terminal carboxylate groups. Different citrate groups are linked via the three Ag+ ions, yielding a three-dimensional network with rather irregular [AgO4] polyhedra.

  19. Effect of pH on complex coacervate core micelles from Fe(III)-based coordination polymer.

    Science.gov (United States)

    Wang, Junyou; de Keizer, Arie; van Leeuwen, Herman P; Yan, Yun; Vergeldt, Frank; van As, Henk; Bomans, Paul H H; Sommerdijk, Nico A J M; Cohen Stuart, Martien A; van der Gucht, Jasper

    2011-12-20

    The effect of pH on iron-containing complex coacervate core micelles [Fe(III)-C3Ms] is investigated in this paper. The Fe(III)-C3Ms are formed by mixing cationic poly(N-methyl-2-vinylpyridinium iodide)-b-poly(ethylene oxide) [P2MVP(41)-b-PEO(205)] and anionic iron coordination polymers [Fe(III)-L(2)EO(4)] at stoichiometric charge ratio. Light scattering and Cryo-TEM have been performed to study the variations of hydrodynamic radius and core structure with changing pH. The hydrodynamic radius of Fe(III)-C3Ms is determined mainly by the corona and does not change very much in a broad pH range. However, Cryo-TEM pictures and magnetic relaxation measurements indicate that the structure of the micellar cores changes upon changing the pH, with a more crystalline, elongated shape and lower relaxivity at high pH. We attribute this to the formation of mixed iron complexes in the core, involving both the bis-ligand and hydroxide ions. These complexes are stabilized toward precipitation by the diblock copolymer.

  20. Heterocyclic tri-urea isocyanurate bridged groups modified periodic mesoporous organosilica synthesized for Fe(III) adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Rana, Vijay Kumar [Department of Polymer Science and Engineering, Pusan National University, Busan 609-735 (Korea, Republic of); Department of Chemical Technology, North Maharashtra University Jalgaon-425001 (India); Division of Polymer Science and Engineering, National Chemical Laboratory, Pune-411 008 (India); Selvaraj, M. [Department of Chemical and Biomolecular Engineering, Pusan National University, Geumjeong-gu, Busan 609-735 (Korea, Republic of); Parambadath, Surendran; Chu, Sang-Wook; Park, Sung Soo [Department of Polymer Science and Engineering, Pusan National University, Busan 609-735 (Korea, Republic of); Mishra, Satyendra [Department of Chemical Technology, North Maharashtra University Jalgaon-425001 (India); Singh, Raj Pal [Division of Polymer Science and Engineering, National Chemical Laboratory, Pune-411 008 (India); Ha, Chang-Sik, E-mail: csha@pnu.edu [Department of Polymer Science and Engineering, Pusan National University, Busan 609-735 (Korea, Republic of)

    2012-10-15

    To achieve a high level of heavy metal adsorption, 1,1 Prime ,1 Double-Prime -(1,3,5-triazine-2,4,6-triyl)tris(3-(3-(triethoxysilyl)propyl)urea) (TTPU) was synthesized as a novel melamine precursor and incorporated on the silica surface of periodic mesoporous organosilica (PMO). The melamine modified PMOs (MPMOs) were synthesized under acidic conditions using TTPU, tetraethylorthosilicate (TEOS) and Pluronic P123 as a template and the modified PMOs were characterized using the relevant instrumental techniques. The characteristic materials were used as adsorbents for the adsorption of Fe(III) ions. Fe(III) adsorption studies revealed MPMO-7.5 to be a good absorbent with higher adsorption efficiency than other MPMOs. - Graphical Abstract: A new organosilica precursor, TTPU, has been successfully synthesized and characterized to incorporate on the silica surface of periodic mesoporous organosilica (PMO). The melamine modified PMOs (MPMOs), in particular, the MPMO-7.5 was found to exhibit good adsorption efficiency for Fe(III). Highlights: Black-Right-Pointing-Pointer Synthesis of new melamine modified periodic mesoporous organosilicas (MPMOs). Black-Right-Pointing-Pointer A new organosilica precursor, TTPU, has been successfully synthesized for the MPMOs. Black-Right-Pointing-Pointer The MPMOs were characterized by the relevant instrumental techniques. Black-Right-Pointing-Pointer MPMO-7.5 exhibits higher adsorption efficiency for Fe(III) ions than other MPMOs.

  1. A comparative study for the ion exchange of Fe(III) and Zn(II) on zeolite NaY.

    Science.gov (United States)

    Ostroski, Indianara C; Barros, Maria A S D; Silva, Edson A; Dantas, João H; Arroyo, Pedro A; Lima, Oswaldo C M

    2009-01-30

    The uptake capacity of Fe(III) and Zn(II) ions in NaY zeolite was investigated. Experiments were carried out in a fixed bed column at 30 degrees C, pH 3.5 and 4.5 for Fe(III) and Zn(II), respectively, and an average particle size of 0.180 mm. In order to minimize the diffusional resistances the influence of flow rate on the breakthrough curves at feed concentrations of 1.56 meq/L for Fe(III) and 0.844 meq/L for Zn(II) was investigated. Flow rate of the minimal resistance in the bed according to mass transfer parameter were 2.0 mL/min for iron and 8.0 mL/min for zinc ions. Freundlich and Langmuir isotherm models have been used to represent the column equilibrium data. The iron dynamic isotherm was successfully modeled by the Langmuir equation and this mathematical model described well the experimental breakthrough curves for feed concentrations from 0.1 up to 3.5 meq/L. The zinc dynamic isotherm was successfully modeled by the Freundlich equation. This equilibrium model was applied to mathematical model. Experimental breakthrough curves could be predicted. Experiments were also carried out in a batch reactor to investigate the kinetics adsorption of the ions Fe(III) and Zn(II). Langmuir kinetic model fit well both experimental data.

  2. Fe(III) shifts the mitochondria permeability transition-eliciting capacity of mangiferin to protection of organelle.

    Science.gov (United States)

    Pardo-Andreu, Gilberto L; Cavalheiro, Renata A; Dorta, Daniel J; Naal, Zeki; Delgado, René; Vercesi, Aníbal E; Curti, Carlos

    2007-02-01

    Mangiferin acts as a strong antioxidant on mitochondria. However, when in the presence of Ca(2+), mangiferin elicits mitochondrial permeability transition (MPT), as evidenced by cyclosporin A-sensitive mitochondrial swelling. We now provide evidence, by means of electrochemical and UV-visible spectroscopical analysis, that Fe(III) coordinates with mangiferin. The resulting mangiferin-Fe(III) complex does not elicit MPT and prevents MPT by scavenging reactive oxygen species. Indeed, the complex protects mitochondrial membrane protein thiols and glutathione from oxidation. Fe(III) also significantly increases the ability of mangiferin to scavenge the 2,2-diphenyl-1-picrylhydrazyl radical, as well as to display antioxidant activity toward antimycin A-induced H(2)O(2) production and t-butyl hydroperoxide-promoted membrane lipid peroxidation in mitochondria. We postulate that coordination with Fe(III) constitutes a potential protective mechanism toward the prooxidant action of mangiferin and other catechol-containing antioxidants regarding MPT induction. Potential therapeutic relevance of this finding for conditions of pathological iron overload is discussed.

  3. Synthesis and characterization of dinuclear complexes containing the Fe(III)-F...(H2O)M(II) motif

    DEFF Research Database (Denmark)

    Ghiladi, M; Jensen, K.B.; Jiang, Jianzhong;

    1999-01-01

    The dinucleating phenolate-hinged ligand 4-tert-butyl-2,6-bis[bis(2-pyridylmethyl)aminomethyl]phenolate(bpb p) has been used to prepare a series of Fe(III)M(II) complexes containing independent species at the exogenous binding sites. These sites are occupied by fluoride and water ligands and show...

  4. The opposite effects of Cu(II) and Fe(III) on the assembly of glucagon amyloid fibrils

    NARCIS (Netherlands)

    Zhou, Xingfei; Tan, Juhua; Zheng, Lifei; Pillai, Saju; Li, Bin; Xu, Peng; Zhang, Bobo; Zhang, Yi

    2012-01-01

    A few transition metal ions are strongly implicated as co-factors in modulating the aggregation of amyloid peptides, which is believed to be a key factor in regulating the cytotoxicity of peptides. In this paper, we explored the effects of Cu(II) and Fe(III) on the aggregation/fibrillation of

  5. Field and laboratory evidence for intrinsic biodegradation of vinyl chloride contamination in a Fe(III)-reducing aquifer

    Science.gov (United States)

    Bradley, P.M.; Chapelle, F.H.; Wilson, J.T.

    1998-01-01

    Intrinsic bioremediation of chlorinated ethenes in anaerobic aquifers previously has not been considered feasible, due, in large part, to 1) the production of vinyl chloride during microbial reductive dechlorination of higher chlorinated contaminants and 2) the apparent poor biodegradability of vinyl chloride under anaerobic conditions. In this study, a combination of field geochemical analyses and laboratory radiotracer ([1,2-14C] vinyl chloride) experiments was utilized to assess the potential for intrinsic biodegradation of vinyl chloride contamination in an Fe(III)-reducing, anaerobic aquifer. Microcosm experiments conducted under Fe(III)-reducing conditions with material from the Fe(III)-reducing, chlorinated-ethene contaminated aquifer demonstrated significant oxidation of [1,2-14C] vinyl chloride to 14CO2 with no detectable production of ethene or other reductive dehalogenation products. Rates of degradation derived from the microcosm experiments (0.9-1.3% d-1) were consistent with field-estimated rates (0.03-0.2% d-1) of apparent vinyl chloride degradation. Field estimates of apparent vinyl chloride biodegradation were calculated using two distinct approaches; 1) a solute dispersion model and 2) a mass balance assessment. These findings demonstrate that degradation under Fe(III) reducing conditions can be an environmentally significant mechanism for intrinsic bioremediation of vinyl chloride in anaerobic ground-water systems.

  6. 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.

  7. 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.

  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. 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

    2017-03-01

    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

  10. Mn(II)/Mn(III) and Fe(III) binding capability of two Aspergillus fumigatus siderophores, desferricrocin and N', N″, N‴-triacetylfusarinine C.

    Science.gov (United States)

    Farkas, Etelka; Szabó, Orsolya; Parajdi-Losonczi, Péter L; Balla, György; Pócsi, István

    2014-10-01

    Manganese(II) and manganese(III) complexes of the exocyclic desferricrocin (H3DFCR) and endocyclic triacetylfusarinine C (H3TAF) in solution have been studied by using pH-potentiometry, UV-Vis spectrophotometry, relaxometry and cyclic voltammetry. A comparison between the present results and the corresponding ones for the open-chain analogues, desferrioxamine B (DFB) and desferricoprogen (DFC), shows (i) The dissociation processes of H3DFCR occur in the expected pH-range (pH7-10.5), but hydrogen bonding is assumed to be responsible for a quite low proton dissociation constant (pK=4.18) of H3TAF and also an unusually high one (10.59). (ii) Moderate stability complexes with 1:1 Mn(II) to ligand ratio are formed with all four siderophores. (iii) The coordination of the three hydroxamates of a siderophore takes place in stepwise processes, except the case of desferricrocin, with which, large-extent overlapping of the processes occurs. (iv) Out of the four tris-chelated [ML] type complexes, the complex of DFCR is the most compact, as it is indicated by the relaxivity values. (v) Following the stoichiometric oxidation of the Mn(II)-siderophore complexes at pH≥9, tris-chelated Mn(III) complexes are formed. To make a comparison between the stability of the Mn(III) and the corresponding Fe(III) complexes of DFCR and TAF, the determination of the stability of the Fe(III) complexes under our condition has also been performed, by using UV-Vis spectrophotometry. Comparable stability of the corresponding complexes was found. (vi) Correlation study of the stability constants resulted in estimation of the constant of the Mn(III) monohydroxo complex, for which there was no data in the literature under our conditions.

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

    Science.gov (United States)

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

    2017-05-05

    Aqueous antimony (Sb) pollution from human activity is of great concern in drinking water due to its adverse health effect. Magnetic Fe3O4 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 Fe3O4, thereby increasing the adsorption efficacy for both Sb(III) and Sb(V). In contrast to un-doped Fe3O4, the adsorption capacity towards Sb(III) and Sb(V) in Ce-doped materials increased from 111.4 to 224.2mg/g and from 37.2 to 188.1mg/g at neutral pH, respectively. Based on the combined results of XPS, XRD, and FTIR, it confirmed that Ce atom successfully doped into the Fe3O4 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 Fe3O4 of great simplicity should be a promising adsorbent for aqueous Sb removal. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Syntheses, crystal structures, and magnetic properties of the oxalato-bridged mixed-valence complexes (FeII(bpm)3]2[FeIII2(ox)5].8H2O and FeII(bpm)3Na(H2O)2Fe(ox)(3).4H2O (bpm = 2,2'-bipyrimidine).

    Science.gov (United States)

    Armentano, D; De Munno, G; Faus, J; Lloret, F; Julve, M

    2001-02-12

    The preparation and crystal structures of two oxalato-bridged FeII-FeIII mixed-valence compounds, [FeII(bpm)3]2[FeIII2(ox)5].8H2O (1) and FeII(bpm)3Na(H2O)2FeIII(ox)(3).4H2O (2) (bpm = 2,2'-bipyrimidine; ox = oxalate dianion) are reported here. Complex 1 crystallizes in the triclinic system, space group P1, with a = 10.998(2) A, b = 13.073(3) A, c = 13.308(3) A, alpha = 101.95(2) degrees, beta = 109.20(2) degrees, gamma = 99.89(2) degrees, and Z = 1. Complex 2 crystallizes in the monoclinic system, space group P2(1)/c, with a = 12.609(2) A, b = 19.670(5) A, c = 15.843(3) A, beta = 99.46(1) degrees, and Z = 4. The structure of complex 1 consists of centrosymmetric oxalato-bridged dinuclear high-spin iron(III) [Fe2(ox)5]2- anions, tris-chelated low-spin iron(II) [Fe(bpm)3]2+ cations, and lattice water molecules. The iron atoms are hexacoordinated: six oxygen atoms (iron(III)) from two bidentate and one bisbidentate oxalato ligands and six nitrogen atoms (iron(II)) from three bidentate bpm groups. The Fe(III)-O(ox) and Fe(II)-N(bpm) bond distances vary in the ranges 1.967(3)-2.099(3) and 1.967(4)-1.995(3) A, respectively. The iron(III)-iron(III) separation across the bridging oxalato is 5.449(2) A, whereas the shortest intermolecular iron(III)-iron(II) distance is 6.841(2) A. The structure of complex 2 consists of neutral heterotrinuclear Fe(bpm)2Na(H2O)2Fe(ox)3 units and water molecules of crystallization. The tris-chelated low-spin iron(II) ([Fe(bpm)3]2+) and high-spin iron(III) ([Fe(ox)3]3-) entities act as bidentate ligands (through two bpm-nitrogen and two oxalato-oxygen atoms, respectively) toward the univalent sodium cation, yielding the trinuclear (bpm)2Fe(II)-bpm-Na(I)-ox-Fe(III)(ox)2 complex. Two cis-coordinated water molecules complete the distorted octahedral surrounding of the sodium atom. The ranges of the Fe(II)-N(bpm) and Fe(III)-O(ox) bond distances [1.968(6)-1.993(5) and 1.992(6)-2.024(6) A, respectively] compare well with those observed in 1. The Na

  13. High chemiluminescence activity of an Fe(III)-TAML activator in aqueous-organic media and its use in the determination of organic peroxides.

    Science.gov (United States)

    Demiyanova, Alexandra S; Sakharov, Ivan Yu

    2015-05-07

    High activity of Fe(III)-TAML, peroxidase mimic, upon the catalytic oxidation of luminol in aqueous-organic media (ethanol, isopropanol and acetonitrile) was determined. Using Fe(III)-TAML the sensitive chemiluminescence assays for the determination of benzoyl peroxide and tert-butyl hydroperoxide in the presence of organic solvents were performed.

  14. Evaluation of siderite and magnetite formation in BIFs by pressure-temperature experiments of Fe(III) minerals and microbial biomass

    Science.gov (United States)

    Halama, Maximilian; Swanner, Elizabeth D.; Konhauser, Kurt O.; Kappler, Andreas

    2016-09-01

    Anoxygenic phototrophic Fe(II)-oxidizing bacteria potentially contributed to the deposition of Archean banded iron formations (BIFs), before the evolution of cyanobacterially-generated molecular oxygen (O2), by using sunlight to oxidize aqueous Fe(II) and precipitate Fe(III) (oxyhydr)oxides. Once deposited at the seafloor, diagenetic reduction of the Fe(III) (oxyhydr)oxides by heterotrophic bacteria produced secondary Fe(II)-bearing minerals, such as siderite (FeCO3) and magnetite (Fe3O4), via the oxidation of microbial organic carbon (i.e., cellular biomass). During deeper burial at temperatures above the threshold for life, thermochemical Fe(III) reduction has the potential to form BIF-like minerals. However, the role of thermochemical Fe(III) reduction of primary BIF minerals during metamorphism, and its impact on mineralogy and geochemical signatures in BIFs, is poorly understood. Consequently, we simulated the metamorphism of the precursor and diagenetic iron-rich minerals (ferrihydrite, goethite, hematite) at low-grade metamorphic conditions (170 °C, 1.2 kbar) for 14 days by using (1) mixtures of abiotically synthesized Fe(III) minerals and either microbial biomass or glucose as a proxy for biomass, and (2) using biogenic minerals formed by phototrophic Fe(II)-oxidizing bacteria. Mössbauer spectroscopy and μXRD showed that thermochemical magnetite formation was limited to samples containing ferrihydrite and glucose, or goethite and glucose. No magnetite was formed from Fe(III) minerals when microbial biomass was present as the carbon and electron sources for thermochemical Fe(III) reduction. This could be due to biomass-derived organic molecules binding to the mineral surfaces and preventing solid-state conversion to magnetite. Mössbauer spectroscopy revealed siderite contents of up to 17% after only 14 days of incubation at elevated temperature and pressure for all samples with synthetic Fe(III) minerals and biomass, whereas 6% of the initial Fe(III) was

  15. Pathways of carbon oxidation in an Arctic fjord sediment (Svalbard) and isolation of psychrophilic and psychrotolerant Fe(III)-reducing bacteria

    DEFF Research Database (Denmark)

    Vandieken, Verona; Finke, Niko; Jørgensen, Bo Barker

    2006-01-01

    reduction was the most important anaerobic mineralization process, accounting for 57 % of anaerobic organic carbon oxidation in anoxic bag incubations of the top 5 cm of the sediment. The remaining 43 % oxidation was attributed to microbial Fe(III) reduction. Both processes occurred concurrently...... to total carbon oxidation: aerobic respiration 53 %, sulfate reduction 34 %, Fe(III) reduction 13 %. In situ, the importance of Fe(III) reduction may vary through competition for substrate with oxygen- and nitrate-reducing bacteria in the surface sediment. Fe (111)-reducing bacteria belonging to the genera...... in the uppermost 2 cm, and the Fe-reducing community appeared to be limited mainly by the availability of Fe(III). Below 2 cm, sulfate reduction was the dominant electron-accepting process, Calculations for the uppermost 10 cm of the sediment yielded the following contribution of the different respiratory pathways...

  16. Citrate Metabolism by Pediococcus halophilus

    OpenAIRE

    Kanbe, Chiyuki; Uchida, Kinji

    1987-01-01

    Several strains of non-citrate-metabolizing Pediococcus halophilus have previously been isolated from soy sauce mash or moromi. The factors controlling the metabolism of citrate in soy pediococci were studied. All the soy pediococcal strains tested which failed to decompose citrate did not possess citrate lyase [citrate (pro-3S)-lyase; EC 4.1.3.6] activity. In P. halophilus, citrate lyase was an inducible enzyme, and the optimum pH for activity was 7.0. The metabolism of citrate in P. halophi...

  17. Synthesis and characterization of dendrimeric melamine cored [salen/salophFe(III)] and [salen/salophCr(III)] capped complexes and their magnetic behaviors

    Energy Technology Data Exchange (ETDEWEB)

    Uysal, Saban, E-mail: uysal77@hotmail.com [Department of Chemistry, Faculty of Science, Selcuk University, Campus of Alaaddin Keykubat, 42075 Selcuklu, Konya (Turkey); Koc, Ziya Erdem [Department of Chemistry, Faculty of Science, Selcuk University, Campus of Alaaddin Keykubat, 42075 Selcuklu, Konya (Turkey)

    2010-03-15

    2,4,6-Tris(4-hydroxybenzimino)-1,3,5-triazine [1] 2 has been synthesized from the reaction of 1 equiv. melamine (2,4,6-triamino-1,3,5-triazine) and 3 equiv. 4-hydroxybenzaldehyde. Then, 2,4,6-tris(4-(4,6-dichloro-1,3,5-triazine-2-yloxy)benzimino)-1,3,5-triazine 3 has been synthesized from the reaction of 1 equiv. 2 and 3 equiv. cyanuric chloride. And then, two new triazine centered dendrimeric ligands 2,4,6-tris(4-(4,6-bis(4-carboxyphenyloxy)-1,3,5-triazine-2-yloxy)benzimino) -1,3,5-triazine 4 and 2,4,6-tris(4-(4,6-bis(3,5-dicarboxyphenyloxy) -1,3,5-triazine-2-yloxy)benzimino)-1,3,5-triazine 5 have been synthesized from the reaction of 1 equiv. 3 and 6 equiv 4-hydroxybenzoic acid or 5-hydroxyisophtalic acid. Finally, eight new multinuclear Fe(III) and Cr(III) complexes involving tetradenta Schiff bases N,N'-bis(salicylidene)ethylenediamine-(salenH{sub 2}) or bis(salicylidene)-o-phenylene diamine-(salophH{sub 2}) with 4 or 5 have been synthesized and characterized by means of elemental analysis, {sup 1}H NMR, FT-IR spectroscopy, thermal analyses and magnetic susceptibility measurements. The complexes can also be characterized as low-spin distorted octahedral Fe(III) and Cr(III) bridged by carboxylic acids.

  18. Acceleration of the Fe(III)EDTA(-) reduction rate in BioDeNO(x) reactors by dosing electron mediating compounds

    NARCIS (Netherlands)

    Maas, van der P.M.F.; Brink, van den P.; Klapwijk, A.; Lens, P.N.L.

    2009-01-01

    BioDeNO(x), a novel technique to remove NOx from industrial flue gases, is based on absorption of gaseous nitric oxide into an aqueous Fe(II)EDTA(2-) solution, followed by the biological reduction of Fe(II)EDTA(2-) complexed NO to N-2. Besides NO reduction, high rate biological Fe(III)EDTA(-) reduct

  19. Acceleration of the Fe(III)EDTA(-) reduction rate in BioDeNO(x) reactors by dosing electron mediating compounds

    NARCIS (Netherlands)

    Maas, van der P.M.F.; Brink, van den P.; Klapwijk, A.; Lens, P.N.L.

    2009-01-01

    BioDeNO(x), a novel technique to remove NOx from industrial flue gases, is based on absorption of gaseous nitric oxide into an aqueous Fe(II)EDTA(2-) solution, followed by the biological reduction of Fe(II)EDTA(2-) complexed NO to N-2. Besides NO reduction, high rate biological Fe(III)EDTA(-)

  20. Comportamento do ácido fítico na presença de Fe(II e Fe(III Behaviour of phytic acid in the presence of iron(II and iron(III

    Directory of Open Access Journals (Sweden)

    Hanna Raquel Quirrenbach

    2009-03-01

    Full Text Available O ácido fítico, dependendo do valor de pH, apresenta alto potencial quelante, complexando íons metálicos, inibindo, assim, a produção de espécies reativas de oxigênio, responsáveis pela destruição oxidativa em sistemas biológicos. Esse potencial quelante tem fundamentado diversos estudos aplicados à ação antioxidante em produtos alimentícios. O objetivo deste trabalho foi estudar o grau de interação do ácido fítico com os íons metálicos Fe(II e Fe(III, de importância biológica, em condições próximas às fisiológicas, e a estabilidade destes complexos. Titulações potenciométricas foram conduzidas para determinar as constantes de formação dos complexos ácido fítico-Fe(II e ácido fítico-Fe(III em solução aquosa, atmosfera inerte, força iônica 0,100 mol.L-1 de cloreto de potássio e à temperatura de 36 ± 0,1 ºC. Estudos espectroscópicos na região do UV-Vis foram realizados para acompanhar a formação dos complexos em solução. Os complexos ácido fítico-Fe(II e ácido fítico-Fe(III foram sintetizados e caracterizados por espectroscopia de absorção na região do infravermelho e por estudos termoanalíticos. Os resultados do conjunto de técnicas utilizadas evidenciaram, tanto em solução como no estado sólido, a presença dos íons metálicos coordenados ao ácido fítico.Depending on the pH value, phytic acid presents high chelating potential bonding metallic ions thus inhibiting the production of reactivated oxygen species, which are responsible for the oxidative destruction in biological systems. Such chelating potential has been the basis of several studies on the antioxidant action in food products. The objective of this work was to study the degree of interaction of the phytic acid with the metallic ions Fe(II and Fe(III, of biological importance, in near-physiological conditions and the stability of these complexes. Potentiometric titrations were applied to determine the constants of

  1. Experimental and molecular modeling studies of the interaction of the polypyridyl Fe(II) and Fe(III) complexes with DNA and BSA.

    Science.gov (United States)

    Behnamfar, Mohammad Taghi; Hadadzadeh, Hassan; Simpson, Jim; Darabi, Farivash; Shahpiri, Azar; Khayamian, Taghi; Ebrahimi, Malihe; Amiri Rudbari, Hadi; Salimi, Mona

    2015-01-01

    Two mononuclear iron complexes, [Fe(tppz)₂](PF₆)₂·H₂O (1) and Fe(tppz)Cl₃·2CHCl₃ (2) where tppz is (2,3,5,6-tetra(2-pyridyl)pyrazine), have been synthesized and characterized by elemental analysis, spectroscopic methods (UV-Vis and IR) and single crystal X-ray structure analysis. The interaction of (1) as the nitrate salt ([Fe(tppz)₂](NO₃)₂) with calf-thymus DNA (CT-DNA) has been monitored by UV-Vis spectroscopy, competitive fluorescence titration, circular dichroism (CD), voltammetric techniques, viscosity measurement, and gel electrophoresis. Gel electrophoresis of DNA with [Fe(tppz)₂](NO₃)₂ demonstrated that the complex also has the ability to cleave supercoiled plasmid DNA. The results have indicated that the complex binds to CT-DNA by three binding modes, viz., electrostatic, groove and partial insertion of the pyridyl rings between the base stacks of double-stranded DNA. Molecular docking of [Fe(tppz)₂](NO₃)₂ with the DNA sequence d(ACCGACGTCGGT)₂ suggests the complex fits into the major groove. The water-insoluble complex (2) can catalyze the cleavage of BSA at 40 °C. There are no reports of the catalytic effect of polypyridyl metal complexes on the BSA cleavage. Molecular docking of (2) with BSA suggests that, when the chloro ligands in the axial positions are replaced by water molecules, the BSA can interact with the Fe(III) complex more easily.

  2. Easy and quantitative access to Fe(II) and Fe(III) di(aryl)alkynylphosphine oxides featuring [Fe(dppe)Cp*] endgroups: terminal P=O functionality blocks the dimerisation of the Fe(III) derivatives.

    Science.gov (United States)

    Tohmé, Ayham; Hagen, Charles T; Essafi, Stéphanie; Bondon, Arnaud; Roisnel, Thierry; Carmichael, Duncan; Paul, Frédéric

    2015-01-25

    A series of paramagnetic di(aryl)alkynylphosphine oxides [PF6] featuring an open-shell [Fe(κ(2)-dppe)(η(5)-C5Me5)](+) endgroup were obtained by oxidation of their neutral Fe(II) parents 3a-c, themselves obtained in a simple and nearly quantitative fashion from the corresponding Fe(II) metallophosphines 1a-c. The new organometallic radicals were characterised by NMR and ESR and were shown to be perfectly stable in solution, in contrast to species such as 1a-b[PF6] which readily dimerise.

  3. Celdas galvánicas. Montaje y comprobación de la celda constituida por los pares Fe(III)/Fe(II)y Cu(II)/Cu.

    OpenAIRE

    Milla González, Miguel

    2013-01-01

    Se dispone de disoluciones de sulfato de cobre(II), sulfato de hierro(II) y nitrato de Fe(III), de un potenciómetro, un puente salino y electrodos de Cu y de grafito. Con las disoluciones citadas, montar una celda galvánica y medir su potencial. Son posibles todas las combinaciones tanto en el compartimento anódico como en el catódico.

  4. Gastrointestinal citrate absorption in nephrolithiasis

    Science.gov (United States)

    Fegan, J.; Khan, R.; Poindexter, J.; Pak, C. Y.

    1992-01-01

    Gastrointestinal absorption of citrate was measured in stone patients with idiopathic hypocitraturia to determine if citrate malabsorption could account for low urinary citrate. Citrate absorption was measured directly from recovery of orally administered potassium citrate (40 mEq.) in the intestinal lavage fluid, using an intestinal washout technique. In 7 stone patients citrate absorption, serum citrate levels, peak citrate concentration in serum and area under the curve were not significantly different from those of 7 normal subjects. Citrate absorption was rapid and efficient in both groups, with 96 to 98% absorbed within 3 hours. The absorption of citrate was less efficient from a tablet preparation of potassium citrate than from a liquid preparation, probably due to a delayed release of citrate from wax matrix. However, citrate absorption from solid potassium citrate was still high at 91%, compared to 98% for a liquid preparation. Thus, hypocitraturia is unlikely to be due to an impaired gastrointestinal absorption of citrate in stone patients without overt bowel disease.

  5. 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.

  6. [CrIII(NCMe)6]3+--a labile CrIII source enabling formation of Cr[M(CN)6] (M=V, Cr, Mn, Fe) Prussian blue-type magnetic materials.

    Science.gov (United States)

    Nelson, Kendric J; Daniels, Matthew C; Reiff, William M; Troff, Shayla A; Miller, Joel S

    2007-11-26

    The kinetic inertness of the hexaaquachromium(III) (kH2O=2.4x10(-6) s(-1)) has led to challenges with respect to incorporating CrIII ions into Prussian blue-type materials; however, hexakis(acetonitrile)chromium(III) was shown to be substantially more labile (approximately 10(4) times) and enables a new synthetic route for the synthesis of these materials via nonaqueous solvents. The synthesis, spectroscopic, and physical properties of Cr[M(CN)6] (M=V, Cr, Mn, Fe) Prussian blue analogues synthesized from [CrIII(NCMe)6]3+ and the corresponding [MIII(CN)6]3- are described. All these compounds {(NEt4)0.02CrIII[VIII(CN)6]0.98(BF4)(0.08).0.10MeCN (1), CrIII[CrIII(CN)6].0.16MeCN (2), CrIII[MnIII(CN)6].0.10MeCN (3), and (NEt4)0.04CrIII0.64CrIV0.40[FeII(CN)6]0.40[FeIII(CN)6]0.60(BF4)(0.16).1.02MeCN (4)} are ferrimagnets exhibiting cluster-glass behavior. Strong antiferromagnetic coupling was observed for M=V, Cr, and Mn with Weiss constants (theta) ranging from -132 to -524 K; and in 2, where the strongest coupling is observed (theta=-524 K), the highest Tc (110 K) value was observed. Weak antiferromagnetic coupling was observed for M=Fe (theta=-12 K) leading to the lowest Tc (3 K) value in this series. Weak coupling and the low Tc value observed in 4 were additionally contributed by the presence of both [FeII(CN)6]4- and [FeIII(CN)6]3- as confirmed by 57Fe-Mössbauer spectroscopy.

  7. Measured rates of fluoride/metal association correlate with rates of superoxide/metal reactions for Fe(III)EDTA(H2O)- and related complexes.

    Science.gov (United States)

    Summers, Jack S; Baker, Joseph B; Meyerstein, Dan; Mizrahi, Amir; Zilbermann, Israel; Cohen, Haim; Wilson, Christopher M; Jones, Jamie R

    2008-02-06

    The effects of 10 paramagnetic metal complexes (Fe(III)EDTA(H2O)-, Fe(III)EDTA(OH)2-, Fe(III)PDTA-, Fe(III)DTPA2-, Fe(III)2O(TTHA)2-, Fe(III)(CN)6(3-), Mn(II)EDTA(H2O)2-, Mn(II)PDTA2-, Mn(II)beta-EDDADP2-, and Mn(II)PO4(-)) on F- ion 19F NMR transverse relaxation rates (R2 = 1/T2) were studied in aqueous solutions as a function of temperature. Consistent with efficient relaxation requiring formation of a metal/F- bond, only the substitution inert complexes Fe(III)(CN)6(3-) and Fe(III)EDTA(OH)2- had no measured effect on T2 relaxation of the F- 19F resonance. For the remaining eight complexes, kinetic parameters (apparent second-order rate constants and activation enthalpies) for metal/F- association were determined from the dependence of the observed relaxation enhancements on complex concentration and temperature. Apparent metal/F- association rate constants for these complexes (k(app,F-)) spanned 5 orders of magnitude. In addition, we measured the rates at which O2*- reacts with Fe(III)PDTA-, Mn(II)EDTA(H2O)2-, Mn(II)PDTA2-, and Mn(II)beta-EDDADP2- by pulse radiolysis. Although no intermediate is observed during the reduction of Fe(III)PDTA- by O2*-, each of the Mn(II) complexes reacts with formation of a transient intermediate presumed to form via ligand exchange. These reactivity patterns are consistent with literature precedents for similar complexes. With these data, both k(app,O2-) and k(app,F-) are available for each of the eight reactive complexes. A plot of log(k(app,O2-)) versus log(k(app,F-)) for these eight showed a linear correlation with a slope approximately 1. This correlation suggests that rapid metal/O2*- reactions of these complexes occur via an inner-sphere mechanism whereas formation of an intermediate coordination complex limits the overall rate. This hypothesis is also supported by the very low rates at which the substitution inert complexes (Fe(III)(CN)6(3-) and Fe(III)EDTA(OH)2-) are reduced by O2*-. These results suggest that F- 19F NMR

  8. Metal Reduction and Iron Biomineralization by a Psychrotolerant Fe(III)-Reducing Bacterium, Shewanella sp. Strain PV-4

    Energy Technology Data Exchange (ETDEWEB)

    Roh, Yul; Gao, Haichun; Vali, Hojatollah; Kennedy, David W.; Yang, Zamin; Gao, Weimin; Dohnalkova, Alice; Stapleton, Raymond D.; Moon, Ji-Won; Phelps, T. J.; Fredrickson, Jim K.; Zhou, Jizhong

    2006-05-01

    A marine psychrotolerant, dissimilatory Fe(III)-reducing bacterium, Shewanella sp. strain PV-4, from the microbial mat at a hydrothermal vent of Loihi Seamount in the Pacific Ocean has been further characterized, with emphases on metal reduction and iron biomineralization. The strain is able to reduce metals such as Fe(III), Co(III), Cr(VI), Mn(IV), and U(VI) as electron acceptors while using lactate, formate, pyruvate, or hydrogen as an electron donor. Growth during iron reduction occurred over the pH range of 7.0 to 8.9, a sodium chloride range of 0.05 to 5%, and a temperature range of 0 to 37°C, with an optimum growth temperature of 18°C. Unlike mesophilic dissimilatory Fe(III)-reducing bacteria, which produce mostly superparamagnetic magnetite (<35 nm), this psychrotolerant bacterium produces well-formed single-domain magnetite (>35 nm) at temperatures from 18 to 37°C. The genome size of this strain is about 4.5 Mb. Strain PV-4 is sensitive to a variety of commonly used antibiotics except ampicillin and can acquire exogenous DNA (plasmid pCM157) through conjugation.

  9. Metal Reduction and Iron Biomineralization by a Psychrotolerant Fe(III)-Reducing Bacterium, Shewanella sp. Strain PV-4

    Energy Technology Data Exchange (ETDEWEB)

    Roh, Yul; Gao, Haichun; Vali, Hojatollah; Kennedy, David W.; Yang, Zamin; Gao, Weimin; Dohnalkova, Alice; Stapleton, Raymond D.; Moon, Ji-Won; Phelps, Tommy J.; Fredrickson, Jim K.; Zhou, Jizhong

    2006-09-01

    A marine psychrotolerant, dissimilatory Fe(III)-reducing bacterium, Shewanella sp. strain PV-4, from the microbial mat at a hydrothermal vent of Loihi Seamount in the Pacific Ocean has been further characterized, with emphases on metal reduction and iron biomineralization. The strain is able to reduce metals such as Fe(III), Co(III), Cr(VI), Mn(IV), and U(VI) as electron acceptors while using lactate, formate, pyruvate, or hydrogen as an electron donor. Growth during iron reduction occurred over the pH range of 7.0 to 8.9, a sodium chloride range of 0.05 to 5%, and a temperature range of 0 to 37 C, with an optimum growth temperature of 18 C. Unlike mesophilic dissimilatory Fe(III)-reducing bacteria, which produce mostly superparamagnetic magnetite (<35 nm), this psychrotolerant bacterium produces well-formed single-domain magnetite (>35 nm) at temperatures from 18 to 37 C. The genome size of this strain is about 4.5 Mb. Strain PV-4 is sensitive to a variety of commonly used antibiotics except ampicillin and can acquire exogenous DNA (plasmid pCM157) through conjugation.

  10. 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

  11. Uranium dioxide in Fe(III)-containing ionic liquids with DMSO: Dissolution, separation, and structural characterization

    Science.gov (United States)

    Yao, Aining; Chu, Taiwei

    2016-11-01

    UO2 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 UO2Cl42- 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 UO2 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.

  12. Bioalteration of synthetic Fe(III)-, Fe(II)-bearing basaltic glasses and Fe-free glass in the presence of the heterotrophic bacteria strain Pseudomonas aeruginosa: Impact of siderophores

    Science.gov (United States)

    Perez, Anne; Rossano, Stéphanie; Trcera, Nicolas; Huguenot, David; Fourdrin, Chloé; Verney-Carron, Aurélie; van Hullebusch, Eric D.; Guyot, François

    2016-09-01

    This study aims to evaluate the role of micro-organisms and their siderophores in the first steps of the alteration processes of basaltic glasses in aqueous media. In this regard, three different types of glasses - with or without iron, in the reduced Fe(II) or oxidized Fe(III) states - were prepared on the basis of a simplified basaltic glass composition. Control and Pseudomonas aeruginosa inoculated experiments were performed in a buffered (pH 6.5) nutrient depleted medium to stimulate the production of the pyoverdine siderophore. Results show that the presence of P. aeruginosa has an effect on the dissolution kinetics of all glasses as most of the calculated elemental release rates are increased compared to sterile conditions. Reciprocally, the composition of the glass in contact with P. aeruginosa has an impact on the bacterial growth and siderophore production. As an essential nutrient for this microbial strain, Fe notably appears to play a central role during biotic experiments. Its presence in the glass stimulates the bacterial growth and minimizes the synthesis of pyoverdine. Moreover the initial Fe2+/Fe3+ ratio in the glasses modulates this synthesis, as pyoverdine is not detected at all in the system in contact with Fe(III)-bearing glass. Finally, the dissolution rates appear to be correlated to siderophore concentrations as they increase with respect to sterile experiments in the order Fe(III)-bearing glass < Fe(II)-bearing glass < Fe-free glass. This increase is attributed to complexation reactions between siderophores and Fe or Al for Fe(II)-bearing glass or Fe-free glass, respectively. The dissolution of an Fe-free glass is significantly improved in the presence of bacteria, as initial dissolution rates are increased by a factor of 3. This study attests to the essential role of siderophores in the P. aeruginosa-promoted dissolution processes of basaltic glasses as well as to the complex relationships between the nutritional potential of the glass and

  13. Co-modification of F{sup −} and Fe(III) ions as a facile strategy towards effective separation of photogenerated electrons and holes

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xuefei; Yu, Rui; Wang, Ping; Chen, Feng [School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070 (China); Yu, Huogen, E-mail: yuhuogen@whut.edu.cn [School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070 (China); State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070 (China)

    2015-10-01

    Graphical abstract: - Highlights: • The Fe(III)/F-TiO{sub 2} photocatalyst was prepared by a facile, wet chemical method. • Fe(III)/F-TiO{sub 2} exhibited higher photocatalytic activity than TiO{sub 2}, Fe(III)/TiO{sub 2} and F-TiO{sub 2}. • The synergistic effect of Fe(III) and F ions contributed to the enhanced activity of TiO{sub 2}. - Abstract: The combination of cocatalysts for simultaneously promoting rapid transfer of photogenerated electrons and holes is one of the effective strategies to improve photocatalytic activity of semiconductor photocatalysts. In this study, highly efficient TiO{sub 2} photocatalyst with co-modification of F and Fe(III) ions was prepared by a facile two wet-chemical method including Fe(III) ions impregnation and then F-ion adsorption on the TiO{sub 2} surface. The photocatalytic results demonstrated that the simultaneously modified Fe(III)/F-TiO{sub 2} photocatalyst exhibited obvious enhancement of photocatalytic performance compared with the pure TiO{sub 2} and single-component modified Fe(III)/TiO{sub 2} and F-TiO{sub 2}. Based on the present experimental results, we propose a possible synergistic effect of Fe(III) and F ions to illustrate the enhanced photocatalytic activity of Fe(III)/F-TiO{sub 2} photocatalyst, namely the Fe(III) ions act as effective active sites to rapidly transfer the photogenerated electrons in the CB of TiO{sub 2} and then reduce oxygen, while F ions work as other effective active sites to rapidly transfer the photogenerated holes in the VB of TiO{sub 2} and then form free hydroxide radical to oxidize the organic substances. As a result, the transfer rate and the interfacial catalytic reaction of photogenerated electrons and holes were simultaneously accelerated, which resulted in the enhanced photocatalytic performance of Fe(III)/F-TiO{sub 2} photocatalyst. Due to the low cost and abundant resource of Fe and F, the obtained photocatalyst is promising for practical application. Furthermore, the

  14. The performance of nonhybrid density functionals for calculating the structures and spin states of Fe(II) and Fe(III) complexes.

    Science.gov (United States)

    Deeth, Robert J; Fey, Natalie

    2004-11-30

    The local density approximation and a range of nonhybrid gradient corrected density functionals (PW91, BLYP, PBE, revPBE, RPBE) have been assessed with respect to the prediction of geometries and spin-state energy preferences for a range of homoleptic Fe(II)L6 and Fe(III)L6 complexes, where L = Cl-, CN-, NH3, pyridine, imidazole, H2O, O=CH2 and tetrahydrofuran. While the qualitative spin-state energies from in vacuo structure optimizations are reasonable the geometries are relatively poorly treated, especially for [FeCl6]3-/4-. Structural results for all the complexes are significantly improved by including environmental effects. The best compromise between structural and spin-state predictive accuracy was obtained for the RPBE functional in combination with the COSMO solvation approach. This approach systematically overestimates the energetic preference for a low spin state, which is partly due to the well-known effect of the lack of exact exchange in nonhybrid functionals and partly due to the larger solvation stabilization of low-spin complexes that have shorter bond lengths and thus smaller molecular volumes than their high-spin partners. Calculations on low spin [Fe(bipy)3]2+ and [Fe(phen)3]2+ and their ortho methyl substituted analogs, which are high spin at room temperature but cross over to low spin at low temperature, suggest the RPBE/COSMO combination generates low spin states which are too stable by approximately 13 kcal mol(-1).

  15. Fe(III) reduction-mediated phosphate removal as vivianite (Fe3(PO4)2⋅8H2O) in septic system wastewater.

    Science.gov (United States)

    Azam, Hossain M; Finneran, Kevin T

    2014-02-01

    Phosphate is a water contaminant from fertilizers, soaps, and detergents that enters municipal and onsite wastewater from households, businesses, and other commercial operations. Phosphate is a limiting nutrient for algae, and is one of the molecules that promotes eutrophication of water bodies. Phosphate is especially problematic in onsite wastewater because there are few removal mechanisms under normal operating conditions; a system must be amended specifically with compounds to bond to or adsorb phosphate in the septic tank or within the leach field. Vivianite (Fe3(PO4)2⋅8H2O) is a stable mineral formed from ferrous iron and phosphate, often as the result of Fe(III) reducing microbial activity. What was unknown was the concentration of phosphate that could be removed by this process, and whether it was relevant to mixed microbial systems like septic tank wastewater. Data presented here demonstrate that significant concentrations of phosphate (12-14mM) were removed as vivianite in growing cultures of Geobacter metallireducens strain GS-15. Vivianite precipitates were identified on the cell surfaces and within multi cell clusters using TEM-EDX; the mineral phases were directly characterized using XRD. Phosphate was also removed in dilute and raw (undiluted) septic wastewater amended with different forms of Fe(III) including solid phase and soluble Fe(III). Vivianite precipitates were recovered and identified using XRD, along with siderite (ferrous carbonate), which was expected given that the systems were likely bicarbonate buffered. These data demonstrate that ferric iron amendments in septic wastewater increase phosphate removal as the mineral vivianite, and this may be a good strategy for phosphate attenuation in the septic tank portion of onsite wastewater systems. Copyright © 2013 Elsevier Ltd. All rights reserved.

  16. Sorption Kinetics Of Selected Heavy Metals Adsorption To Natural And Fe(III Modified Zeolite Tuff Containing Clinoptilolite Mineral

    Directory of Open Access Journals (Sweden)

    Sirotiak Maroš

    2015-06-01

    Full Text Available In the research described in this paper, studied was sorption capacity of natural and ferric modification of zeolite tuff containing mineral clinoptilolite from the Nižný Hrabovec deposit to remove potentially toxic metals (ionic forms of chromium, nickel, copper and aluminium from their water solutions. We reported that the Fe (III zeolite has an enhanced ability to sorption of Cu (II, and a slight improvement occurs in the case of Cr (VI and Ni (II. On the other hand, the deterioration was observed in the case of Al (III adsorption.

  17. Sorption Kinetics Of Selected Heavy Metals Adsorption To Natural And Fe(III) Modified Zeolite Tuff Containing Clinoptilolite Mineral

    Science.gov (United States)

    Sirotiak, Maroš; Lipovský, Marek; Bartošová, Alica

    2015-06-01

    In the research described in this paper, studied was sorption capacity of natural and ferric modification of zeolite tuff containing mineral clinoptilolite from the Nižný Hrabovec deposit to remove potentially toxic metals (ionic forms of chromium, nickel, copper and aluminium) from their water solutions. We reported that the Fe (III) zeolite has an enhanced ability to sorption of Cu (II), and a slight improvement occurs in the case of Cr (VI) and Ni (II). On the other hand, the deterioration was observed in the case of Al (III) adsorption.

  18. Self-Assembly of Two Chiral Supramolecules with Three-Dimensional Porous Host Frameworks: (Delta){[Fe(II)(phen)(3)][Fe(III)Na(C(2)O(4))(3)]}(n)() and Its Enantiomer.

    Science.gov (United States)

    Li, Pei-zhou; Lu, Xiao-ming; Liu, Bo; Wang, Shuo; Wang, Xiao-jun

    2007-07-23

    Two chiral supramolecules with enantiomeric three-dimensional porous host frameworks, (Delta){[Fe(II)(phen)(3)][Fe(III)Na(C(2)O(4))(3)]}(n) (1) and (Lambda){[Fe(II)(phen)(3)][Fe(III)Na(C(2)O(4))(3)]}(n) (2) (phen = 1,10-phenanthroline), have been synthesized, and their crystal structures have been determined. The structural analysis shows that compounds 1 and 2 are a pair of enantiomers, both consisting of a three-dimensional porous skeleton formed by (Delta)/(Lambda){[Fe(III)Na(C(2)O(4))(3)](2-)}(n) and guest (Delta)/(Lambda)[Fe(phen)(3)](2+) units. The circular dichroism spectrum measurements confirmed the optical activity and the enantiomeric nature of complexes 1 and 2.

  19. Final report on the safety assessment of acetyl triethyl citrate, acetyl tributyl citrate, acetyl trihexyl citrate, and acetyl trioctyl citrate.

    Science.gov (United States)

    Johnson, Wilbur

    2002-01-01

    Acetyl Triethyl Citrate, Acetyl Tributyl Citrate, Acetyl Trihexyl Citrate, and Acetyl Trioctyl Citrate all function as plasticizers in cosmetics. Additionally, the Trihexyl and Trioctyl forms are described as skin-conditioning agents-emollients, although there are currently no reported uses of Acetyl Trihexyl Citrate or Acetyl Trioctyl Citrate. Acetyl Triethyl Citrate and Acetyl Tributyl Citrate are used in nail products at concentrations up to 7%. Recognizing that there are no reported uses of Acetyl Trihexyl or Trioctyl Citrate, if they were to be used in the future, their concentration of use is expected to be no higher than that reported for Acetyl Triethyl and Tributyl Citrate. These ingredients were sufficiently similar in structure that safety test data on one were considered applicable to all. Approximately 99% of orally administered Acetyl Tributyl Citrate is excreted-intermediate metabolites include acetyl citrate, monobutyl citrate, acetyl monobutyl citrate, dibutyl citrate, and acetyl dibutyl citrate. In acute, short-term, subchronic, and chronic feeding studies, these ingredients were relatively nontoxic. Differences from controls were either not statistically significant or not related to any organ toxicity. Ocular exposures produced moderate reactions that cleared by 48 hours after instillation. Dermal application was not toxic in rabbits. In a guinea pig maximization test, Acetyl Triethyl Citrate was a sensitizer whereas Acetyl Tributyl Citrate was not. Limited clinical testing of Acetyl Triethyl Citrate and Acetyl Tributyl Citrate was negative for both skin irritation and sensitization. These clinical data were considered more relevant than the guinea pig maximization data, suggesting to the Cosmetic Ingredient Review Expert Panel that none of these ingredients would be a sensitizer. Physiologic effects noted with intravenous delivery of Acetyl Triethyl Citrate or Acetyl Tributyl Citrate include dose-related decreases in blood pressure and

  20. 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.

  1. 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

  2. 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.

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

    Science.gov (United States)

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

    2016-11-01

    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.

  4. Intervalence charge transfer transition in mixed valence complexes synthesised from RuIII(edta)- and FeII(CN)5-cores

    Indian Academy of Sciences (India)

    H C Bajaj; Atindra D Shukla; Amitava Das

    2002-08-01

    Intervalence charge transfer properties were studied for a set of mixed valence complexes incorporating Ru(III) and Fe(II)-centres linked by various saturated and unsaturated bridging ligands (BL). Studies reveal that degree of ground state electronic interaction and coupling between Ru(III) and Fe(II)-centres can be attenuated by changing the nature of the bridging ligand. Further, inclusion of the bridging ligand with interrupted -electron system in a -CD cavity initiate an optical electron transfer from Fe(II) to Ru(III) which is otherwise not observed.

  5. Reactions of nitrogen oxides with the five-coordinate Fe(III)(porphyrin) nitrito intermediate Fe(Por)(ONO) in sublimed solids.

    Science.gov (United States)

    Kurtikyan, Tigran S; Hovhannisyan, Astghik A; Hakobyan, Manya E; Patterson, James C; Iretskii, Alexei; Ford, Peter C

    2007-03-28

    Detailed experimental studies are described for reactions of several nitrogen oxides with iron porphyrin models for heme/NxOy systems. It is shown by FTIR and optical spectroscopy and by isotope labeling experiments that reaction of small increments of NO2 with sublimed thin layers of the iron(II) complex Fe(Por) (Por = meso-tetraphenylporphyrinato dianion, TPP, or meso-tetra-p-tolylporphyrinato dianion, TTP) leads to formation of the 5-coordinate nitrito complexes Fe(Por)(eta1-ONO) (1), which are fairly stable but very slowly decompose under vacuum giving mostly the corresponding nitrosyl complexes Fe(Por)(NO). Further reaction of 1 with new NO2 increments leads to formation of the nitrato complex Fe(Por)(eta2-O2NO) (2). The interaction of NO with 1 at low temperature involves ligand addition to give the nitrito-nitrosyl complexes Fe(Por)(eta1-ONO)(NO) (3); however, these isomerize to the nitro-nitrosyl analogs Fe(Por)(eta1-NO2)(NO) (4) upon warming. Experiments with labeled nitrogen oxides argue for an intramolecular isomerization ("flipping") mechanism rather than one involving dissociation and rebinding of NO2. The Fe(III) centers in the 6-coordinate species 3 and 4 are low spin in contrast to 1, which appears to be high-spin, although DFT computations of the porphinato models Fe(P)(nitrite) suggest that the doublet nitro species and the quartet and sextet nitrito complexes are all relatively close in energy. The nitro-nitrosyl complex 4 is stable under an NO atmosphere but decomposes under intense pumping to give a mixture of the ferrous nitrosyl complex Fe(Por)(NO) and the ferric nitrito complex Fe(Por)(eta1-ONO) indicating the competitive dissociation of NO and NO2. Hence, loss of NO from 4 is accompanied with nitro --> nitrito isomerization consistent with 1 being the more stable of the 5-coordinate NO2 complexes of iron porphyrins.

  6. Comparative adsorption of Fe(III) and Cd(II) ions on glutaraldehyde crosslinked chitosan–coated cristobalite

    OpenAIRE

    Rahmi; Fathurrahmi; Irwansyah; Arie Purnaratrie

    2015-01-01

    In this study, chitosan was crosslinked with glutaraldehyde and coated on the surface of cristobalite through a dip and phase inversion process. The adsorbent was used in batch experiments to evaluate the adsorption of Fe(III) and Cd(II) ions. A maximum adsorption capacity was observed at a glutaraldehyde concentration in sorbent preparation of 1% (w/w). The equilibrium adsorption quantity was determined to be a function of the solution pH, initial concentration and agitation period. Langmuir...

  7. 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.

  8. 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.

  9. Interaction of Imidazole Containing Hydroxamic Acids with Fe(III: Hydroxamate Versus Imidazole Coordination of the Ligands

    Directory of Open Access Journals (Sweden)

    Etelka Farkas

    2007-01-01

    Full Text Available Solution equilibrium studies on Fe(III complexes formed with imidazole-4-carbohydroxamic acid (Im-4-Cha, N-Me-imidazole-4-carbohydroxamic acid (N-Me-Im-4-Cha, imidazole-4-acetohydroxamic acid (Im-4-Aha, and histidinehydroxamic acid (Hisha have been performed by using pH-potentiometry, UV-visible spectrophotometry, EPR, ESI-MS, and H-NMR methods. All of the obtained results demonstrate that the imidazole moiety is able to play an important role very often in the interaction with Fe(III, even if this metal ion prefers the hydroxamate chelates very much. If the imidazole moiety is in α-position to the hydroxamic one (Im-4-Cha and N-Me-Im-4-Cha its coordination to the metal ion is indicated unambiguously by our results. Interestingly, parallel formation of (Nimidazole, Ohydroxamate, and (Ohydroxamate, Ohydroxamate type chelates seems probable with N-Me-Im-4-Cha. The imidazole is in β-position to the hydroxamic moiety in Im-4-Aha and an intermolecular noncovalent (mainly H-bonding interaction seems to organize the intermediate-protonated molecules in this system. Following the formation of mono- and bishydroxamato mononuclear complexes, only EPR silent species exists in the Fe(III-Hisha system above pH 4, what suggests the rather significant “assembler activity” of the imidazole (perhaps together with the ammonium moiety.

  10. Interaction of imidazole containing hydroxamic acids with Fe(III): hydroxamate versus imidazole coordination of the ligands.

    Science.gov (United States)

    Farkas, Etelka; Bátka, Dávid; Csóka, Hajnalka; Nagy, Nóra V

    2007-01-01

    Solution equilibrium studies on Fe(III) complexes formed with imidazole-4-carbohydroxamic acid (Im-4-Cha), N-Me-imidazole-4-carbohydroxamic acid (N-Me-Im-4-Cha), imidazole-4-acetohydroxamic acid (Im-4-Aha), and histidinehydroxamic acid (Hisha) have been performed by using pH-potentiometry, UV-visible spectrophotometry, EPR, ESI-MS, and H1-NMR methods. All of the obtained results demonstrate that the imidazole moiety is able to play an important role very often in the interaction with Fe(III), even if this metal ion prefers the hydroxamate chelates very much. If the imidazole moiety is in alpha-position to the hydroxamic one (Im-4-Cha and N-Me-Im-4-Cha) its coordination to the metal ion is indicated unambiguously by our results. Interestingly, parallel formation of (Nimidazole, Ohydroxamate), and (Ohydroxamate, Ohydroxamate) type chelates seems probable with N-Me-Im-4-Cha. The imidazole is in beta-position to the hydroxamic moiety in Im-4-Aha and an intermolecular noncovalent (mainly H-bonding) interaction seems to organize the intermediate-protonated molecules in this system. Following the formation of mono- and bishydroxamato mononuclear complexes, only EPR silent species exists in the Fe(III)-Hisha system above pH 4, what suggests the rather significant "assembler activity" of the imidazole (perhaps together with the ammonium moiety).

  11. Chemometrics-assisted kinetic-potentiometric methods for simultaneous determination of Fe(II), Al(III), and Zr(IV) using a fluoride ion-selective electrode.

    Science.gov (United States)

    Karimi, Mohammad Ali; Ardakani, Mohammad Mazloum; Ardakani, Reza Behjatmanesh; Mashhadizadeh, Mohammad Hossein; Monfared, Mohammad Reza Zand; Tadayon, Maryam

    2010-01-01

    Partial least-squares (PLS) and principal component regression (PCR) were used for the simple, accurate, and simultaneous determination of Fe(III), Al(III), and Zr(IV) using the kinetic data from a novel potentiometric method. The complex forming reaction rate of Fe(III), Al(III), and Zr(IV) with fluoride ions was monitored by a fluoride ion-selective electrode. The experimental data showed the good ability of ion-selective electrodes as detectors, not only for the direct determination of fluoride ion, but also for simultaneous kinetic-potentiometric analysis using the PLS and PCR methods. The methods are based on the differences observed in the complexation rate of fluoride ions. Results have demonstrated that the simultaneous determination of Fe(III), Al(III), and Zr(IV) can be performed in concentration ranges of 0.5-18.5, 0.2-14.0, and 0.4-21.0 microg/mL, respectively. After the application of PLS, the total root mean square error of prediction (RMSEP) was found to be 0.121, 0.122, and 0.129 for the 10-sample experiment of Fe(III), Al(III), and Zr(IV), respectively. For PCR, the RMSEP was found to be 0.156, 0.162, and 0.178 for the 10-sample experiment of Fe(III), Al(III), and Zr(IV), respectively. The effects of certain foreign ions upon the reaction rate were determined for assessing the selectivity of the method. The proposed methods (H-point standard addition, PLS, and PCR) were evaluated using a set of synthetic sample mixtures, and applied for the simultaneous determination of Fe(III), Al(III), and Zr(IV) in water samples.

  12. Evidence of iron (III) reduction in γ-Fe2O3 nanoparticles due to meso-2,3-dimercaptosuccinic acid functionalization

    Science.gov (United States)

    Nunes, Eloiza S.; Lima, Emilia C. D.; Soler, Maria A. G.; Silva, Fabio R. L.; Azevedo, Ricardo B.; Morais, Paulo C.

    2014-03-01

    In this study we report on the meso-2,3-dimercaptosuccinic acid (DMSA) surface functionalization of nanosized maghemite particles which were obtained from oxidation of freshly-precipitated magnetite nanoparticles. Stable magnetic sols were produced while using [DMSA]/[Fe] in a wide range (2 to 90%) of values for the surface functionalization protocol. We found experimental evidence of Fe (III) reduction down to Fe (II) in the whole range of [DMSA]/[Fe] values employed, though presenting differences for lower and higher values of DMSA/Fe molar ratio. At lower (up to 10%) [DMSA]/[Fe] values the DMSA-functionalized iron oxide core remains essentially maghemite while the reduced Fe (II) ions move out to the bulk solution as soluble species. In contrast, at higher (20% and above) [DMSA]/[Fe] values the DMSA-functionalized iron oxide core holds the reduced Fe (II) on its crystal structure. The thiol group oxidation, via disulfide bridge formation, plays a key role in the Fe (III) reduction to Fe (II) during the surface functionalization process. We hypothesize that at higher [DMSA]/[Fe] values (20% and above) intermolecular disulfide bridge formation dominates, leading to the onset of a network at the nanoparticle’s surface, thus preventing the surface reduced Fe (II) ions moving out into the bulk solution. Experimental evidence based on visual inspection and different techniques (UV-vis-IR spectroscopy, chemical analysis, x-ray diffraction, and Raman spectroscopy) are present to support the model picture herein introduced.

  13. Reactivity of nano-size zinc powder in the aqueous solution of [Fe(III)(edta)(H2O)]().

    Science.gov (United States)

    Augustyniak, Adam W; Suchecki, Tomasz T; Kumazawa, Hidehiro

    2017-01-01

    Nitrogen mono-oxide and sulfur dioxide can be removed by simultaneous absorption into aqueous mixed solutions of sulfite and [Fe(II)(edta)]H2O)](2-), ferrous ion coordinated to an anion of ethylene-diaminetetraacetic acid (EDTA or edta). In the industrial system with coexisting oxygen in the gas phase, [Fe(II)(edta)](H2O)](2-) complex is oxidized to [Fe(III)(edta)](H2O)](-) by molecular oxygen. Because the ferric complex has no capability for reaction with NO, the suppression of this undesired oxidation process is a very important technological problem to be overcome. In our preceding work, we discussed the reduction kinetics of ferric ion by metal powder on the basis of the kinetic data regarding the ferric ion reduction in aqueous solutions of [Fe(III)(edta)](H2O)](-) containing aluminum, tin or zinc powders. Zinc powder of normal size was recognized as an effective reducing agent. In the present work, augmentation of reducing capability of zinc powder was examined more. The rate of reduction of nano-size zinc powder was found to be about 11 times higher than that of normal-size zinc one.

  14. Tripraseodymium pentairon(III dodecaoxide, Pr3Fe5O12: a synchrotron radiation study

    Directory of Open Access Journals (Sweden)

    Takashi Komori

    2009-11-01

    Full Text Available The title compound, pentairon tripraseodymium dodecaoxide (PrIG, has an iron garnet structure. There are two Fe site symmetries. One of the Fe atoms is coordinated by six O atoms, forming a slightly distorted octahedron, and has overline{3} site symmetry. The other Fe atom is coordinated by four O atoms, forming a slightly distorted tetrahedron, and has overline{4} site symmetry. FeO6 octahedra and FeO4 tetrahedra are linked together by corners. The Pr atom is coordinated by eight O atoms, forming a distorted dodecahedron, and has 222 site symmetry. The O atoms occupy the general positions.

  15. 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.

  16. Manganese(II)-catalyzed and clay-minerals-mediated reduction of chromium(VI) by citrate.

    Science.gov (United States)

    Sarkar, Binoy; Naidu, Ravi; Krishnamurti, Gummuluru S R; Megharaj, Mallavarapu

    2013-01-01

    Unlike lower valent iron (Fe), the potential role of lower valent manganese (Mn) in the reduction of hexavalent chromium (Cr(VI)) in soil is poorly documented. In this study, we report that citrate along with Mn(II) and clay minerals (montmorillonite and kaolinite) reduce Cr(VI) both in aqueous phase and in the presence of dissolved organic carbon (SDOC) extracted from a forest soil. The reduction was favorable at acidic pH (up to pH 5) and followed the pseudo-first-order kinetic model. The citrate (10 mM) + Mn(II) (182.02 μM) + clay minerals (3% w/v) system in SDOC accounted for complete reduction of Cr(VI) (192.32 μM) in about 72 h at pH 4.9. In this system, citrate was the reductant, Mn(II) was a catalyst, and the clay minerals acted as an accelerator for both the reductant and catalyst. The clay minerals also serve as a sink for Cr(III). This study reveals the underlying mechanism of the Mn(II)-induced reduction of Cr(VI) by organic ligand in the presence of clay minerals under certain environmental conditions.

  17. 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.

  18. Use of coal mining waste for the removal of acidity and metal ions Al(III), Fe(III) and Mn(II) in acid mine drainage

    Energy Technology Data Exchange (ETDEWEB)

    Geremias, R.; Laus, R.; Macan, J.M.; Pedrosa, R.C.; Laranjeira, M.C.M.; Silvan, J.; Favere, F.V. [Universidade Federal de Santa Catarina, Florianopolis (Brazil)

    2008-08-15

    The coal industry may generate acid mine drainage (AMD) and mining wastes, which may adversely affect the quality of the environment. In this study we propose the use of this waste in the removal of acidity and metal ions, as well as in the reduction of the toxicity of AMD. A physico-chemical analysis of the waste shows the presence of mainly SiO{sub 2}, Al{sub 2}O{sub 3} and Fe{sub 2}O{sub 3} and a superficial area of 4.316 m{sup 2} g{sup -1}. The treatment of AMD with the waste resulted in an increase in pH from 2.6 to 7.8 and removed 100% of the Al(III), 100% of the Fe(III) and 89% of the Mn (II). We also observed that the high toxicity of the AMD towards Daphnia magna (LC50 = 3.68%) and Artemia sp. (LC50 = 4.97%) was completely eliminated after treatment with the waste. The data obtained allow us to propose that the waste can be used in the treatment of AMD, providing an economic use for the waste.

  19. 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.

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

    Directory of Open Access Journals (Sweden)

    Liang-Jin Chen

    Full Text Available 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.

  1. Silicon isotope fractionation during microbial reduction of Fe(III)-Si gels under Archean seawater conditions and implications for iron formation genesis

    Science.gov (United States)

    Reddy, Thiruchelvi R.; Zheng, Xin-Yuan; Roden, Eric E.; Beard, Brian L.; Johnson, Clark M.

    2016-10-01

    Microbial dissimilatory iron reduction (DIR) is a deeply rooted metabolism in the Bacteria and Archaea. In the Archean and Proterozoic, the most likely electron acceptor for DIR in marine environments was Fe(III)-Si gels. It has been recently suggested that the Fe and Si cycles were coupled through sorption of aqueous Si to iron oxides/hydroxides, and through release of Si during DIR. Evidence for the close association of the Fe and Si cycles comes from banded iron formations (BIFs), which consist of alternating bands of Fe-bearing minerals and quartz (chert). Although there has been extensive study of the stable Fe isotope fractionations produced by DIR of Fe(III)-Si gels, as well as studies of stable Fe isotope fractionations in analogous abiologic systems, no studies to date have investigated stable Si isotope fractionations produced by DIR. In this study, the stable Si isotope fractionations produced by microbial reduction of Fe(III)-Si gels were investigated in simulated artificial Archean seawater (AAS), using the marine iron-reducing bacterium Desulfuromonas acetoxidans. Microbial reduction produced very large 30Si/28Si isotope fractionations between the solid and aqueous phase at ˜23 °C, where Δ30Sisolid-aqueous isotope fractionations of -3.35 ± 0.16‰ and -3.46 ± 0.09‰ were produced in two replicate experiments at 32% Fe(III) reduction (solid-phase Fe(II)/FeTotal = 0.32). This isotopic fractionation was substantially greater than that observed in two abiologic controls that had solid-phase Fe(II)/FeTotal = 0.02-0.03, which produced Δ30Sisolid-aqueous isotope fractionations of -2.83 ± 0.24‰ and -2.65 ± 0.28‰. In a companion study, the equilibrium Δ30Sisolid-aqueous isotope fractionation was determined to be -2.3‰ for solid-phase Fe(II)/FeTotal = 0. Collectively, these results highlight the importance of Fe(II) in Fe-Si gels in producing large changes in Si isotope fractionations. These results suggest that DIR should produce highly

  2. Dissimilatory reduction of FeIII (EDTA) with microorganisms in the system of nitric oxide removal from the flue gas by metal chelate absorption

    Institute of Scientific and Technical Information of China (English)

    MA Bi-yao; LI Wei; JING Guo-hua; SHI Yao

    2004-01-01

    In the system of nitric oxide removal from the flue gas by metal chelate absorption, it is an obstacle that ferrous absorbents are easily oxidized by oxygen in the flue gas to ferric counterparts, which are not capable of binding NO. By adding iron metal or electrochemical method, FeIII (EDTA) can be reduced to FeII (EDTA). However, there are various drawbacks associated with these techniques. The dissimilatory reduction of FeIII (EDTA) with microorganisms in the system of nitric oxide removal by metal chelate absorption was investigated. Ammonium salt instead of nitrate was used as the nitrogen source, as nitrates inhibited the reduction of FeIII due to the competition between the two electron acceptors. Supplemental glucose and lactate stimulated the formation of FeII more than ethanol as the carbon sources. The microorganisms cultured at 50℃ were not very sensitive to the other experimental temperature, the reduction percentage of FeIII varied little with the temperature range of 30~50℃. Concentrated Na2CO3 solution was added to adjust the solution pH to an optimal pH range of 6~7. The overall results revealed that the dissimilatory ferric reducing microorganisms present in the mix-culture are probably neutrophilic, moderately thermophilic FeIII reducers.

  3. mer-[Fe(pcq)(CN)3]-: a novel cyanide-containing building block and its application to assembling cyanide-bridged trinuclear FeIII2MnII complexes [pcq- = 8-(pyridine-2-carboxamido)quinoline anion].

    Science.gov (United States)

    Ni, Zhong-Hai; Kou, Hui-Zhong; Zhang, Li-Fang; Ni, Wei-Wei; Jiang, Yun-Bo; Cui, Ai-Li; Ribas, Joan; Sato, Osamu

    2005-12-26

    A new cyanide-containing building block K[Fe(pcq)(CN)(3)] [1; pcq(-) = 8-(pyridine-2-carboxamido)quinoline anion] containing a low-spin Fe(III) center with three cyanide groups in a meridional arrangement has been successfully designed and synthesized. Three cyanide-bridged trinuclear Fe(III)(2)Mn(II) complexes, [Fe(pcq)(CN)(3)](2)[Mn(CH(3)OH)(2)(H(2)O)(2)].2H(2)O (2), [Fe(pcq)(CN)(3)](2)[Mn(bipy)(2)].CH(3)OH.2H(2)O (3), and [Fe(pcq)(CN)(3)](2)[Mn(phen)(2)].CH(3)OH.2H(2)O (4), have been synthesized and structurally characterized. The magnetic susceptibilities of the three heterometallic complexes have been investigated.

  4. Iron Deficiency Decreases the Fe(III)-Chelate Reducing Activity of Leaf Protoplasts1

    Science.gov (United States)

    González-Vallejo, Elena B.; Morales, Fermín; Cistué, Luis; Abadía, Anunciación; Abadía, Javier

    2000-01-01

    The ferric-chelate reductase (FC-R) activity of mesophyll protoplasts isolated from Fe-sufficient (control) and Fe-deficient sugar beet (Beta vulgaris L.) leaves has been characterized. Measurements were made in an ionic environment similar to that in the apoplastic space of the sugar beet mesophyll cells. The FC-R activity of Fe-sufficient and Fe-deficient protoplasts was dependent on light. Fe deficiency decreased markedly the FC-R activity per protoplast surface unit. The optimal pH for the activity of the FC-R in mesophyll protoplasts was in the range 5.5 to 6.0, typical of the apoplastic space. Beyond pH 6.0, the activity of the FC-R in mesophyll protoplasts decreased markedly in both Fe-sufficient and Fe-deficient protoplasts. These data suggest that both the intrinsic decrease in FC-R activity per protoplast surface and a possible shift in the pH of the apoplastic space could lead to the accumulation of physiologically inactive Fe pools in chlorotic leaves. PMID:10677427

  5. Fe (III) speciation in the high nutrient, low chlorophyll Pacific region of the Southern Ocean

    NARCIS (Netherlands)

    Nolting, R.F.; Gerringa, L.J.A.; Swagerman, M.J.W.; Timmermans, K.R.; Baar, H.J.W. de

    1998-01-01

    Fe speciation was measured with competitive ligand equilibration adsorptive cathodic stripping voltammetry in the Pacific part of the Southern Ocean between 58° and 68°30′S along the 90°W meridian. The conditional stability constant (K′ with respect to [Fe3+]) was between 10^20.6 and 10^21.6 when

  6. Fe(III) in a low-spin state in caesium bis[3-ethoxysalicylaldehyde 4-methylthiosemicarbazonato(2-)-κ3O2,N1,S]ferrate(III) methanol monosolvate.

    Science.gov (United States)

    Powell, Robyn E; Schwalbe, Carl H; Tizzard, Graham J; Koningsbruggen, Petra J van

    2014-06-01

    The synthesis and crystal structure (at 100 K) of the title compound, Cs[Fe(C11H13N3O2S2)2]·CH3OH, is reported. The asymmetric unit consists of an octahedral [Fe(III)(L)2](-) fragment, where L(2-) is 3-ethoxysalicylaldehyde 4-methylthiosemicarbazonate(2-) {systematic name: [2-(3-ethoxy-2-oxidobenzylidene)hydrazin-1-ylidene](methylamino)methanethiolate}, a caesium cation and a methanol solvent molecule. Each L(2-) ligand binds through the thiolate S, the imine N and the phenolate O atoms as donors, resulting in an Fe(III)S2N2O2 chromophore. The O,N,S-coordinating ligands are orientated in two perpendicular planes, with the O and S atoms in cis positions and the N atoms in trans positions. The Fe(III) cation is in the low-spin state at 100 K.

  7. Mn(2+)-mediated homogeneous Fenton-like reaction of Fe(III)-NTA complex for efficient degradation of organic contaminants under neutral conditions.

    Science.gov (United States)

    Li, Yifan; Sun, Jianhui; Sun, Sheng-Peng

    2016-08-05

    In this work, we report a novel Mn(2+)-mediated Fenton-like process based on Fe(III)-NTA complex that is super-efficient at circumneutral pH range. Kinetics experiments showed that the presence of Mn(2+) significantly enhanced the effectiveness of Fe(III)-NTA complex catalyzed Fenton-like reaction. The degradation rate constant of crotamiton (CRMT), a model compound, by the Fe(III)- NTA_Mn(2+) Fenton-like process was at least 1.6 orders of magnitude larger than that in the absence of Mn(2+). Other metal ions such as Ca(2+), Mg(2+), Co(2+) and Cu(2+) had no impacts or little inhibitory effect on the Fe(III)-NTA complex catalyzed Fenton-like reaction. The generation of hydroxyl radical (HO) and superoxide radical anion (O2(-)) in the Fe(III)-NTA_Mn(2+) Fenton-like process were suggested by radicals scavenging experiments. The degradation efficiency of CRMT was inhibited significantly (approximately 92%) by the addition of HO scavenger 2-propanol, while the addition of O2(-) scavenger chloroform resulted in 68% inhibition. Moreover, the results showed that other chelating agents such as EDTA- and s,s-EDDS-Fe(III) catalyzed Fenton-like reactions were also enhanced significantly by the presence of Mn(2+). The mechanism involves an enhanced generation of O2(-) from the reactions of Mn(2+)-chelates with H2O2, indirectly promoting the generation of HO by accelerating the reduction rate of Fe(III)-chelates to Fe(II)- chelates. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Humic substance-mediated Fe(III) reduction by a fermenting Bacillus strain from the alkaline gut of a humus-feeding scarab beetle larva.

    Science.gov (United States)

    Hobbie, Sven N; Li, Xiangzhen; Basen, Mirko; Stingl, Ulrich; Brune, Andreas

    2012-06-01

    Humus-feeding macroinvertebrates play an important role in the transformation of soil organic matter. Their diet contains significant amounts of redox-active components such as iron minerals and humic substances. In soil-feeding termites, acid-soluble Fe(III) and humic acids are almost completely reduced during gut passage. Here, we show that the reduction of Fe(III) and humic acids takes place also in the alkaline guts of scarab beetle larvae. Sterilized gut homogenates of Pachnoda ephippiata no longer converted Fe(III) to Fe(II), indicating an essential role of the gut microbiota in the process. From Fe(III)-reducing enrichment cultures inoculated with highly diluted gut homogenates, we isolated several facultatively anaerobic, alkali-tolerant bacteria that were closely related to metal-reducing isolates in the Bacillus thioparans group. Strain PeC11 showed a remarkable capacity for dissimilatory Fe(III) reduction, both at pH 7 and 10. Rates were strongly stimulated by the addition of the redox mediator 2,6-antraquinone disulfonate and by redox-active components in the fulvic-acid fraction of humus. Although the contribution of strain PeC11 to intestinal Fe(III) reduction in P. ephippiata remains to be further elucidated, our results corroborate the hypothesis that the lack of oxygen and the solubilization of humic substances in the extremely alkaline guts of humivorous soil fauna provide favorable conditions for the efficient reduction of Fe(III) and humic substances by a primarily fermentative microbiota.

  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. Luminescence investigation of Fe (III) – rhodamine B complexes obtained by solvent extraction

    Energy Technology Data Exchange (ETDEWEB)

    Czoik, Rozalia, E-mail: rozalia.czoik@us.edu.pl [Institute of Chemistry, University of Silesia, 9 Szkolna Street, 40-007 Katowice (Poland); Żur, Lidia; Szpikowska-Sroka, Barbara; Połedniok, Justyna [Institute of Chemistry, University of Silesia, 9 Szkolna Street, 40-007 Katowice (Poland); Swinarew, Andrzej S. [Institute of Materials Science, University of Silesia, 12 Bankowa Street, 40-007 Katowice (Poland); Pisarski, Wojciech A. [Institute of Chemistry, University of Silesia, 9 Szkolna Street, 40-007 Katowice (Poland)

    2013-07-15

    Optical properties of complexes of rhodamine B (RB) and Fe{sup 3+} ions have been investigated using optical spectroscopy. The ionic-association coordination compounds of rhodamine B and iron ions (FeRB) were prepared in the acid environment by means of solvent extraction to chloroform phase. Emission and excitation spectra and luminescence decay curves were analyzed as a function of metal ion concentration. It was found that Fe{sup 3+} ions at such conditions were effective in quenching fluorescence and that the intensity of luminescence clearly depended on the metal ion concentration. The emission decrease was observed in the concentration range from 1 to 60 μg Fe/mL solution. Similar relationship was also recorded for the luminescence lifetimes of the investigated systems. Basis on the lifetime and fluorescence intensity measurements and the Stern-Volmer relation the values of quenching rate constant k{sub q} and K{sub sv} constant for the investigated system at chloroform phase were also determined. -- Highlights: ► The complexes of rhodamine B and Fe{sup 3+} were prepared by extraction to chloroform phase. ► Optical properties of FeRB complexes were studied as a function of Fe{sup 3+} concentration. ► The emission intensities and lifetimes decrease with increasing of quencher content. ► The quenching rate constant k{sub q} and K{sub sv} constant for the study systems were determined.

  11. 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.

  12. A family of enantiopure Fe(III)4 single molecule magnets: fine tuning of energy barrier by remote substituent.

    Science.gov (United States)

    Zhu, Yuan-Yuan; Cui, Chang; Qian, Kang; Yin, Ji; Wang, Bing-Wu; Wang, Zhe-Ming; Gao, Song

    2014-08-21

    A new family of enantiopure star-shaped Fe(III)4 single-molecule magnets (SMMs) with the general formula [Fe4(L(K))6] (H2L = (R or S)-2-((2-hydroxy-1-phenylethylimino methyl)phenol); K = H (), Cl (), Br (), I (), and t-Bu ()), were structurally and magnetically characterized. Complex was reported in our previous paper (Chem. Commun., 2011, 47, 8049-8051). Detailed magnetic measurements and a systematic magneto-structural correlation study revealed that the SMM properties of this series of compounds can be finely tuned by the remote substituent of the ligands. Although the change in the coordination environment of the central Fe(3+) ions is very small, the properties of SMM behavior are changed considerably. All five complexes display frequency dependence of the ac susceptibility. However, the χ peaks of complexes and cannot be observed down to 0.5 K. The fitted anisotropy energy barriers (Ueff) of complexes , , and were 5.9, 7.1, and 11.0 K, respectively. Moreover, the hysteresis loops of these three complexes can be also observed around 0.5 K. Magneto-structural correlation analyses revealed that the coordination symmetry of the central Fe(3+) ion and the intermolecular interaction are two key factors affecting the SMM properties. Deviation to a trigonal prism coordination environment and the existence of intermolecular interactions between neighboring clusters may both reduce the anisotropy energy barriers.

  13. Synthesis, spectral characterization, structures, and oxidation state distributions in [(corrolato)Fe(III)(NO)](n) (n = 0, +1, -1) complexes.

    Science.gov (United States)

    Sinha, Woormileela; Deibel, Naina; Agarwala, Hemlata; Garai, Antara; Schweinfurth, David; Purohit, Chandra Shekhar; Lahiri, Goutam Kumar; Sarkar, Biprajit; Kar, Sanjib

    2014-02-03

    Two novel trans-A2B-corroles and three [(corrolato){FeNO}(6)] complexes have been prepared and characterized by various spectroscopic techniques. In the native state, all these [(corrolato){FeNO}(6)] species are diamagnetic and display "normal" chemical shifts in the (1)H NMR spectra. For two of the structurally characterized [(corrolato){FeNO}(6)] derivatives, the Fe-N-O bond angles are 175.0(4)° and 171.70(3)° (DFT: 179.94°), respectively, and are designated as linear nitrosyls. The Fe-N (NO) bond distances are 1.656(4) Å and 1.650(3) Å (DFT: 1.597 Å), which point toward a significant Fe(III) → NO back bonding. The NO bond lengths are 1.159(5) Å and 1.162(3) Å (DFT: 1.162 Å) and depict their elongated character. These structural data are typical for low-spin Fe(III). Electrochemical measurements show the presence of a one-electron oxidation and a one-electron reduction process for all the complexes. The one-electron oxidized species of a representative [(corrolato){FeNO}(6)] complex exhibits ligand to ligand charge transfer (LLCT) transitions (cor(π) → cor(π*)) at 399 and 637 nm, and the one-electron reduced species shows metal to ligand charge transfer (MLCT) transition (Fe(dπ) → cor(π*)) in the UV region at 330 nm. The shift of the νNO stretching frequency of a representative [(corrolato){FeNO}(6)] complex on one-electron oxidation occurs from 1782 cm(-1) to 1820 cm(-1), which corresponds to 38 cm(-1), and on one-electron reduction occurs from 1782 cm(-1) to 1605 cm(-1), which corresponds to 177 cm(-1). The X-band electron paramagnetic resonance (EPR) spectrum of one-electron oxidation at 295 K in CH2Cl2/0.1 M Bu4NPF6 displays an isotropic signal centered at g = 2.005 with a peak-to-peak separation of about 15 G. The in situ generated one-electron reduced species in CH2Cl2/0.1 M Bu4NPF6 at 295 K shows an isotropic signal centered at g = 2.029. The 99% contribution of corrole to the HOMO of native species indicates that oxidation occurs from

  14. Fabrication of magnetic porous Fe-Mn binary oxide nanowires with superior capability for removal of As(III) from water.

    Science.gov (United States)

    Cui, Hao-Jie; Cai, Jie-Kui; Zhao, Huan; Yuan, Baoling; Ai, Cui-Ling; Fu, Ming-Lai

    2014-08-30

    Magnetic porous Fe-Mn binary oxide nanowires were successfully fabricated to efficient removal of As(III) from water. The adsorption capacity of the porous nanowires for As(III) obviously increased with increasing of manganese oxide in the composite, accompanying decrease of the saturation magnetization of the adsorbents. Magnetic porous Fe-Mn binary oxide nanowires with an initial Fe:Mn molar ratio of 1:3 exhibited the highest absorption capacity for As(III) and enable magnetic separation from water. The maximal adsorption capacity value is 171mgg(-1) at pH 7.0. In the initial pH range from 3 to 9, 200μgL(-1) of As(III) could be easily decreased to below 10μgL(-1) by the magnetic porous Fe-Mn binary oxide nanowires (0.05gL(-1)) within 75min, and the corresponding residual As was completely oxidized to less toxic As(V). The coexisting chloride, nitrate and sulfate had no significant effect on arsenic removal, whereas, phosphate and humic acid reduced the removal of As(III) by competing with arsenic species for adsorption sites. The resulting magnetic porous Fe-Mn binary oxide nanowires could be a promising adsorbent for As(III) removal from water. Copyright © 2014 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

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

    2008-09-01

    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 xTi 1- xO 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 xTi 1- xO 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.

  16. A low-spin Fe(III) complex with 100-ps ligand-to-metal charge transfer photoluminescence

    DEFF Research Database (Denmark)

    Chabera, Pavel; Liu, Yizhu; Prakash, Om

    2017-01-01

    of innovative molecular designs(6,8-10), it remains a formidable scientific challenge(11) to access Earth-abundant transition-metal complexes with long-lived charge-transfer excited states. No known iron complexes are considered(12) photoluminescent at room temperature, and their rapid excited...... sufficiently to realize a long charge-transfer lifetime of 100 picoseconds (ps) and room-temperature photoluminescence. This species is a low-spin Fe(III) d(5) complex, and emission occurs from a long-lived doublet ligand-to-metal charge-transfer ((LMCT)-L-2) state that is rarely seen for transition...

  17. 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

    . As alternatives to Fe(III), they reduced fumarate, S-0 and Mn(IV). Based on 16S rRNA gene sequence similarity, strain 112(T) was most closely related to Desulfuromonas acetoxidans (97.0%) and Desulfuromonas thiophila NZ27(T) (95.5 %), and strain 102(T) to Malonomonas rubra Gra Mal 1(T) (96.3%) and Desulfuromusa...... succinoxidans Gylac(T) (95.9%) within the Deltaproteobacteria. Strains 112(T) and 102(T) therefore represent novel species, for which the names Desulfuromonas svalbardensis sp. nov. (type strain 112(T) = DSM 16958(T) = JCM 12927(T)) and Desulfuromusa ferrireducens sp. nov. (type strain 102(T) = DSM 16956 (T...

  18. Comparative adsorption of Fe(III and Cd(II ions on glutaraldehyde crosslinked chitosan–coated cristobalite

    Directory of Open Access Journals (Sweden)

    Rahmi

    2015-12-01

    Full Text Available In this study, chitosan was crosslinked with glutaraldehyde and coated on the surface of cristobalite through a dip and phase inversion process. The adsorbent was used in batch experiments to evaluate the adsorption of Fe(III and Cd(II ions. A maximum adsorption capacity was observed at a glutaraldehyde concentration in sorbent preparation of 1% (w/w. The equilibrium adsorption quantity was determined to be a function of the solution pH, initial concentration and agitation period. Langmuir and Freundlich adsorption models were used to describe adsorption isotherms.

  19. Stability of continuously produced Fe(II)/Fe(III)/As(V) co-precipitates under periodic exposure to reducing agents.

    Science.gov (United States)

    Doerfelt, Christoph; Feldmann, Thomas; Daenzer, Renaud; Demopoulos, George P

    2015-11-01

    Arsenic mobilized during ore processing necessitates its effective removal from process effluents and disposal in environmentally stable tailings. The most common method to accomplish this involves co-precipitation with excess ferric iron during lime neutralization. The precipitates produced are stable under oxic conditions. This may not be true, however, under sub-oxic or anoxic conditions. In this context, the potential stabilizing role of ferrous iron on arsenic removal/retention becomes important. As such, this work investigates the removal and redox stability of arsenic with ferrous, ferric and mixtures of both. The stability of produced solids is monitored in terms of arsenic release over time. It was found that ferrous was very effective for arsenic (V) removal with Fe(II)/As(V)=4, reducing its concentration down to reducing agent exposure. Copyright © 2015 Elsevier Ltd. All rights reserved.

  20. Investigation of photocatalytic degradation of phenol by Fe(III)-doped TiO2 and TiO2 nanoparticles.

    Science.gov (United States)

    Hemmati Borji, Saeedeh; Nasseri, Simin; Mahvi, Amir Hossein; Nabizadeh, Ramin; Javadi, Amir Hossein

    2014-01-01

    In this study Fe (III)-doped TiO2 nanoparticles were synthesized by sol-gel method at two atomic ratio of Fe/Ti, 0.006 and 0.034 percent. Then the photoactivity of them was investigated on degradation of phenol under UV (light (>380 nm). Results showed that at appropriate atomic ratio of Fe to Ti (% 0.034) photoactivity of Fe(III)-doped TiO2 nanoparticles increased. In addition, the effects of various operational parameters on photocatalytic degradation, such as pH, initial concentration of phenol and amount of photocatalyst were examined and optimized. At all different initial concentration, highest degradation efficiency occurred at pH = 3 and 0.5 g/L Fe(III)-doped TiO2 dosage. With increase in initial concentration of phenol, photocatalytic degradation efficiency decreased. Photoactivity of Fe (III)-doped TiO2 under UV irradiation and visible light at optimal condition (pH = 3 and catalyst dosage = and 0.5 g/L) was compared with P25 TiO2 nanoparticles. Results showed that photoactivity of Fe(III)-doped TiO2 under visible light was more than P25 TiO2 photoactivity, but it was less than P25 TiO2 photoactivity under UV irradiation. Also efficiency of UV irradiation alone and amount of phenol adsorption on Fe(III)-doped TiO2 at dark condition was investigated.

  1. 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.

  2. Fe(III) hydroxide nucleation and growth on quartz in the presence of Cu(II), Pb(II), and Cr(III): metal hydrolysis and adsorption.

    Science.gov (United States)

    Dai, Chong; Hu, Yandi

    2015-01-06

    Fe(III) hydroxide nanoparticles are an essential carrier for aqueous heavy metals. Particularly, iron hydroxide precipitation on mineral surfaces can immobilize aqueous heavy metals. Here, we used grazing-incidence small-angle X-ray scattering (GISAXS) to quantify nucleation and growth of iron hydroxide on quartz in 0.1 mM Fe(NO3)3 solution in the presence of Na(+), Cu(2+), Pb(2+), or Cr(3+) at pH = 3.7 ± 0.1. In 30 min, the average radii of gyration (R(g)) of particles on quartz grew from around 2 to 6 nm in the presence of Na(+) and Cu(2+). Interestingly, the particle sizes remained 3.3 ± 0.3 nm in the presence of Pb(2+), and few particles formed in the presence of Cr(3+). Quartz crystal microbalance dissipation (QCM-D) measurements showed that only Cr(3+) adsorbed onto quartz, while Cu(2+) and Pb(2+) did not. Cr(3+) adsorption changed the surface charge of quartz from negative to positive, thus inhibiting the precipitation of positively charged iron hydroxide on quartz. Masses and compositions of the precipitates were also quantified. This study provided new insights on interactions among quartz, iron hydroxide, and metal ions. Such information is helpful not only for environmental remediation but also for the doping design of iron oxide catalysts.

  3. Abiologic silicon isotope fractionation between aqueous Si and Fe(III)-Si gel in simulated Archean seawater: Implications for Si isotope records in Precambrian sedimentary rocks

    Science.gov (United States)

    Zheng, Xin-Yuan; Beard, Brian L.; Reddy, Thiruchelvi R.; Roden, Eric E.; Johnson, Clark M.

    2016-08-01

    Precambrian Si-rich sedimentary rocks, including cherts and banded iron formations (BIFs), record a >7‰ spread in 30Si/28Si ratios (δ30Si values), yet interpretation of this large variability has been hindered by the paucity of data on Si isotope exchange kinetics and equilibrium fractionation factors in systems that are pertinent to Precambrian marine conditions. Using the three-isotope method and an enriched 29Si tracer, a series of experiments were conducted to constrain Si isotope exchange kinetics and fractionation factors between amorphous Fe(III)-Si gel, a likely precursor to Precambrian jaspers and BIFs, and aqueous Si in artificial Archean seawater under anoxic conditions. Experiments were conducted at room temperature, and in the presence and absence of aqueous Fe(II) (Fe(II)aq). Results of this study demonstrate that Si solubility is significantly lower for Fe-Si gel than that of amorphous Si, indicating that seawater Si concentrations in the Precambrian may have been lower than previous estimates. The experiments reached ˜70-90% Si isotope exchange after a period of 53-126 days, and the highest extents of exchange were obtained where Fe(II)aq was present, suggesting that Fe(II)-Fe(III) electron-transfer and atom-exchange reactions catalyze Si isotope exchange through breakage of Fe-Si bonds. All experiments except one showed little change in the instantaneous solid-aqueous Si isotope fractionation factor with time, allowing extraction of equilibrium Si isotope fractionation factors through extrapolation to 100% isotope exchange. The equilibrium 30Si/28Si fractionation between Fe(III)-Si gel and aqueous Si (Δ30Sigel-aqueous) is -2.30 ± 0.25‰ (2σ) in the absence of Fe(II)aq. In the case where Fe(II)aq was present, which resulted in addition of ˜10% Fe(II) in the final solid, creating a mixed Fe(II)-Fe(III) Si gel, the equilibrium fractionation between Fe(II)-Fe(III)-Si gel and aqueous Si (Δ30Sigel-aqueous) is -3.23 ± 0.37‰ (2σ). Equilibrium

  4. Synthesis and characterization of Fe(III)-piperazine-derived complexes encapsulated in zeolite Y

    Energy Technology Data Exchange (ETDEWEB)

    Berezuk, Marcio E., E-mail: berezuk@utfpr.edu.br [Universidade Tecnologica Federal do Parana (UTFPR), Apucarana, PR (Brazil); Paesano Junior, Andrea [Dept. de Fisica, Universidade Estadual de Maringa, Maringa, (Brazil); Carvalho, Nakedia M.F. [Departament of Chemistry, Massachusetts Institute of Technology, Cambridge, MA (United States); Horn Junior, Adolfo; Arroyo, Pedro A. [Laboratorio de Ciencias Quimicas, Universidade Estadual do Norte Fluminense (UENF), Campos dos Goytacazes, RJ (Brazil); Cardozo-Filho, Lucio [Dept. de Engenharia Quimica, Universidade Estadual de Maringa, PR (Brazil)

    2012-07-01

    Zeolite-encapsulated complexes have been widely applied in hydrocarbon oxidation catalysis. The 'ship-in-a-bottle' encapsulation of iron(III) complexes containing piperazine and piperazine-derivative ligands in zeolite-Y is described. The flexible ligand methodology was employed and the efficiency and reproducibility of the procedure was investigated. The catalysts were characterized employing several techniques and the results indicate the presence of coordinated and uncoordinated iron(III) ions inside and outside the zeolitic cage. (author)

  5. Synthesis and characterization of Fe(III-piperazine-derived complexes encapsulated in zeolite Y

    Directory of Open Access Journals (Sweden)

    Márcio E. Berezuk

    2012-01-01

    Full Text Available Zeolite-encapsulated complexes have been widely applied in hydrocarbon oxidation catalysis. The "ship-in-a-bottle" encapsulation of iron(III complexes containing piperazine and piperazine-derivative ligands in zeolite-Y is described. The flexible ligand methodology was employed and the efficiency and reproducibility of the procedure was investigated. The catalysts were characterized employing several techniques and the results indicate the presence of coordinated and uncoordinated iron(III ions inside and outside the zeolitic cage.

  6. Alverine citrate induced acute hepatitis

    Institute of Scientific and Technical Information of China (English)

    Mehmet Arhan; Seyfettin K(o)klü; Aydln S K(o)ksal; (O)mer F Yolcu; Senem Koruk; Irfan Koruk; Ertugrul Kayacetin

    2004-01-01

    Alverine citrate is a commonly used smooth muscle relaxant agent. A MEDLINE search on January 2004 revealed only 1 report implicating the hepatotoxicity of this agent. A 34-year-old woman was investigated because of the finding of elevated liver function tests on biochemical screening. Other etiologies of hepatitis were appropriately ruled out and elevated enzymes were ascribed to alverine citrate treatment.Although alverine citrate hepatotoxicity was related to an immune mechanism in the first case, several features such as absence of predictable dose-dependent toxicity of alverine citrate in a previous study and absence of hypersensitivity manifestations in our patient are suggestive of a metabolic type of idiosyncratic toxicity.

  7. Constraining the Absolute Orientation of Eta Carinae's Binary Orbit: A 3-D Dynamical Model for the Broad [Fe III] Emission

    CERN Document Server

    Madura, Thomas I; Owocki, Stanley P; Groh, Jose H; Okazaki, Atsuo T; Russell, Christopher M P

    2011-01-01

    We present a three-dimensional (3-D) dynamical model for the broad [Fe III] emission observed in Eta Carinae using the Hubble Space Telescope/Space Telescope Imaging Spectrograph (HST/STIS). This model is based on full 3-D Smoothed Particle Hydrodynamics (SPH) simulations of Eta Car's binary colliding winds. Radiative transfer codes are used to generate synthetic spectro-images of [Fe III] emission line structures at various observed orbital phases and STIS slit position angles (PAs). Through a parameter study that varies the orbital inclination i, the PA {\\theta} that the orbital plane projection of the line-of-sight makes with the apastron side of the semi-major axis, and the PA on the sky of the orbital axis, we are able, for the first time, to tightly constrain the absolute 3-D orientation of the binary orbit. To simultaneously reproduce the blue-shifted emission arcs observed at orbital phase 0.976, STIS slit PA = +38 degrees, and the temporal variations in emission seen at negative slit PAs, the binary ...

  8. Synthesis of a novel heptacoordinated Fe(III) dinuclear complex: experimental and theoretical study of the magnetic properties.

    Science.gov (United States)

    Craig, Gavin A; Barrios, Leoní A; Sánchez Costa, José; Roubeau, Olivier; Ruiz, Eliseo; Teat, Simon J; Wilson, Chick C; Thomas, Lynne; Aromí, Guillem

    2010-05-28

    A new functionalized bis-pyrazol-pyridine ligand has been prepared by reaction with hydrazine of the corresponding bis-β-diketone precursor, also unprecedented. The aerobic reaction of this ligand with ferrous thiocyanate in the presence of ascorbic or oxalic acid affords the dinuclear complex of seven-coordinate Fe(III), [Fe₂(H₄L2)₂(ox)(NCS)₄] (1), as revealed by single crystal X-ray diffraction. This may represent an entry into a new family of [Fe₂] compounds with heptacoordinate metal centres. The capacity of this unusual chromophore to undergo magnetic super-exchange was investigated by means of bulk magnetization and DFT calculations. Both approaches confirmed the presence of antiferromagnetic interactions within the molecule. The theoretical investigation has served to describe the magnetic orbitals of Fe(III) in this unusual coordination geometry, as well as the exchange mechanism. A brief review of the scarce number of iron heptacoordinate complexes reported in the literature is also included and discussed.

  9. Fe(III) fertilization mitigating net global warming potential and greenhouse gas intensity in paddy rice-wheat rotation systems in China.

    Science.gov (United States)

    Liu, Shuwei; Zhang, Ling; Liu, Qiaohui; Zou, Jianwen

    2012-05-01

    A complete accounting of net greenhouse gas balance (NGHGB) and greenhouse gas intensity (GHGI) affected by Fe(III) fertilizer application was examined in typical annual paddy rice-winter wheat rotation cropping systems in southeast China. Annual fluxes of soil carbon dioxide (CO(2)), methane (CH(4)) and nitrous oxide (N(2)O) were measured using static chamber method, and the net ecosystem exchange of CO(2) (NEE) was determined by the difference between soil CO(2) emissions (R(H)) and net primary production (NPP). Fe(III) fertilizer application significantly decreased R(H) without adverse effects on NPP of rice and winter wheat. Fe(III) fertilizer application decreased seasonal CH(4) by 27-44%, but increased annual N(2)O by 65-100%. Overall, Fe(III) fertilizer application decreased the annual NGHGB and GHGI by 35-47% and 30-36%, respectively. High grain yield and low greenhouse gas intensity can be reconciled by Fe(III) fertilizer applied at the local recommendation rate in rice-based cropping 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.

    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.

  11. Detailed spectroscopic, thermodynamic, and kinetic studies on the protolytic equilibria of Fe(III)cydta and the activation of hydrogen peroxide.

    Science.gov (United States)

    Brausam, Ariane; Maigut, Joachim; Meier, Roland; Szilágyi, Petra A; Buschmann, Hans-Jürgen; Massa, Werner; Homonnay, Zoltán; van Eldik, Rudi

    2009-08-17

    The crystal structure of the as-yet-unknown salt K[Fe(III)(cydta)(H(2)O)].3H(2)O, where cydta = (+/-)-trans-1,2-cyclohexanediaminetetraacetate, has been resolved: orthorhombic space group Pbca with R1 = 0.0309, wR2 = 0.0700, and GOF = 0.99. There are two independent [Fe(III)(cydta)(H(2)O)](-) anions in the asymmetric unit, and the ligand is (R,R)-cydta in both cases. The coordination polyhedron is a seven-coordinate capped trigonal prism where the quadrilateral face formed by the four ligand donor oxygen atoms is capped by the coordinated water molecule. The speciation of [Fe(III)(cydta)(H(2)O)](-) in water was studied in detail by a combination of techniques: (i) Measurements of the pH dependence of the Fe(III/II)cydta redox potentials by cyclic voltammetry enabled the estimation of the stability constants (0.1 M KNO(3), 25 degrees C) of [Fe(III)(cydta)(H(2)O)](-) (log beta(III)(110) = 29.05 +/- 0.01) and [Fe(II)(cydta)(H(2)O)](2-) (log beta(II)(110) = 17.96 +/- 0.01) as well as pK(III)(a1OH) = 9.57 and pK(II)(a1H) = 2.69. The formation enthalpy of [Fe(III)(cydta)(H(2)O)](-) (DeltaH degrees = -23 +/- 1 kJ mol(-1)) was measured by direct calorimetry and is compared to the corresponding value for [Fe(III)(edta)(H(2)O)](-) (DeltaH degrees = -31 +/- 1 kJ mol(-1)). (ii) pH-dependent spectrophotometric titrations of Fe(III)cydta lead to pK(III)(a1OH) = 9.54 +/- 0.01 for deprotonation of the coordinated water and a dimerization constant of log K(d) = 1.07. These data are compared with those of Fe(III)pdta (pdta = 1,2-propanediaminetetraacetate; pK(III)(a1OH) = 7.70 +/- 0.01, log K(d) = 2.28) and Fe(III)edta (pK(III)(a1OH) = 7.52 +/- 0.01, log K(d) = 2.64). Temperature- and pressure-dependent (17)O NMR measurements lead to the following kinetic parameters for the water-exchange reaction at [Fe(III)(cydta)(H(2)O)](-) (at 298 K): k(ex) = (1.7 +/- 0.2) x 10(7) s(-1), DeltaH(++) = 40.2 +/- 1.3 kJ mol(-1), DeltaS(++) = +28.4 +/- 4.7 J mol(-1) K(-1), and DeltaV(++) = +2.3 +/- 0

  12. Crystal structure of Fe(HPO sub 3 ). Structure cristalline du phosphite acide de Fe sup III , Fe(HPO sub 3 H) sub 3

    Energy Technology Data Exchange (ETDEWEB)

    Sghyar, M.; Rafiq, M. (Faculte des Sciences, Fes (Morocco). Lab. de Chimie Minerale Appliquee); Durand, J.; Cox, L. (Centre National de la Recherche Scientifique, 34 - Montpellier (France). Lab. de Physicochimie des Materiaux)

    1991-01-15

    Fe(HPO{sub 3}H){sub 3}, M{sub r}=298.8, monoclinic, Cc, a=13.619(4), b=6.422(1), c=9.699(3) A, {beta}=106.27(2)deg, V=814.3(7) A{sup 3}, Z=4, D{sub m}=2.507 (by picnometry), D{sub x}=2.438 Mg m{sup -3}, {lambda}(Mo K{alpha})=0.71069 A, {mu}=2.21 mm{sup -1}, F(000)=428, room temperature. Final R=0.051, wR=0.35 for 642 independent reflections. Fe(HPO{sub 3}H){sub 3} has been studied by single-crystal X-ray analysis with an automatic diffractometer. The structure is built up of a three-dimensional network of FeO{sub 6} octahedra and HPO{sub 3}H{sup -} tetrahedra. Three hydrogenphosphite anions are hydrogen bonded and constituted an (HPO{sub 3}H){sub 3}{sup 3-} anion. (orig.).

  13. The ferroxidase center is essential for ferritin iron loading in the presence of phosphate and minimizes side reactions that form Fe(III)-phosphate colloids.

    Science.gov (United States)

    Hilton, Robert J; David Andros, N; Watt, Richard K

    2012-04-01

    Ferritin iron loading was studied in the presence of physiological serum phosphate concentrations (1 mM), elevated serum concentrations (2-5 mM), and intracellular phosphate concentrations (10 mM). Experiments compared iron loading into homopolymers of H and L ferritin with horse spleen ferritin. Prior to studying the reactions with ferritin, a series of control reactions were performed to study the solution chemistry of Fe(2+) and phosphate. In the absence of ferritin, phosphate catalyzed Fe(2+) oxidation and formed soluble polymeric Fe(III)-phosphate complexes. The Fe(III)-phosphate complexes were characterized by electron microscopy and atomic force microscopy, which revealed spherical nanoparticles with diameters of 10-20 nm. The soluble Fe(III)-phosphate complexes also formed as competing reactions during iron loading into ferritin. Elemental analysis on ferritin samples separated from the Fe(III)-phosphate complexes showed that as the phosphate concentration increased, the iron loading into horse ferritin decreased. The composition of the mineral that does form inside horse ferritin has a higher iron/phosphate ratio (~1:1) than ferritin purified from tissue (~10:1). Phosphate significantly inhibited iron loading into L ferritin, due to the lack of the ferroxidase center in this homopolymer. Spectrophotometric assays of iron loading into H ferritin showed identical iron loading curves in the presence of phosphate, indicating that the ferroxidase center of H ferritin efficiently competes with phosphate for the binding and oxidation of Fe(2+). Additional studies demonstrated that H ferritin ferroxidase activity could be used to oxidize Fe(2+) and facilitate the transfer of the Fe(3+) into apo transferrin in the presence of phosphate.

  14. Anaerobic humus and Fe(III) reduction and electron transport pathway by a novel humus-reducing bacterium, Thauera humireducens SgZ-1.

    Science.gov (United States)

    Ma, Chen; Yu, Zhen; Lu, Qin; Zhuang, Li; Zhou, Shun-Gui

    2015-04-01

    In this study, an anaerobic batch experiment was conducted to investigate the humus- and Fe(III)-reducing ability of a novel humus-reducing bacterium, Thauera humireducens SgZ-1. Inhibition tests were also performed to explore the electron transport pathways with various electron acceptors. The results indicate that in anaerobic conditions, strain SgZ-1 possesses the ability to reduce a humus analog, humic acids, soluble Fe(III), and Fe(III) oxides. Acetate, propionate, lactate, and pyruvate were suitable electron donors for humus and Fe(III) reduction by strain SgZ-1, while fermentable sugars (glucose and sucrose) were not. UV-visible spectra obtained from intact cells of strain SgZ-1 showed absorption peaks at 420, 522, and 553 nm, characteristic of c-type cytochromes (cyt c). Dithionite-reduced cyt c was reoxidized by Fe-EDTA and HFO (hydrous ferric oxide), which suggests that cyt c within intact cells of strain SgZ-1 has the ability to donate electrons to extracellular Fe(III) species. Inhibition tests revealed that dehydrogenases, quinones, and cytochromes b/c (cyt b/c) were involved in reduction of AQS (9, 10-anthraquinone-2-sulfonic acid, humus analog) and oxygen. In contrast, only NADH dehydrogenase was linked to electron transport to HFO, while dehydrogenases and cyt b/c were found to participate in the reduction of Fe-EDTA. Thus, various different electron transport pathways are employed by strain SgZ-1 for different electron acceptors. The results from this study help in understanding the electron transport processes and environmental responses of the genus Thauera.

  15. A new ion-selective electrode based on aluminium tungstate for Fe(III) determination in rock sample, pharmaceutical sample and water sample

    Indian Academy of Sciences (India)

    Mu Naushad

    2008-12-01

    An inorganic cation exchanger, aluminum tungstate (AT), has been synthesized by adding 0.1 M sodium tungstate gradually into 0.1 M aluminium nitrate at pH 1.2 with continuous stirring. The ion exchange capacity for Na+ ion and distribution coefficients of various metal ions was determined on the column of aluminium tungstate. The distribution studies of various metal ions showed the selectivity of Fe(III) ions by this cation exchange material. So, a Fe(III) ion-selective membrane electrode was prepared by using this cation exchange material as an electroactive material. The effect of plasticizers viz. dibutyl phthalate (DBP), dioctylphthalate (DOP), di-(butyl) butyl phosphate (DBBP) and tris-(2-ethylhexylphosphate) (TEHP), has also been studied on the performance of membrane sensor. It was observed that the membrane containing the composition AT: PVC: DBP in the ratio 2 : 20 : 15 displayed a useful analytical response with excellent reproducibility, low detection limit, wide working pH range (1–3.5), quick response time (15 s) and applicability over a wide concentration range of Fe(III) ions from 1 × 10-7 M to 1 × 10-1 M with a slope of 20 ± 1 mV per decade. The selectivity coefficients were determined by the mixed solution method and revealed that the electrode was selective for Fe(III) ions in the presence of interfering ions. The electrode was used for atleast 5 months without any considerable divergence in response characteristics. The constructed sensor was used as indicator electrode in the potentiometric titration of Fe(III) ions against EDTA and Fe(III) determination in rock sample, pharmaceutical sample and water sample. The results are found to be in good agreement with those obtained by using conventional methods.

  16. Comparing the effects of Fe(III) and Cu(II) on the binding affinity of erlotinib to bovine serum albumin using spectroscopic methods

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yan [The State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Chen, Mingmao [Institute of Biomedical and Pharmaceutical Technology, Fuzhou University, Fuzhou, Fujian 350002 (China); Song, Ling, E-mail: songling@fjirsm.ac.cn [The State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China)

    2013-02-15

    The interactions between erlotinib (ET) and bovine serum albumin (BSA) in the absence and presence of Cu(II) and Fe(III) in aqueous solution were investigated by using fluorescence, circular dichroism and three-dimensional (3D) fluorescence spectroscopic methods under simulative physiological conditions. Erlotinib effectively quenched the intrinsic fluorescence of BSA with slight redshifts in the absence and presence of Cu(II) and Fe(III). Cu(II) decreased the binding affinity and reduced the binding sites of erlotinib to BSA, while Fe(III) increased the binding affinity and binding sites of erlotinib to BSA. The negative values of {Delta}H and {Delta}S illustrate that the binding is mainly driven by the hydrogen bond and van der Waals force. The conformation of BSA was changed through ET binding in the presence of Cu(II) and Fe(III), which was revealed by circular dichroism, synchronous fluorescence and 3D fluorescence spectroscopic methods. The results indicate that the binding capability of erlotinib to BSA is affected by the types of metal ions. Highlights: Black-Right-Pointing-Pointer Interaction of erlotinib (ET) with BSA in the presence of Cu(II) and Fe(III) was studied. Black-Right-Pointing-Pointer Using various spectroscopic methods such as UV, CD, fluorescence and three-dimensional (3D) fluorescence. Black-Right-Pointing-Pointer Effects of metal ions on the binding activity of ET to BSA have not been reported. Black-Right-Pointing-Pointer Ternary system Cu(II)/Fe(III)-ET-BSA induced the conformational change of BSA.

  17. Characterization and Properties of Activated Carbon Prepared from Tamarind Seeds by KOH Activation for Fe(III) Adsorption from Aqueous Solution.

    Science.gov (United States)

    Mopoung, Sumrit; Moonsri, Phansiri; Palas, Wanwimon; Khumpai, Sataporn

    2015-01-01

    This research studies the characterization of activated carbon from tamarind seed with KOH activation. The effects of 0.5 : 1-1.5 : 1 KOH : tamarind seed charcoal ratios and 500-700°C activation temperatures were studied. FTIR, SEM-EDS, XRD, and BET were used to characterize tamarind seed and the activated carbon prepared from them. Proximate analysis, percent yield, iodine number, methylene blue number, and preliminary test of Fe(III) adsorption were also studied. Fe(III) adsorption was carried out by 30 mL column with 5-20 ppm Fe(III) initial concentrations. The percent yield of activated carbon prepared from tamarind seed with KOH activation decreased with increasing activation temperature and impregnation ratios, which were in the range from 54.09 to 82.03 wt%. The surface functional groups of activated carbon are O-H, C=O, C-O, -CO3, C-H, and Si-H. The XRD result showed high crystallinity coming from a potassium compound in the activated carbon. The main elements found in the activated carbon by EDS are C, O, Si, and K. The results of iodine and methylene blue adsorption indicate that the pore size of the activated carbon is mostly in the range of mesopore and macropore. The average BET pore size and BET surface area of activated carbon are 67.9764 Å and 2.7167 m(2)/g, respectively. Finally, the tamarind seed based activated carbon produced with 500°C activation temperature and 1.0 : 1 KOH : tamarind seed charcoal ratio was used for Fe(III) adsorption test. It was shown that Fe(III) was adsorbed in alkaline conditions and adsorption increased with increasing Fe(III) initial concentration from 5 to 20 ppm with capacity adsorption of 0.0069-0.019 mg/g.

  18. Fe(III)-based metal-organic framework-derived core-shell nanostructure: Sensitive electrochemical platform for high trace determination of heavy metal ions.

    Science.gov (United States)

    Zhang, Zhihong; Ji, Hongfei; Song, Yingpan; Zhang, Shuai; Wang, Minghua; Jia, Changchang; Tian, Jia-Yue; He, Linghao; Zhang, Xiaojing; Liu, Chun-Sen

    2017-03-07

    A new core-shell nanostructured composite composed of Fe(III)-based metal-organic framework (Fe-MOF) and mesoporous Fe3O4@C nanocapsules (denoted as Fe-MOF@mFe3O4@mC) was synthesized and developed as a platform for determining trace heavy metal ions in aqueous solution. Herein, the mFe3O4@mC nanocapsules were prepared by calcining the hollow Fe3O4@C that was obtained using the SiO2 nanoparticles as the template, followed by composing the Fe-MOF. The Fe-MOF@mFe3O4@mC nanocomposite demonstrated excellent electrochemical activity, water stability and high specific surface area, consequently resulting in the strong biobinding with heavy-metal-ion-targeted aptamer strands. Furthermore, by combining the conformational transition interaction, which is caused by the formation of the G-quadruplex between a single-stranded aptamer and high adsorbed amounts of heavy metal ions, the developed aptasensor exhibited a good linear relationship with the logarithm of heavy metal ion (Pb(2+) and As(3+)) concentration over the broad range from 0.01 to 10.0nM. The detection limits were estimated to be 2.27 and 6.73 pM toward detecting Pb(2+) and As(3+), respectively. The proposed aptasensor showed good regenerability, excellent selectivity, and acceptable reproducibility, suggesting promising applications in environment monitoring and biomedical fields.

  19. 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.

  20. Isolation of Fe(III)-reducing fermentative bacterium Bacteroides sp. W7 in the anode suspension of a microbial electrolysis cell (MEC)

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Aijie; Ren, Nanqi [State Key Laboratory of Urban Water Resource and Environment (SKLUWRE, HIT), Harbin 150090 (China); School of Municipal and Environmental Engineering, Harbin Institute of Technology, P.O. Box 2614, 202 Haihe Road, Harbin 150090 (China); Liu, Lihong; Sun, Dan [School of Municipal and Environmental Engineering, Harbin Institute of Technology, P.O. Box 2614, 202 Haihe Road, Harbin 150090 (China); Lee, Duu-Jong [School of Municipal and Environmental Engineering, Harbin Institute of Technology, P.O. Box 2614, 202 Haihe Road, Harbin 150090 (China); Department of Chemical Engineering, National Taiwan University, Taipei (China)

    2010-04-15

    The electron-donating strains in anode suspension of microbial electrolysis cell (MEC) have not been probed. This work for the first time isolated from the anode suspension in a double-chamber MEC a Fe(III)-reducing strain W7, which is a Gram-negative, short rod, polar flagellum, non-spore-forming bacterium. Physiological-biochemical characterization and 16S rRNA gene sequence analysis suggested that this strain is a typical fermentative bacterium and is designated to the strain Bacteroides sp. W7 (GeneBank accession no. FJ862827). The strain W7 could reduce Fe(III) to form 8.5 mmol L{sup -1} of Fe(II) in 39 h cultivation. Moreover, this strain can transfer electrons to Fe(III) during its growth by adopting glucose, yeast extract and sodium lactate as carbon source. The presence of this Fe(III)-reducing fermentative bacterium suggests the possible contribution of suspended organisms to the efficiency of MEC. (author)

  1. Characterization and Properties of Activated Carbon Prepared from Tamarind Seeds by KOH Activation for Fe(III) Adsorption from Aqueous Solution

    OpenAIRE

    Sumrit Mopoung; Phansiri Moonsri; Wanwimon Palas; Sataporn Khumpai

    2015-01-01

    This research studies the characterization of activated carbon from tamarind seed with KOH activation. The effects of 0.5 : 1–1.5 : 1 KOH : tamarind seed charcoal ratios and 500–700°C activation temperatures were studied. FTIR, SEM-EDS, XRD, and BET were used to characterize tamarind seed and the activated carbon prepared from them. Proximate analysis, percent yield, iodine number, methylene blue number, and preliminary test of Fe(III) adsorption were also studied. Fe(III) adsorption was carr...

  2. Potential for quantifying expression of the Geobacteraceae citrate synthase gene to assess the activity of Geobacteraceae in the subsurface and on current-harvesting electrodes

    Science.gov (United States)

    Holmes, Dawn E.; Nevin, Kelly P.; O'Neil, Regina A.; Ward, Joy E.; Adams, Lorrie A.; Woodard, Trevor L.; Vrionis, Helen A.; Lovely, Derek R.

    2005-01-01

    The Geobacteraceae citrate synthase is phylogenetically distinct from those of other prokaryotes and is a key enzyme in the central metabolism of Geobacteraceae. Therefore, the potential for using levels of citrate synthase mRNA to estimate rates of Geobacter metabolism was evaluated in pure culture studies and in four different Geobacteraceae-dominated environments. Quantitative reverse transcription-PCR studies with mRNA extracted from cultures of Geobacter sulfurreducens grown in chemostats with Fe(III) as the electron acceptor or in batch with electrodes as the electron acceptor indicated that transcript levels of the citrate synthase gene, gltA, increased with increased rates of growth/Fe(III) reduction or current production, whereas the expression of the constitutively expressed housekeeping genes recA, rpoD, and proC remained relatively constant. Analysis of mRNA extracted from groundwater collected from a U(VI)-contaminated site undergoing in situ uranium bioremediation revealed a remarkable correspondence between acetate levels in the groundwater and levels of transcripts of gltA. The expression of gltA was also significantly greater in RNA extracted from groundwater beneath a highway runoff recharge pool that was exposed to calcium magnesium acetate in June, when acetate concentrations were high, than in October, when the levels had significantly decreased. It was also possible to detect gltA transcripts on current-harvesting anodes deployed in freshwater sediments. These results suggest that it is possible to monitor the in situ metabolic rate of Geobacteraceae by tracking the expression of the citrate synthase gene.

  3. 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.

  4. 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)

  5. The role of multihaem cytochromes in the respiration of nitrite in Escherichia coli and Fe(III) in Shewanella oneidensis.

    Science.gov (United States)

    Clarke, Thomas A; Holley, Tracey; Hartshorne, Robert S; Fredrickson, Jim K; Zachara, John M; Shi, Liang; Richardson, David J

    2008-10-01

    The periplasmic nitrite reductase system from Escherichia coli and the extracellular Fe(III) reductase system from Shewanella oneidensis contain multihaem c-type cytochromes as electron carriers and terminal reductases. The position and orientation of the haem cofactors in multihaem cytochromes from different bacteria often show significant conservation despite different arrangements of the polypeptide chain. We propose that the decahaem cytochromes of the iron reductase system MtrA, MtrC and OmcA comprise pentahaem 'modules' similar to the electron donor protein, NrfB, from E. coli. To demonstrate this, we have isolated and characterized the N-terminal pentahaem module of MtrA by preparing a truncated form containing five covalently attached haems. UV-visible spectroscopy indicated that all five haems were low-spin, consistent with the presence of bis-His ligand co-ordination as found in full-length MtrA.

  6. Adsorption of Ni(II, Cu(II and Fe(III from Aqueous Solutions Using Activated Carbon

    Directory of Open Access Journals (Sweden)

    A. Edwin Vasu

    2008-01-01

    Full Text Available An activated carbon was tested for its ability to remove transition metal ions from aqueous solutions. Physical, Chemical and liquid-phase adsorption characterizations of the carbon were done following standard procedures. Studies on the removal of Ni(II, Cu(II and Fe(III ions were attempted by varying adsorbate dose, pH of the metal ion solution and time in batch mode. The equilibrium adsorption data were fitted with Freundlich, Langmuir and Redlich-Peterson isotherms and the isotherm constants were evaluated. Time variation studies indicate that adsorptions follow pseudo-second order kinetics. pH was found to have a significant role to play in the adsorption. The processes were endothermic and the thermodynamic parameters were evaluated. Desorption studies indicate that ion-exchange mechanism is operating.

  7. Characterization of phosphoproteins from electrophoretic gels by nanoscale Fe(III) affinity chromatography with off-line mass spectrometry analysis

    DEFF Research Database (Denmark)

    Stensballe, A; Andersen, Søren; Jensen, Ole Nørregaard

    2001-01-01

    Detailed characterization of phosphoproteins as well as other post-translationally modified proteins is required to fully understand protein function and regulatory events in cells and organisms. Here we present a mass spectrometry (MS) based experimental strategy for the identification and mapping...... chromatography (Fe(III)-IMAC) columns were employed for enrichment of phosphorylated peptides from crude peptide mixtures prior to off-line analysis by matrix-assisted laser desorption/ionization (MALDI) MS or nanoelectrospray tandem mass spectrometry (MS/MS). An optimized and sensitive procedure for alkaline...... of phosphorylation sites. The advantages and limitations of the experimental strategy was demonstrated by enrichment, identification and sequencing of phosphopeptides from the model proteins ovalbumin and bovine beta-casein isolated by gel electrophoresis. Furthermore, an autophosphorylation site at Ser-3...

  8. Preparation and XPS studies of macromolecule mixed-valent Cu(I, II) and Fe(II, III) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Wang Bo [Institute of Energy Chemistry, College of Chemistry and Materials Science, Shaanxi Normal University, Xi' An 710062 (China)]. E-mail: wangbo@snnu.edu.cn; Gao Fengqin [Institute of Energy Chemistry, College of Chemistry and Materials Science, Shaanxi Normal University, Xi' An 710062 (China); Department of Chemistry, Xianyang Normal University, Xianyang (China); Ma Hongzhu [Institute of Energy Chemistry, College of Chemistry and Materials Science, Shaanxi Normal University, Xi' An 710062 (China)

    2007-06-01

    A new macromolecule ligand and its mixed-valent Cu(I, II) and Fe(II, III) complexes have been prepared by using ethylenediamine as core and maleic anhydride as branched units and characterized by UV-vis, FT-IR, thermal analysis and X-ray photoelectron spectroscopy (XPS). The data obtained from these studies suggested that the coordinate bonds of N {sup {yields}} M, Cl {sup {yields}} M, Ph-OH {sup {yields}} M and H{sub 2}O {sup {yields}} M have been formed and possible binding models are proposed for these complexes. The thermal analysis (TG-DTG) reveals that these complexes possess thermal stable property below 800 deg. C.

  9. 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.

  10. Constraining the Absolute Orientation of eta Carinae's Binary Orbit: A 3-D Dynamical Model for the Broad [Fe III] Emission

    Science.gov (United States)

    Madura, T. I.; Gull, T. R.; Owocki, S. P.; Groh, J. H.; Okazaki, A. T.; Russell, C. M. P.

    2011-01-01

    We present a three-dimensional (3-D) dynamical model for the broad [Fe III] emission observed in Eta Carinae using the Hubble Space Telescope/Space Telescope Imaging Spectrograph (HST/STIS). This model is based on full 3-D Smoothed Particle Hydrodynamics (SPH) simulations of Eta Car's binary colliding winds. Radiative transfer codes are used to generate synthetic spectro-images of [Fe III] emission line structures at various observed orbital phases and STIS slit position angles (PAs). Through a parameter study that varies the orbital inclination i, the PA(theta) that the orbital plane projection of the line-of-sight makes with the apastron side of the semi-major axis, and the PA on the sky of the orbital axis, we are able, for the first time, to tightly constrain the absolute 3-D orientation of the binary orbit. To simultaneously reproduce the blue-shifted emission arcs observed at orbital phase 0.976, STIS slit PA = +38deg, and the temporal variations in emission seen at negative slit PAs, the binary needs to have an i approx. = 130deg to 145deg, Theta approx. = -15deg to +30deg, and an orbital axis projected on the sky at a P A approx. = 302deg to 327deg east of north. This represents a system with an orbital axis that is closely aligned with the inferred polar axis of the Homunculus nebula, in 3-D. The companion star, Eta(sub B), thus orbits clockwise on the sky and is on the observer's side of the system at apastron. This orientation has important implications for theories for the formation of the Homunculus and helps lay the groundwork for orbital modeling to determine the stellar masses.

  11. 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

  12. Electron transfer capacity dependence of quinone-mediated Fe(III) reduction and current generation by Klebsiella pneumoniae L17.

    Science.gov (United States)

    Li, Xiaomin; Liu, Liang; Liu, Tongxu; Yuan, Tian; Zhang, Wei; Li, Fangbai; Zhou, Shungui; Li, Yongtao

    2013-06-01

    Quinone groups in exogenous electron shuttles can accelerate extracellular electron transfer (EET) from bacteria to insoluble terminal electron acceptors, such as Fe(III) oxides and electrodes, which are important in biogeochemical redox processes and microbial electricity generation. However, the relationship between quinone-mediated EET performance and electron-shuttling properties of the quinones remains incompletely characterized. This study investigates the effects of a series of synthetic quinones (SQs) on goethite reduction and current generation by a fermenting bacterium Klebsiella pneumoniae L17. In addition, the voltammetric behavior and electron transfer capacities (ETCs) of SQ, including electron accepting (EAC) and donating (EDC) capacities, is also examined using electrochemical methods. The results showed that SQ can significantly increase both the Fe(III) reduction rates and current outputs of L17. Each tested SQ reversibly accepted and donated electrons as indicated by the cyclic voltammograms. The EAC and EDC results showed that Carmine and Alizarin had low relative capacities of electron transfer, whereas 9,10-anthraquinone-2,6-disulfonic acid (AQDS), 2-hydroxy-1,4-naphthoquinone (2-HNQ), and 5-hydroxy-1,4-naphthoquinone (5-HNQ) showed stronger relative ETC, and 9,10-anthraquinone-2-carboxylic acid (AQC) and 9,10-anthraquinone-2-sulfonic acid (AQS) had high relative ETC. Enhancement of microbial goethite reduction kinetics and current outputs by SQ had a good linear relationship with their ETC, indicating that the effectiveness of quinone-mediated EET may be strongly dependent on the ETC of the quinones. Therefore, the presence of quinone compounds and fermenting microorganisms may increase the diversity of microbial populations that contribute to element transformation in natural environments. Moreover, ETC determination of different SQ would help to evaluate their performance for microbial EET under anoxic conditions. Copyright © 2013 Elsevier

  13. 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.

  14. Grafting of functionalized [Fe(III)(salten)] complexes to Au(111) surfaces via thiolate groups: surface spectroscopic characterization and comparison of different linker designs.

    Science.gov (United States)

    Jacob, Hanne; Kathirvel, Ketheeswari; Petersen, Finn; Strunskus, Thomas; Bannwarth, Alexander; Meyer, Sven; Tuczek, Felix

    2013-07-01

    Functionalization of surfaces with spin crossover complexes is an intensively studied topic. Starting from dinuclear iron(III)-salten complexes [Fe(salten)(pyS)]2(BPh4)2 and [Fe(thiotolylsalten)(NCS)]2 with disulfide-containing bridging ligands, corresponding mononuclear complexes [Fe(salten)(pyS)](+) and [Fe(thiotolylsalten)(NCS)] are covalently attached to Au(111) surfaces (pySH, pyridinethiol; salten, bis(3-salicylidene-aminopropyl)amine). The adsorbed monolayers are investigated by infrared reflection absorption spectroscopy (IRRAS) in combination with X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS). Comparison of the surface vibrational spectra with bulk data allows us to draw conclusions with respect to the geometry of the adsorbed complexes. An anomaly is observed in the spectra of the surface-adsorbed monolayer of [Fe(salten)(pyS)](+), which suggests that the salten ligand is partially decoordinated from the Fe(III) center and one of its phenolate arms binds to the Au(111) surface. For complex [Fe(thiotolylsalten)(NCS)] that is bound to the Au(111) surface via a thiolate-functionalized salten ligand, this anomaly is not observed, which indicates that the coordination sphere of the complex in the bulk is retained on the surface. The implications of these results with respect to the preparation of surface-adsorbed monolayers of functional transition-metal complexes are discussed.

  15. Thiol-functionalized Fe3O4/SiO2 microspheres with superparamagnetism and their adsorption properties for Au(III) ion separation

    Science.gov (United States)

    Peng, Xiangqian; Zhang, Wei; Gai, Ligang; Jiang, Haihui; Tian, Yan

    2016-08-01

    Thiol-functionalized Fe3O4/SiO2 microspheres (Fe3O4/SiO2-SH) with high saturation magnetization (69.3 emu g-1), superparamagnetism, and good dispersibility have been prepared by an ethylene glycol reduction method in combination with a modified Stöber method. The as-prepared composite magnetic spheres are characterized with fourier transform infrared spectroscopy (FT-IR), zeta potential, X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and superconducting quantum interference magnetometer, and tested in separation of Au(III) ions from aqueous solutions. The data for Au(III) adsorption on Fe3O4/SiO2-SH are analyzed with the Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich isotherm models, and the pseudo-first-order, pseudo-second-order, and intraparticle diffusion kinetics models. The adsorption behaviors of Au(III) on Fe3O4/SiO2-SH follow the Langmuir isotherm model, and the adsorption process conforms to the pseudo-second-order kinetic model. The maximum adsorption capacity of Au(III) on Fe3O4/SiO2-SH is 43.7 mg g-1. Acetate anions play an important role yet Cu(II) ions have little interference in the adsorption of Au(III) on the adsorbent. A satisfactory recovery percentage of 89.5% is acquired by using an eluent with 1 M thiourea and 5% HCl, although thiols have a high affinity to Au(III) ions based on the hard-soft acid-base (HSAB) theory by Pearson.

  16. Molecular Hydrogen and [Fe II] in Active Galactic Nuclei III: LINERS and Star Forming Galaxies

    CERN Document Server

    Riffel, R; Aleman, I; Brotherton, M S; Pastoriza, M G; Bonatto, C J; Dors, O L

    2013-01-01

    We study the kinematics and excitation mechanisms of H2 and [Fe II] lines in a sample of 67 emission-line galaxies with Infrared Telescope Facility SpeX near-infrared (NIR, 0.8-2.4 micrometers) spectroscopy together with new photoionisation models. H2 emission lines are systematically narrower than narrow-line region (NLR) lines, suggesting that the two are, very likely, kinematically disconnected. The new models and emission-line ratios show that the thermal excitation plays an important role not only in active galactic nuclei but also in star forming galaxies. The importance of the thermal excitation in star forming galaxies may be associated with the presence of supernova remnants close to the region emitting H2 lines. This hypothesis is further supported by the similarity between the vibrational and rotational temperatures of H2. We confirm that the diagram involving the line ratios H2 2.121/Br_gamma and [Fe II] 1.257/Pa_beta is an efficient tool for separating emission-line objects according to their dom...

  17. Hydrothermal Synthesis and Properties of Open-Framework Mixed-valence Iron Phosphates FeIII2FeII1.5(PO4)3 with Three-dimensional Structure

    Institute of Scientific and Technical Information of China (English)

    DUAN,Li-Ying(段丽颖); LIU,Fu-Chen(刘福臣); WANG,En-Bo(王恩波); LI,Yang-Guang(李阳光); HU,Chang-Wen(胡长文); XU,Lin(许林)

    2004-01-01

    The open-framework iron phosphate FeIII2FeII1.5(PO4)3 was hydrothermally synthesized and characterized by elemental analysis, IR, EPR, XPS and single crystal X-ray diffraction analysis. The title compound crystallized in the triclinic, space group P1 with a=0.64724(4) nm, b=0.79651(6) nm, c=0.94229(5) nm, α=104.447(2)°, β=108.919(4)°, γ=101.741(4)°, V=0.42302(5) nm3, Z=1 and R1 (wR2)=0.0307 (0.0793). Crystal data were collected on a Rigaku R-AXIS RAPID IP diffractometer with Mo Kα (λ=0.071073 nm) at 293(2) K in the range of 2.43°<θ<27.46°. The structure of 1 consists of 19 non-hydrogen atoms including three and a half crystallographically independent Fe and three P atoms. Fe(1) connects its symmetrical Fe(1A) through bridging oxygen forming a dimer and the dimers are connected by Fe(4) forming an infinite staircase-like chain. Fe(2) and Fe(3) connect the infinite chains into a layer with bridging oxygen. Layers are interconnected via Fe(4) forming the six-membered and eight-membered channel systems.

  18. Impacts of Shewanella putrefaciens strain CN-32 cells and extracellular polymeric substances on the sorption of As(V) and As(III) on Fe(III)-(hydr)oxides.

    Science.gov (United States)

    Huang, Jen-How; Elzinga, Evert J; Brechbuehl, Yves; Voegelin, Andreas; Kretzschmar, Ruben

    2011-04-01

    We investigated the effects of Shewanella putrefaciens cells and extracellular polymeric substances on the sorption of As(III) and As(V) to goethite, ferrihydrite, and hematite at pH 7.0. Adsorption of As(III) and As(V) at solution concentrations between 0.001 and 20 μM decreased by 10 to 45% in the presence of 0.3 g L(-1) EPS, with As(III) being affected more strongly than As(V). Also, inactivated Shewanella cells induced desorption of As(V) from the Fe(III)-(hydr)oxide mineral surfaces. ATR-FTIR studies of ternary As(V)-Shewanella-hematite systems indicated As(V) desorption concurrent with attachment of bacterial cells at the hematite surface, and showed evidence of inner-sphere coordination of bacterial phosphate and carboxylate groups at hematite surface sites. Competition between As(V) and bacterial phosphate and carboxylate groups for Fe(III)-(oxyhydr)oxide surface sites is proposed as an important factor leading to increased solubility of As(V). The results from this study have implications for the solubility of As(V) in the soil rhizosphere and in geochemical systems undergoing microbially mediated reduction and indicate that the presence of sorbed oxyanions may affect Fe-reduction and biofilm development at mineral surfaces.

  19. Core-double-shell Fe3O4@carbon@poly(In(III)-carboxylate) microspheres: cycloaddition of CO2 and epoxides on coordination polymer shells constituted by imidazolium-derived Al(III)-Salen bifunctional catalysts.

    Science.gov (United States)

    An, Qiao; Li, Zifeng; Graff, Robert; Guo, Jia; Gao, Haifeng; Wang, Changchun

    2015-03-01

    A hydrid microsphere Fe3O4@carbon@poly(In(III)-carboxylate) consisting of a cluster of Fe3O4 nanoparticles as the core, a carbon layer as the inner shell and a porous In(III)-carboxylate coordination polymer as the outer shell was prepared and applied as a recyclable catalyst for the cycloaddition reaction of CO2 and epoxides. Construction of this hybrid microsphere was achieved in the two steps, including (1) the one-pot solvothermal synthesis of Fe3O4@C particles with the abundant carboxylic groups on the carbon surface and (2) the subsequent growth of the outer shell polymers based on the precipitation coordination polymerization. Imidazolium-substituted Salen ligands were synthesized and chelated with the In(III) ions using the terminal carboxylic groups. The coordination polymer shell was formed on the Fe3O4@C particles, and the structures including shell thickness, surface area and porosity could be varied by tuning the feeding ratios of the In(III) ions and the ligands. The optimal structure of the coordination polymers showed a shell thickness of ca. 45 nm with ∼5 nm of mesopore, 174.7 m(2)/g of surface area and 0.2175 cm(3)/g of pore volume. In light of gas uptake capability, catalytic activity and magnetic susceptibility, cycloaddition of CO2 with a series of epoxides were studied by using Al-complexed Fe3O4@C@In(III)-[IL-Salen] microspheres. The results validated that the self-supporting catalytic layer with high surface area was of remarkable advantages, which were attributed from great increment of effective active sites and combination of nucleophilic/electrophilic synergistic property and CO2 uptake capability. Therefore, these hybrid microspheres provided excellent catalytic activity, prominent selectivity to cyclic carbonates and outstanding recyclability with the assistance of an applied magnetic field.

  20. Silica (NPs) supported Fe (III) as a reusable heterogeneous catalyst for the one-pot synthesis of 1, 4-dihydropyridines under mild conditions

    Indian Academy of Sciences (India)

    Javad Safaei-Ghomi; Abolfazl Ziarati; Safura Zahedi

    2012-07-01

    A cheap and recyclable silica (NPs) supported Fe (III) was prepared as heterogeneous catalyst for the synthesis of various substituted 1,4-dihydropyridines via condensation of aldehydes with ethyl acetoacetate and ammonium acetate in ethanol. The products were separated from the catalyst simply by filtration and the catalyst could be recycled and reused for several times without noticeable decrease in the catalytic activity.

  1. A strictly anaerobic betaproteobacterium Georgfuchsia toluolica gen. nov., sp. nov. degrades aromatic compounds with Fe(III), Mn(IV) or nitrate as an electron acceptor

    NARCIS (Netherlands)

    Weelink, S.A.B.; Doesburg, van W.C.J.; Talarico Saia, F.; Rijpstra, I.; Smidt, H.; Röling, W.; Stams, A.J.M.

    2009-01-01

    A bacterium (strain G5G6) that grows anaerobically with toluene was isolated from a polluted aquifer (Banisveld, the Netherlands). The bacterium uses Fe(III), Mn(IV) and nitrate as terminal electron acceptors for growth on aromatic compounds. The bacterium does not grow on sugars, lactate or acetate

  2. Nanowires, Capacitors, and Other Novel Outer-Surface Components Involved in Electron Transfer to Fe(III) Oxides in Geobacter Species

    Energy Technology Data Exchange (ETDEWEB)

    Lovley, Derek, R.

    2008-12-22

    The overall goal of this project was to better understand the mechanisms by which Geobacter species transfer electrons outside the cell onto Fe(III) oxides. The rationale for this study was that Geobacter species are often the predominant microorganisms involved in in situ uranium bioremediation and the growth and activity of the Geobacter species during bioremediation is primarily supported by electron transfer to Fe(III) oxides. These studies greatly expanded the understanding of electron transfer to Fe(III). Novel concepts developed included the potential role of microbial nanowires for long range electron transfer in Geobacter species and the importance of extracytoplasmic cytochromes functioning as capacitors to permit continued electron transfer during the hunt for Fe(III) oxide. Furthermore, these studies provided target sequences that were then used in other studies to tract the activity of Geobacter species in the subsurface through monitoring the abundance of gene transcripts of the target genes. A brief summary of the major accomplishments of the project is provided.

  3. Pathways of carbon oxidation in an Arctic fjord sediment (Svalbard) and isolation of psychrophilic and psychrotolerant Fe(III)-reducing bacteria

    DEFF Research Database (Denmark)

    Vandieken, Verona; Finke, Niko; Jørgensen, Bo Barker

    2006-01-01

    , Desulfuromusa, Shewanella and Desulfovibrio were isolated from enrichment cultures of 2 fjord sediments from Svalbard. Strains related to Desulfovibrio reduced Fe(III) without energy generation for growth. All isolates were psychrophilic or psychrotolerant and grew at –2°C, the freezing point of sea water...

  4. Pathways of carbon oxidation in an Arctic fjord sediment (Svalbard) and isolation of psychrophilic and psychrotolerant Fe(III)-reducing bacteria

    DEFF Research Database (Denmark)

    Vandieken, Verona; Finke, Niko; Jørgensen, Bo Barker

    2006-01-01

    Desulfuromonas, Desulfuromusa, Shewanella and Desulfovibrio were isolated from enrichment cultures of 2 fjord sediments from Svalbard. Strains related to Desulfovibrio reduced Fe(III) without energy generation for growth. All isolates were psychrophilic or psychro-tolerant and grew at -2 degrees C, the freezing...

  5. Microbial Mineral Transformations at the Fe(II)/Fe(III) Redox Boundary for Solid Phase Capture of Strontium and Other Metal/Radionuclide Contaminants

    Energy Technology Data Exchange (ETDEWEB)

    F. G. Ferris; E. E. Roden

    2000-01-31

    The migration of {sup 90}Sr in groundwater is a significant environmental concern at former nuclear weapons production sites in the US and abroad. Although retardation of {sup 90}Sr transport relative to mean groundwater velocity is known to occur in contaminated aquifers, Sr{sup 2+} does not sorb as strongly to iron oxides and other mineral phases as do other metal-radionuclides contaminants. Thus, some potential exists for extensive {sup 90}Sr migration from sources of contamination. Chemical or biological processes capable of retarding or immobilizing Sr{sup 2+} in groundwater environments are of interest from the standpoint of understanding controls on subsurface Sr{sup 2+} migration. In addition, it may be possible to exploit such processes for remediation of subsurface Sr contamination. In this study the authors examined the potential for the solid phase sorption and incorporation of Sr{sup 2+} into carbonate minerals formed during microbial Fe(III) oxide reduction as a first step toward evaluating whether this process could be used to promote retardation of {sup 90}Sr migrations in anaerobic subsurface environments. The demonstration of Sr{sup 2+} capture in carbonate mineral phases formed during bacterial HFO reduction and urea hydrolysis suggests that microbial carbonate mineral formation could contribute to Sr{sup 2+} retardation in groundwater environments. This process may also provide a mechanism for subsurface remediation of Sr{sup 2+} and other divalent metal contaminants that form insoluble carbonate precipitates.

  6. Gold Nanoparticle-based Surface-enhanced Raman Scattering Fe(III) Ion Sensor

    Energy Technology Data Exchange (ETDEWEB)

    Ly, Nguyen Hoang; Joo, Sang-Woo [Soongsil University, Seoul (Korea, Republic of); Cho, Kwang Hwi [School of Systems Biomedical Science, Seoul (Korea, Republic of)

    2015-01-15

    We performed density functional theory (DFT) calculations of 4-aminobenzo-15-crown-5 (4AB15C5) in conjugation with 4-mercaptobenzoic acid (4MCB) with the polarizable continuum model (PCM) while considering the aqueous media. After specific binding of the ferric ion onto the 4MCB.4AB15C5 compound, the Raman frequencies and intensities were estimated by DFT calculations with the PCM. It was predicted that the Raman intensities became significantly increased upon binding of the ferric ion. 4MCB.4AB15C5 could be assembled on gold nanoparticles (AuNPs) via the cleavage of the thiol bond. Colorimetric and UV.Vis absorption spectroscopy indicated that AuNPs became significantly aggregated in the presence of 1.10 mM of the ferric ion. Surface-enhanced Raman scattering (SERS) of 4MCB.4AB15C5 was used to identify the dissimilar spectral behaviors that yield a difference in intensity in the presence of the ferric ion. These changes were not observed in the other biological ions Zn{sup 2+}, Mn{sup 2+}, Fe{sup 2+}, Na{sup +}, K{sup +}, Ca{sup 2+}, Mg{sup 2+}, NH{sup 4+}, and Co{sup 2+}. This study indicated that 4AB15C5 could be used to detect ferric ions in aqueous AuNP solutions by a combined method of colorimetric, UV.Vis absorption, and Raman spectroscopy. AuNPs.[4MCB. 4AB15C5] can thus be utilized as a selective turn-on sensor to Fe3{sup +} in aqueous solutions above 1 mM.

  7. Properties of Square-Pyramidal Alkyl-Thiolate FeIII-Complexes, Including an Analogue of the Unmodified Form of Nitrile Hydratase

    Science.gov (United States)

    Lugo-Mas, Priscilla; Taylor, Wendy; Schweitzer, Dirk; Theisen, Roslyn M.; Xu, Liang; Shearer, Jason; Swartz, Rodney D.; Gleaves, Morgan C.; DiPasquale, Antonio; Kaminsky, Werner; Kovacs, Julie A.

    2009-01-01

    The syntheses and structures of three new coordinatively unsaturated, monomeric, square pyramidal thiolate-ligated Fe(III) complexes are described, [FeIII((tame—N3)S2Me2)]+ (1), [FeIII(Et—N2S2Me2)(py)]1- (3), and [FeIII((tame—N2S)S2Me2)]2- (15). The anionic bis-carboxamide, tris-thiolate N2S3 coordination sphere of 15 is potentially similar to that of the yet-to-be characterized unmodified form of NHase. Comparison of the magnetic and reactivity properties of these reveals how anionic charge build-up (from cationic 1 to anionic 3 and dianionic 15) and spin-state influence apical ligand affinity. For all of the ligand-field combinations examined, an intermediate S= 3/2 spin-state was shown to be favored by a strong N2S2 basal plane ligand-field, and this was found to reduce the affinity for apical ligands, even when they are built-in. This is in contrast to the post-translationaly modified NHase active site, which is low-spin, and displays a higher affinity for apical ligands. Cationic 1 and its reduced FeII precursor are shown to bind NO and CO, respectively, to afford [FeIII((tame-N3)S2Me(NO)]+ (18, νNO= 1865 cm-1), an analogue of NO-inactivated NHase, and [FeII((tame-N3)S2Me)(CO)] (16; νCO stretch (1895 cm-1). Anions (N3-, CN-) are shown to be unreactive towards 1, 3 and 15, and neutral ligands unreactive towards 3 and 15, even when present in 100-fold excess, and at low—temperatures. The curtailed reactivity of 15, an analogue of the unmodified form of NHase, and its apical-oxygenated S= 3/2 derivative [FeIII((tame—N2SO2)S2Me2)]2- (20) suggests that regioselective post—translational oxygenation of the basal plane NHase cysteinate sulfurs plays an important role in promoting substrate binding. This is supported by previously reported theoretical (DFT) calculations.1 PMID:18989922

  8. 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.

  9. Spectrophotometric Determination of Kinetic Constants of Fe (Iii-Amines’s Charge Transfere Complexes

    Directory of Open Access Journals (Sweden)

    Kamel Bentayeb

    2016-05-01

    Full Text Available Using UV-visible spectrophotometric data of (1:1, electron donor-acceptor complexes (AD1, AD2 and AD3 have been investigated. The complexes concerned are n-butyl amine (D1 and cyclohexyl amine (D2 and phenyl hydrazine (D3 as electron donors with iron (III ion as an electron acceptor (A in methanol at 25°C. The values of formation constant (KAD, molar extinction coefficient (εAD, and absorption band energy of complexes were estimated. The ionization potential of the donors ID, were calculated from the complex band energies. The kinetics of the above association and reverse reactions were studied and some kinetic parameters have been estimated.

  10. The Geoglobus acetivorans genome: Fe(III) reduction, acetate utilization, autotrophic growth, and degradation of aromatic compounds in a hyperthermophilic archaeon.

    Science.gov (United States)

    Mardanov, Andrey V; Slododkina, Galina B; Slobodkin, Alexander I; Beletsky, Alexey V; Gavrilov, Sergey N; Kublanov, Ilya V; Bonch-Osmolovskaya, Elizaveta A; Skryabin, Konstantin G; Ravin, Nikolai V

    2015-02-01

    Geoglobus acetivorans is a hyperthermophilic anaerobic euryarchaeon of the order Archaeoglobales isolated from deep-sea hydrothermal vents. A unique physiological feature of the members of the genus Geoglobus is their obligate dependence on Fe(III) reduction, which plays an important role in the geochemistry of hydrothermal systems. The features of this organism and its complete 1,860,815-bp genome sequence are described in this report. Genome analysis revealed pathways enabling oxidation of molecular hydrogen, proteinaceous substrates, fatty acids, aromatic compounds, n-alkanes, and organic acids, including acetate, through anaerobic respiration linked to Fe(III) reduction. Consistent with the inability of G. acetivorans to grow on carbohydrates, the modified Embden-Meyerhof pathway encoded by the genome is incomplete. Autotrophic CO2 fixation is enabled by the Wood-Ljungdahl pathway. Reduction of insoluble poorly crystalline Fe(III) oxide depends on the transfer of electrons from the quinone pool to multiheme c-type cytochromes exposed on the cell surface. Direct contact of the cells and Fe(III) oxide particles could be facilitated by pilus-like appendages. Genome analysis indicated the presence of metabolic pathways for anaerobic degradation of aromatic compounds and n-alkanes, although an ability of G. acetivorans to grow on these substrates was not observed in laboratory experiments. Overall, our results suggest that Geoglobus species could play an important role in microbial communities of deep-sea hydrothermal vents as lithoautotrophic producers. An additional role as decomposers would close the biogeochemical cycle of carbon through complete mineralization of various organic compounds via Fe(III) respiration.

  11. Flux analysis of central metabolic pathways in Geobactermetallireducens during reduction of solubleFe(III)-NTA

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Yinjie J.; Chakraborty, Romy; Garcia-Martin, Hector; Chu,Jeannie; Hazen, Terry C.; Keasling, Jay D.

    2007-01-01

    We analyzed the carbon fluxes in the central metabolism ofGeobacter metallireducens strain GS-15 using 13C isotopomer modeling.Acetate labeled in the 1st or 2nd position was the sole carbon source,and Fe-NTA was the sole terminal electron acceptor. The measured labeledacetate uptake rate was 21 mmol/gdw/h in the exponential growth phase.The resulting isotope labeling pattern of amino acids allowed an accuratedetermination of the in vivo global metabolic reaction rates (fluxes)through the central metabolic pathways using a computational isotopomermodel. The tracer experiments showed that G. metallireducens containedcomplete biosynthesis pathways for essential metabolism, and this strainmight also have an unusual isoleucine biosynthesis route (usingacetyl-CoA and pyruvate as the precursors). The model indicated that over90 percent of the acetate was completely oxidized to CO2 via a completetricarboxylic acid (TCA) cycle while reducing iron. Pyruvate carboxylaseand phosphoenolpyruvate carboxykinase were present under theseconditions, but enzymes in the glyoxylate shunt and malic enzyme wereabsent. Gluconeogenesis and the pentose phosphate pathway were mainlyemployed for biosynthesis and accounted for less than 3 percent of totalcarbon consumption. The model also indicated surprisingly highreversibility in the reaction between oxoglutarate and succinate. Thisstep operates close to the thermodynamic equilibrium possibly becausesuccinate is synthesized via a transferase reaction, and the conversionof oxoglutarate to succinate is a rate limiting step for carbonmetabolism. These findings enable a better understanding of therelationship between genome annotation and extant metabolic pathways inG. metallireducens.

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

    Science.gov (United States)

    Ferencz, Zs.; Szabados, M.; Varga, G.; Csendes, Z.; Kukovecz, Á.; Kónya, Z.; Carlson, S.; Sipos, P.; Pálinkó, I.

    2016-01-01

    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.

  13. Solid-phase extraction of Fe(III), Pb(II) and Cr(III) in environmental samples on amberlite XAD-7 and their determinations by flame atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Divrikli, Umit [Pamukkale University, Faculty of Arts and Science, Department of Chemistry, Denizli 20020 (Turkey)], E-mail: udivrikli@pamukkale.edu.tr; Akdogan, Abdullah [Pamukkale University, Faculty of Arts and Science, Department of Chemistry, Denizli 20020 (Turkey); Soylak, Mustafa [Erciyes University, Faculty of Arts and Science, Department of Chemistry, Kayseri 38039 (Turkey); Elci, Latif [Pamukkale University, Faculty of Arts and Science, Department of Chemistry, Denizli 20020 (Turkey)

    2007-10-22

    This paper describes a simple and accurate procedure for preconcentration of trace amounts of Fe(III), Pb(II) and Cr(III) ions. The preconcentration procedure is based on retention of p-xylenol blue chelates on Amberlite XAD-7. The analytes retained were eluted from Amberlite XAD-7 by using 1 mol L{sup -1} HCl. The influences of the analytical parameters including amounts of reagents, pH and type of eluent were also investigated. The detection limits of Fe, Pb and Cr were found to be 3.07, 18.6 and 3.27 {mu}g L{sup -1}, respectively. The accuracy of the procedure was checked by the analysis of an electrolytic copper wire sample. The relative error was less than 5%. The presented method was applied to the determination of Fe(III), Pb(II) and Cr(III) in water samples from Denizli, Turkey with good results such as recoveries more than 95%, relative standard deviations below 10%.

  14. Solid-phase extraction of Fe(III), Pb(II) and Cr(III) in environmental samples on amberlite XAD-7 and their determinations by flame atomic absorption spectrometry.

    Science.gov (United States)

    Divrikli, Umit; Akdogan, Abdullah; Soylak, Mustafa; Elci, Latif

    2007-10-22

    This paper describes a simple and accurate procedure for preconcentration of trace amounts of Fe(III), Pb(II) and Cr(III) ions. The preconcentration procedure is based on retention of p-xylenol blue chelates on Amberlite XAD-7. The analytes retained were eluted from Amberlite XAD-7 by using 1 mol L(-1) HCl. The influences of the analytical parameters including amounts of reagents, pH and type of eluent were also investigated. The detection limits of Fe, Pb and Cr were found to be 3.07, 18.6 and 3.27 microg L(-1), respectively. The accuracy of the procedure was checked by the analysis of an electrolytic copper wire sample. The relative error was less than 5%. The presented method was applied to the determination of Fe(III), Pb(II) and Cr(III) in water samples from Denizli, Turkey with good results such as recoveries more than 95%, relative standard deviations below 10%.

  15. Prediction of 3-hydroxypyridin-4-one (HPO) log K1 values for Fe(III).

    Science.gov (United States)

    Chen, Yu-Lin; Barlow, Dave J; Kong, Xiao-Le; Ma, Yong-Min; Hider, Robert C

    2012-09-21

    As a means to aid in the design of 3-hydroxypyridin-4-ones (HPOs) intended for use as therapeutic Fe(3+) chelating agents, a novel methodology has been developed using quantum mechanical (QM) calculations for predicting the iron binding affinities of the compounds (more specifically, their log K(1) values). The reported/measured HPO log K(1) values were verified through their correlation with the corresponding sum of the compounds' ligating group pK(a) values. Using a training set of eleven HPOs with known log K(1) values, reliable predictions are shown to be obtained with QM calculations using the B3LYP/6-31+G(d)/CPCM model chemistry (with Bondi radii, and water as solvent). With this methodology, the observed log K(1) values for the training set compounds are closely matched by the predicted values, with the correlation between the observed and predicted values giving r(2) = 0.9. Predictions subsequently made by this method for a test set of 42 HPOs of known log K(1) values gave predicted values accurate to within ±0.32 log units. In order to further investigate the predictive power of the method, four novel HPOs were synthesised and their log K(1) values were determined experimentally. Comparison of these predicted log K(1) values against the measured values gave absolute deviations of 0.22 (13.87 vs. 14.09), 0.02 (14.31 vs. 14.29), 0.12 (14.62 vs. 14.50), and 0.13 (15.04 vs. 15.17). The prediction methodology reported here is the first to be provided for predicting the absolute log K(1) values of iron-chelating agents in the absence of pK(a) values.

  16. Reaction mechanism for the highly efficient catalytic decomposition of peroxynitrite by the amphipolar iron(III) corrole 1-Fe.

    Science.gov (United States)

    Avidan-Shlomovich, Shlomit; Gross, Zeev

    2015-07-21

    The amphipolar iron(III) corrole 1-Fe is one of the most efficient catalysts for the decomposition of peroxynitrite, the toxin involved in numerous diseases. This research focused on the mechanism of that reaction at physiological pH, where peroxynitrite is in equilibrium with its much more reactive conjugated acid, by focusing on the elementary steps involved in the catalytic cycle. Kinetic investigations uncovered the formation of a reaction intermediate in a process that is complete within a few milliseconds (k1 ∼ 3 × 10(7) M(-1) s(-1) at 5 °C, about 7 orders of magnitude larger than the first order rate constant for the non-catalyzed process). Multiple evidence points towards iron-catalyzed homolytic O-O bond cleavage to form nitrogen dioxide and hydroxo- or oxo-iron(iv) corrole. The iron(iv) intermediate was found to decay via multiple pathways that proceed at similar rates (k2 about 10(6) M(-1) s(-1)): reaction with nitrogen dioxide to form nitrate, nitration of the corrole macrocyclic, and dimerization to binuclear iron(iv) corrole. Catalysis in the presence of substrates affects the decay of the iron intermediate by either oxidative nitration (phenolic substrates) or reduction (ascorbate). A large enough excess of ascorbate accelerates the catalytic decomposition of PN by 1-Fe by orders of magnitude, prevents other decay routes of the iron intermediate, and eliminates nitration products as well. This suggests that the beneficial effect of the iron corrole under the reducing conditions present in most biological media might be even larger than in the purely chemical system. The acquired mechanistic insight is of prime importance for the design of optimally acting catalysts for the fast and safe decomposition of reactive oxygen and nitrogen species.

  17. Safety Assessment of Citric Acid, Inorganic Citrate Salts, and Alkyl Citrate Esters as Used in Cosmetics.

    Science.gov (United States)

    Fiume, Monice M; Heldreth, Bart A; Bergfeld, Wilma F; Belsito, Donald V; Hill, Ronald A; Klaassen, Curtis D; Liebler, Daniel C; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan

    2014-05-26

    The CIR Expert Panel (Panel) assessed the safety of citric acid, 12 inorganic citrate salts, and 20 alkyl citrate esters as used in cosmetics, concluding that these ingredients are safe in the present practices of use and concentration. Citric acid is reported to function as a pH adjuster, chelating agent, or fragrance ingredient. Some of the salts are also reported to function as chelating agents, and a number of the citrates are reported to function as skin-conditioning agents but other functions are also reported. The Panel reviewed available animal and clinical data, but because citric acid, calcium citrate, ferric citrate, manganese citrate, potassium citrate, sodium citrate, diammonium citrate, isopropyl citrate, stearyl citrate, and triethyl citrate are generally recognized as safe direct food additives, dermal exposure was the focus for these ingredients in this cosmetic ingredient safety assessment.

  18. 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.

  19. 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.

  20. Peroxidase-like catalytic activity of water-insoluble complex linked Fe(III)-thiacalix[4]arenetetrasulfonate with tetrakis(1-methylpyridinium-4-yl)porphine via ionic interaction.

    Science.gov (United States)

    Odo, Junichi; Sumihiro, Manabu; Okadome, Takuma; Inoguchi, Masahiko; Akashi, Haruo; Nakagoe, Kazunori

    2009-12-01

    A new water-insoluble Fe(3+)-TCAS[4]/TMPyP complex linked tetraanionic Fe(III)-thiacalix[4]arenetetrasulfonate (Fe(3+)-TCAS[4]) with tetracationic tetrakis(1-methylpyridinium-4-yl)porphine (TMPyP) via ionic interaction was prepared. The peroxidase-like catalytic activity of the Fe(3+)-TCAS[4]/TMPyP complex was investigated based on the dye formation reaction by oxidation of 4-aminoantipyrine and phenol with H(2)O(2) catalyzed by peroxidase. This Fe(3+)-TCAS[4]/TMPyP complex showed the highest activity in pH 5.5 acetate buffer solutions, and it was applied to the photometric determination of trace amounts of H(2)O(2). The calibration curve was linear over the range from 1.0 to 35 microg of H(2)O(2) in a 1.0 ml sample solution. Moreover, the method using glucoseoxidase and the Fe(3+)-TCAS[4]/TMPyP complex was applied to the determination of glucose, and the results were satisfactory even in control sera. The Fe(3+)-TCAS[4]/TMPyP complex can be applied to a practical sample, such as blood or urine, as an analytical reagent for the photometric determination of H(2)O(2) in place of peroxidase.

  1. Enhancement of Aminoacylase Activity by Sodium Citrate

    Institute of Scientific and Technical Information of China (English)

    于范利; 曹志方; 李森; 周海梦

    2001-01-01

    Kidney and other tissues of animals and humans have a high concentration of citrate which is an important intermediate substance in the citrate cycle. Citrate may play an important physiological role in metabolism. In this paper, we studied the interaction of the sodium salt of citrate with aminoacylase which is an important enzyme in metabolism and found sodium citrate can enhance the activity of aminoacylase. The maximum enzyme activity induced by sodium citrate increased approximately 3 folds over the enzyme activity without sodium citrate. The initial reaction rates (Ⅴ) for different concentrations of sodium citrate were obtained, showing that sodium citrate is a non-competitive activator. The result of the ANS binding fluorescence measurements for aminoacylase indicated that increasing sodium citrate concentrations markedly increased the ANS binding fluorescence with a blue shift of the emission spectra peak. This suggests the formation of more hydrophobic regions. Aggregates formed quickly when aminoacylase was incubated with sodium citrate (0.3 mol/L) and guanidinium chloride (0- 3. 5 mol/L). Aminoacylase lost enzyme activity in the guanidinium chloride more quickly in the presence of sodium citrate than in the absence of sodium citrate. The intrinsic fluorescence emission intensity decreased more quickly and the red shift of the emission spectra peak was larger than that without sodium citrate.

  2. Characterisation of the dissimilatory reduction of Fe(III)-oxyhydroxide at the microbe-mineral interface: the application of STXM-XMCD.

    Science.gov (United States)

    Coker, V S; Byrne, J M; Telling, N D; VAN DER Laan, G; Lloyd, J R; Hitchcock, A P; Wang, J; Pattrick, R A D

    2012-07-01

    A combination of scanning transmission X-ray microscopy and X-ray magnetic circular dichroism was used to spatially resolve the distribution of different carbon and iron species associated with Shewanella oneidensis MR-1 cells. S. oneidensis MR-1 couples the reduction of Fe(III)-oxyhydroxides to the oxidation of organic matter in order to conserve energy for growth. Several potential mechanisms may be used by S. oneidensis MR-1 to facilitate Fe(III)-reduction. These include direct contact between the cell and mineral surface, secretion of either exogenous electron shuttles or Fe-chelating agents and the production of conductive 'nanowires'. In this study, the protein/lipid signature of the bacterial cells was associated with areas of magnetite (Fe₃O₄), the product of dissimilatory Fe(III) reduction, which was oversaturated with Fe(II) (compared to stoichiometric magnetite). However, areas of the sample rich in polysaccharides, most likely associated with extracellular polymeric matrix and not in direct contact with the cell surface, were undersaturated with Fe(II), forming maghemite-like (γ-Fe₂O₃) phases compared to stoichiometric magnetite. The reduced form of magnetite will be much more effective in environmental remediation such as the immobilisation of toxic metals. These findings suggest a dominant role for surface contact-mediated electron transfer in this study and also the inhomogeneity of magnetite species on the submicron scale present in microbial reactions. This study also illustrates the applicability of this new synchrotron-based technique for high-resolution characterisation of the microbe-mineral interface, which is pivotal in controlling the chemistry of the Earth's critical zone.

  3. 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.

  4. Characterization and Properties of Activated Carbon Prepared from Tamarind Seeds by KOH Activation for Fe(III Adsorption from Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Sumrit Mopoung

    2015-01-01

    Full Text Available This research studies the characterization of activated carbon from tamarind seed with KOH activation. The effects of 0.5 : 1–1.5 : 1 KOH : tamarind seed charcoal ratios and 500–700°C activation temperatures were studied. FTIR, SEM-EDS, XRD, and BET were used to characterize tamarind seed and the activated carbon prepared from them. Proximate analysis, percent yield, iodine number, methylene blue number, and preliminary test of Fe(III adsorption were also studied. Fe(III adsorption was carried out by 30 mL column with 5–20 ppm Fe(III initial concentrations. The percent yield of activated carbon prepared from tamarind seed with KOH activation decreased with increasing activation temperature and impregnation ratios, which were in the range from 54.09 to 82.03 wt%. The surface functional groups of activated carbon are O–H, C=O, C–O, –CO3, C–H, and Si–H. The XRD result showed high crystallinity coming from a potassium compound in the activated carbon. The main elements found in the activated carbon by EDS are C, O, Si, and K. The results of iodine and methylene blue adsorption indicate that the pore size of the activated carbon is mostly in the range of mesopore and macropore. The average BET pore size and BET surface area of activated carbon are 67.9764 Å and 2.7167 m2/g, respectively. Finally, the tamarind seed based activated carbon produced with 500°C activation temperature and 1.0 : 1 KOH : tamarind seed charcoal ratio was used for Fe(III adsorption test. It was shown that Fe(III was adsorbed in alkaline conditions and adsorption increased with increasing Fe(III initial concentration from 5 to 20 ppm with capacity adsorption of 0.0069–0.019 mg/g.

  5. Fe(III)-photocatalytic partial oxidation of benzyl alcohol to benzaldehyde under UV-solar simulated radiation.

    Science.gov (United States)

    Spasiano, Danilo; Marotta, Raffaele; Di Somma, Ilaria; Andreozzi, Roberto; Caprio, Vincenzo

    2013-11-01

    A great deal of interest is recorded among researchers in the identification of new catalytic systems that make possible the selective oxidation of organic species in the presence of non-toxic solvents, primarily water, through the use of inexpensive catalysts. The possibility to selectively oxidize benzyl alcohol to benzaldehyde is studied in the present work by using ferric ions as homogeneous catalysts and oxygen as an oxidant under UV-solar simulated radiation. Due to the possibility that Fe(III) aquo-complex photolysis could generate undesired reactive OH radicals with the consequent occurrence of side reactions, most of the runs are carried out at pH = 0.5 at which these events have a reduced incidence. The results indicate that benzyl alcohol can be partially converted into benzaldehyde with yield and selectivity values higher than 40% and 80% respectively for the conditions adopted, with a minor occurrence of benzoic acid formation. Reaction schemes to account for the experimental observations are provided.

  6. Paenibacillus guangzhouensis sp. nov., an Fe(III)- and humus-reducing bacterium from a forest soil.

    Science.gov (United States)

    Li, Jibing; Lu, Qin; Liu, Ting; Zhou, Shungui; Yang, Guiqin; Zhao, Yong

    2014-11-01

    A Gram-reaction-variable, rod-shaped, motile, facultatively aerobic and endospore-forming bacterium, designated strain GSS02(T), was isolated from a forest soil. Strain GSS02(T) was capable of reducing humic substances and Fe(III) oxides. Strain GSS02(T) grew optimally at 35 °C, at pH 78 and in the presence of 1% NaCl. The predominant menaquinone was MK-7. The major cellular fatty acids were anteiso-C(15:0) and iso-C(16:0) and the polar lipid profile contained mainly phosphatidylethanolamine, diphosphatidylglycerol and phosphatidylglycerol, with moderate amounts of two unknown aminophospholipids and a minor amount of one unknown lipid. The DNA G+C content was 53.4 mol%. Comparative 16S rRNA gene sequence analysis showed that strain GSS02(T) was related most closely to Paenibacillus terrigena JCM 21741(T) (98.1% similarity). Mean DNA-DNA relatedness between strain GSS02(T) and P. terrigena JCM 21741(T) was 58.8 ± 0.5%. The phylogenetic, chemotaxonomic and phenotypic results clearly demonstrated that strain GSS02(T) belongs to the genus Paenibacillus and represents a novel species, for which the name Paenibacillus guangzhouensis sp. nov. is proposed. The type strain is GSS02(T) ( =KCTC 33171(T) =CCTCC AB 2013236(T)).

  7. One- and two-step spin-crossover behavior of [Fe(II)(isoxazole)(6)](2+) and the structure and magnetic properties of triangular [Fe(III)(3)O(OAc)(6)(isoxazole)(3)][ClO(4)].

    Science.gov (United States)

    Hibbs, Wendy; van Koningsbruggen, Petra J; Arif, Atta M; Shum, William W; Miller, Joel S

    2003-09-08

    The structure and spin-crossover magnetic behavior of [Fe(II)1(6)][BF(4)](2) (1 = isoxazole) and [Fe(II)1(6)][ClO(4)](2) have been studied. [Fe(II)1(6)][BF(4)](2) undergoes two reversible spin-crossover transitions at 91 and 192 K, and is the first two-step spin transition to undergo a simultaneous crystallographic phase transition, but does not exhibit thermal hysteresis. The single-crystal structure determinations at 260 [space group P3, a = 17.4387(4) A, c = 7.6847(2) A] and at 130 K [space group P1, a = 17.0901(2) A, b = 16.7481(2) A, c = 7.5413(1) A, alpha = 90.5309(6) degrees, beta = 91.5231(6) degrees, gamma = 117.8195(8) degrees ] reveal two different iron sites, Fe1 and Fe2, in a 1:2 ratio. The room-temperature magnetic moment of 5.0 mu(B) is consistent with high-spin Fe(II). A plateau in mu(T) having a moment of 3.3 mu(B) centered at 130 K suggests a mixed spin system of some high-spin and some low-spin Fe(II) molecules. On the basis of the Fe-N bond distances at the two temperatures, and the molar fraction of high-spin molecules at the transition plateau, Fe1 and Fe2 can be assigned to the 91 and 192 K transitions, respectively. [Fe(II)1(6)][ClO(4)](2) [space group P3, a = 17.5829(3) A, c = 7.8043(2) A, beta = 109.820 (3) degrees, T = 295 K] also possesses Fe1:Fe2 in a 1:2 ratio, and magnetic measurements show a single spin transition at 213 K, indicating that both Fe1 and Fe2 undergo a simultaneous spin transition. [Fe(II)1(6)][ClO(4)](2) slowly decomposes in solutions containing acetic anhydride to form [Fe(III)(3)O(OAc)(6)1(3)][ClO(4)] [space group I2, a = 10.1547(7) A, b = 16.5497(11) A, c = 10.3205(9) A, beta = 109.820 (3) degrees, T = 200 K]. The isosceles Fe(3) unit contains two Fe.Fe distances of 3.2844(1) A and a third Fe.Fe distance of 3.2857(1) A. The magnetic data can be fit to a trinuclear model with H = -2J(S(1)xS(2) + S(2)xS(3)) - 2J(13)(S(1)xS(3)), where J = -27.1 and J(13) = -32.5 cm(-1).

  8. A missing high-spin molecule in the family of cyano-bridged heptanuclear heterometal complexes, [(LCuII)6FeIII(CN)6]3+, and its CoIII and CrIII analogues, accompanied in the crystal by a novel octameric water cluster

    CERN Document Server

    Maxim, Catalin; Khuntia, Panchanana; Madalan, Augustin M; Lascialfari, Alessandro; Caneschi, Andrea; Journauxe, Yves; Andruh, Marius; 10.1039/b924505g

    2010-01-01

    Three isostructural cyano-bridged heptanuclear complexes, [{CuII(saldmen)(H2O)}6{MIII(CN)6}](ClO4)3$\\cdotp$8H2O (M = FeIII 2; CoIII, 3; CrIII 4), have been obtained by reacting the binuclear copper(II) complex, [Cu2(saldmen)2(mu-H2O)(H2O)2](ClO4)2$\\cdotp$2H2O 1, with K3[Co(CN)6], K4[Fe(CN)6], and, respectively, K3[Cr(CN)6] (Hsaldmen is the Schiff base resulted from the condensation of salicylaldehyde with N,N-dimethylethylenediamine). A unique octameric water cluster, with bicyclo[2,2,2]octane-like structure, is sandwiched between the heptanuclear cations in 2, 3 and 4. The cryomagnetic investigations of compounds 2 and 4 reveal ferromagnetic couplings of the central FeIII or CrIII ions with the CuII ions (JCuFe = +0.87 cm-1, JCuCr = +30.4 cm-1). The intramolecular Cu-Cu exchange interaction in 3, across the diamagnetic cobalt(III) ion, is -0.3 cm-1. The solid-state1H-NMR spectra of compounds 2 and 3 have been investigated.

  9. Structural, magnetic and optical properties of an Fe(III) dimer bridged by the meridional planar divergent N,N'-bis(salicyl)hydrazide and its photo- and electro-chemistry in solution.

    Science.gov (United States)

    Cheaib, Khaled; Martel, David; Clément, Nicolas; Eckes, Fabrice; Kouaho, Stéphanie; Rogez, Guillaume; Dagorne, Samuel; Kurmoo, Mohamedally; Choua, Sylvie; Welter, Richard

    2013-02-07

    {Fe(III)Cl(DMF)(2)}(2)(L) where L is N,N'-bis(salicyl)hydrazide has been synthesized as red crystals and characterized using single-crystal diffraction, infrared and UV-vis spectroscopies, and its magnetic properties studied. The dimeric unit in the structure is formed through the two meridional sets of divergent O, N, O coordinating atoms of the hexacoordinated and quadruply charged ligand. With the presence of the inversion symmetry the Fe atoms are strictly planar with the ligand. The magnetic exchange interaction is found to be antiferromagnetic with a J = -5.98(3) cm(-1) through the rare Fe-N-N-Fe pathway. Irradiation of the FeCl(3)/H(4)L red DMF solution in the visible region of the spectrum resulted in its complete discoloration and from which the unknown colorless salt [Fe(II)(DMF)(6)][Fe(II)Cl(4)] and the neutral ligand have been identified by single crystal diffraction. The UV-visible spectra of FeCl(3), H(4)L and their mixture in DMF solution indicate that the iron complex is the absorbing species and the presence of the free ligand in the irradiated solution suggests that the ligand is potentially acting as a catalyst to the photoreduction of Fe(III) to Fe(II), while electrochemistry points to a mixed-valent (Fe(II)-Fe(III)) intermediate in the process.

  10. Synthesis and characterization particles of Ba{sub 0,50}Sr{sub 0,50}Co{sub 0,80}Fe{sub 0,20}O{sub 3} obtained by the citrate-EDTA technique; Sintese e caracterizacao de particulados de Ba{sub 0,50}Sr{sub 0,50}Co{sub 0,80}Fe{sub 0,20}O{sub 3} obtidos pela tecnica dos citratos-EDTA

    Energy Technology Data Exchange (ETDEWEB)

    Bonturim, E.; Vargas, R.A.; Andreoli, M.; Seo, E.S.M., E-mail: ebonturim@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (CCTM/IPEN/CNEN-SP), Sao Paulo, SP (Brazil). Centro de Ciencia e Tecnologia de Materiais

    2010-07-01

    The Ba{sub (1-x)}Sr{sub (x)}Co{sub (1-y)}Fe{sub (y)}O{sub (3)} (BSCF) has been studied as a cathode material for Intermediate Temperature Solid Oxide Fuel Cell, due to its better ion and electron conduction. This work aims to study the synthesis of the compound obtained from the citrate-EDTA technique. Thermogravimetric analysis indicated the formation of the compound above 800 deg C. The materials calcined at temperatures of 700, 800 and 900 deg C for 5 h showed cubic pseudo-perovskite structure, according to the literature. By analysis of X-ray fluorescence were obtained powders with nominal chemical composition in the temperature range studied. The micrographs obtained by SEM and particle size distribution analysis showed the formation of particle with diameters below 1 micron. (author)

  11. 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.

  12. Sequential extraction method for determination of Fe(II/III) and U(IV/VI) in suspensions of iron-bearing phyllosilicates and uranium.

    Science.gov (United States)

    Luan, Fubo; Burgos, William D

    2012-11-06

    Iron-bearing phyllosilicates strongly influence the redox state and mobility of uranium because of their limited hydraulic conductivity, high specific surface area, and redox reactivity. Standard extraction procedures cannot be accurately applied for the determination of clay-Fe(II/III) and U(IV/VI) in clay mineral-U suspensions such that advanced spectroscopic techniques are required. Instead, we developed and validated a sequential extraction method for determination of clay-Fe(II/III) and U(IV/VI) in clay-U suspensions. In our so-called "H(3)PO(4)-HF-H(2)SO(4) sequential extraction" method, H(3)PO(4)-H(2)SO(4) is used first to solubilize and remove U, and the remaining clay pellet is subject to HF-H(2)SO(4) digestion. Physical separation of U and clay eliminates valence cycling between U(IV/VI) and clay-Fe(II/III) that otherwise occurred in the extraction solutions and caused analytical discrepancies. We further developed an "automated anoxic KPA" method to measure soluble U(VI) and total U (calculate U(IV) by difference) and modified the conventional HF-H(2)SO(4) digestion method to eliminate a series of time-consuming weighing steps. We measured the kinetics of uraninite oxidation by nontronite using this sequential extraction method and anoxic KPA method and measured a stoichiometric ratio of 2.19 ± 0.05 mol clay-Fe(II) produced per mol U(VI) produced (theoretical value of 2.0). We found that we were able to recover 98.0-98.5% of the clay Fe and 98.1-98.5% of the U through the sequential extractions. Compared to the theoretical stoichiometric ratio of 2.0, the parallel extractions of 0.5 M HCl for clay-Fe(II) and 1 M NaHCO(3) for U(VI) leached two-times more Fe(II) than U(VI). The parallel extractions of HF-H(2)SO(4) for clay Fe(II) and 1 M NaHCO(3) for U(VI) leached six-times more Fe(II) than U(VI).

  13. New route to the mixed valence semiquinone-catecholate based mononuclear FeIII and catecholate based dinuclear MnIII complexes: first experimental evidence of valence tautomerism in an iron complex.

    Science.gov (United States)

    Shaikh, Nizamuddin; Goswami, Sanchita; Panja, Anangamohan; Wang, Xin-Yi; Gao, Song; Butcher, Ray J; Banerjee, Pradyot

    2004-09-20

    The semiquinone-catecholate based mixed valence complex, [FeIII(bispicen)(Cl4Cat)(Cl4SQ)] x DMF (1), and catecholate based (H2bispictn)[Mn2III(Cl4Cat)4(DMF)2] (2) (bispicen = N,N'-bis(2-pyridylmethyl)-1,2-ethanediamine, bispictn = N,N'-bis(2-pyridylmethyl)-1,3-propanediamine, Cl4Cat = tetrachlorocatecholate dianion, and Cl4SQ = tetrachlorosemiquinone radical anion) were synthesized directly utilizing a facile route. Both the complexes have been characterized by single crystal X-ray diffraction study. The electronic structures have been elucidated by UV-vis-NIR absorption spectroscopy, cyclic voltammetry, EPR, and magnetic properties. The structural as well as spectroscopic features support the mixed valence tetrachlorosemiquinone-tetrachlorocatecholate charge distribution in 1. The ligand based mixed valence state was further confirmed by the presence of an intervalence charge transfer (IVCT) band in the 1900 nm region both in solution and in the solid. The intramolecular electron transfer, a phenomenon known as valence tautomerism (VT), has been followed by electronic absorption spectroscopy. For 1, the isomeric form [FeIII(bispicen)(Cl4Cat)(Cl4SQ)] is favored at low temperature, while at an elevated temperature, the [FeII(bispicen)(Cl4SQ)2] redox isomer dominates. Infrared as well as UV-vis-NIR spectral characterization for 2 suggest that the MnIII(Cat)2- moiety is admixed with its mixed valence semiquinone-catecholate isomer MnII(SQ)(Cat)-, and the electronic absorption spectrum is dominated by the mixed charged species. The origin of the intervalence charge transfer band in the 1900 nm range is associated with the mixed valence form, MnII(Cl4Cat)(Cl4SQ)-. The observation of VT in complex 1 is the first example where a mixed valence semiquinone-catecholate iron(III) complex undergoes intramolecular electron transfer similar to manganese and cobalt complexes.

  14. SYNTHESIS, CHARACTERIZATION AND BI OLOGICAL ACTIVITY OF FE-III AND CO-II COMPLEXES DERIVED FROM 4-CHLORO-2-[(2-FURANYLMETHYL-AMINO]-5 SULFAMOYLBENZOIC ACID

    Directory of Open Access Journals (Sweden)

    Suman Malik

    2015-05-01

    Full Text Available The present investigation is an attempt to synth esize and characterize the ligand 4-chloro-2-[(2- furanylmethyl - amino]-5-sulfamoylbenzoic acid, and its Fe-III and Co-II complexes. The nature of bonding and the geometry of the complexes have be en deduced from elemental analysis, magnetic moment measurements and conductivity measurements. Conduc tometric titrations have suggested meta l-ligand ratio of 1:2 for both Fe(III and Co(II complexes. The ligand behaves as a bidentate with N, O donor atoms. The electronic absorption spectra and magnetic susceptibility measurements of th e complexes indicates octahedral geometry for both the complexes. IR, UV-Visible and SEM studies have been carried out to s uggest the tentative structure for the complexes. The synthesized ligand as well as their metal complexes were scree ned for diuretic activity. The results revealed that the complexes are more potent diuretic than the ligand.

  15. Cu(II), Fe(III) and Mn(II) combinations as environmental stress factors have distinguishing effects on Enterococcus hirae.

    Science.gov (United States)

    Vardanyan, Zaruhi; Trchounian, Armen

    2015-02-01

    Pollution by various heavy metals as environmental stress factors might affect bacteria. It was established that iron (Fe(III)), manganese (Mn(II)) and copper (Cu(II)) ion combinations caused effects on Enterococcus hirae that differed from the sum of the effects when the metals were added separately. It was shown that the Cu2+-Fe3+ combination decreased the growth and ATPase activity of membrane vesicles of wild-type E. hirae ATCC9790 and atpD mutant (with defective FoF1-ATPase) MS116. Addition of Mn2+-Fe3+ combinations within the same concentration range had no effects on growth compared to control (without heavy metals). ATPase activity was increased in the presence of Mn2+-Fe3+, while together with 0.2 mmol/L N,N'-dicyclohexylcarbodiimide (DCCD), ATPase activity was decreased compared to control (when only 0.2 mmol/L DCCD was present). These results indicate that heavy metals ion combinations probably affect the FOF1-ATPase, leading to conformational changes. Moreover the action may be direct or be mediated by environment redox potential. The effects observed when Fe3+ was added separately disappeared in both cases, which might be a result of competing processes between Fe3+ and other heavy metals. These findings are novel and improve the understanding of heavy metals ions effects on bacteria, and could be applied for regulation of stress response patterns in the environment.

  16. 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.

  17. 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.

  18. Degradation of atrazine by homogeneous photocatalysis using Fe(III)/UV/air system and evaluation of potential toxicity of atrazine and its metabolites

    OpenAIRE

    KELTNEROVÁ, Lucie

    2016-01-01

    Atrazine photochemical degradation in homogeneous phase using Fe(III)/UV/air system was studied. Two toxicity assessments, a Lemna minor growth inhibition test and a Daphnia magna acute immobilisation test, were employed to test potential toxicity of atrazine and its degradation products. The occurrence of atrazine in rivers from the Vltava River basin was evaluated from the analyses performed by Povodí Vltavy, State Enterprise.

  19. Regulation of AhFRO1, an Fe(III)-chelate reductase of peanut, during iron deficiency stress and intercropping with maize.

    Science.gov (United States)

    Ding, Hong; Duan, Lihong; Wu, Huilan; Yang, Rongxin; Ling, Hongqing; Li, Wen-Xue; Zhang, Fusuo

    2009-07-01

    Iron deficiency-induced chlorosis in peanut during anthesis was alleviated when peanut was intercropped with maize in field and pot experiments. Iron acquisition of graminaceous plants is characterized by the synthesis and secretion of the iron-chelating phytosiderophores. Compared to the roots of monocropped maize, the roots of maize intercropped with peanut always secreted higher amounts of phytosiderophores during peanut anthesis. For non-graminaceous plants, reduction of ferric to ferrous iron on the root surface is the rate-limiting step for mobilizing iron from soil. The full-length cDNA, AhFRO1, which is encoding an Fe(III)-chelate reductase, was isolated from peanut. AhFRO1 expression in yeast conferred Fe(III)-chelate reductase activity to the cells. Consistent with its function in iron uptake, AhFRO1 was determined to be a membrane protein by transient expression analysis. AhFRO1 mRNA accumulated under iron deficiency conditions. During pre-anthesis, the Fe(III)-chelate reductase activity and the transcript levels of AhFRO1 were similar in monocropped and intercropped peanut. When the iron deficiency-induced chlorosis developed in the monocropped peanuts, both the Fe(III)-chelate reductase activity of peanut and the transcript levels of AhFRO1 were higher in intercropped than in monocropped peanuts, which is consistent with the secretion of phytosiderophores by maize roots. We conclude that AhFRO1 in peanut and phytosiderophores from maize co-operate to improve the iron nutrition of peanut when intercropped with maize.

  20. Microbial community profiling of the Chinoike Jigoku ("Blood Pond Hell") hot spring in Beppu, Japan: isolation and characterization of Fe(III)-reducing Sulfolobus sp. strain GA1.

    Science.gov (United States)

    Masaki, Yusei; Tsutsumi, Katsutoshi; Hirano, Shin-Ichi; Okibe, Naoko

    2016-09-01

    Chinoike Jigoku ("Blood Pond Hell") is located in the hot spring town of Beppu on the southern island of Kyushu in Japan, and is the site of a red-colored acidic geothermal pond. This study aimed to investigate the microbial population composition in this extremely acidic environment and to isolate/characterize acidophilic microorganism with metal-reducing ability. Initially, PCR (using bacteria- and archaea-specific primers) of environmental DNA samples detected the presence of bacteria, but not archaea. This was followed by random sequencing analysis, confirming the presence of wide bacterial diversity at the site (123 clones derived from 18 bacterial and 1 archaeal genera), including those closely related to known autotrophic and heterotrophic acidophiles (Acidithiobacillus sp., Sulfobacillus sp., Alicyclobacillus sp.). Nevertheless, successive culture enrichment with Fe(III) under micro-aerobic conditions led to isolation of an unknown archaeal organism, Sulfolobus sp. GA1 (with 99.7% 16S rRNA gene sequence identity with Sulfolobus shibatae). Unlike many other known Sulfolobus spp., strain GA1 was shown to lack sulfur oxidation ability. Strain GA1 possessed only minor Fe(II) oxidation ability, but readily reduced Fe(III) during heterotrophic growth under micro-aerobic conditions. Strain GA1 was capable of reducing highly toxic Cr(VI) to less toxic/soluble Cr(III), demonstrating its potential utility in bioremediation of toxic metal species.

  1. Effect of Fe(III) on 1,1,2,2-tetrachloroethane degradation and vinyl chloride accumulation in wetland sediments of the Aberdeen proving ground

    Science.gov (United States)

    Jones, E.J.P.; Voytek, M.A.; Lorah, M.M.

    2004-01-01

    1,1,2,2-Tetrachloroethane (TeCA) contaminated groundwater at the Aberdeen Proving Ground discharges through an anaerobic wetland in West Branch Canal Creek, MD, where dechlorination occurred. Two microbially mediated pathways, dichloroelimination and hydrogenolysis, account for most of the TeCA degradation at this site. The dichloroelimination pathways led to the formation of vinyl chloride (VC), a recalcitrant carcinogen of great concern. The effect of adding Fe(III) to TeCA-amended microcosms of wetland sediment was studied. Differences were identified in the TeCA degradation pathway between microcosms treated with amorphous ferric oxyhydroxide (AFO-treated) and untreated (no AFO) microcosms. TeCA degradation was accompanied by a lower accumulation of VC in AFO-treated microcosms than no AFO microcosms. The microcosm incubations and subsequent experiments with the microcosm materials showed that AFO treatment resulted in lower production of VC by shifting TeCA degradation from dichloroelimination pathways to production of a greater proportion of chlorinated ethane products, and decreasing the microbial capability to produce VC from 1,2-dichloroethylene. VC degradation was not stimulated in the presence of Fe(III). Rather, VC degradation occurred readily under methanogenic conditions and was inhibited under Fe(III)-reducing conditions.

  2. Characterization of extracellular minerals produced during dissimilatory Fe(III) and U(VI) reduction at 100 degrees C by Pyrobaculum islandicum.

    Science.gov (United States)

    Kashefi, K; Moskowitz, B M; Lovley, D R

    2008-03-01

    In order to gain insight into the significance of biotic metal reduction and mineral formation in hyperthermophilic environments, metal mineralization as a result of the dissimilatory reduction of poorly crystalline Fe(III) oxide, and U(VI) reduction at 100 degrees C by Pyrobaculum islandicum was investigated. When P. islandicum was grown in a medium with poorly crystalline Fe(III) oxide as an electron acceptor and hydrogen as an electron donor, the Fe(III) oxide was reduced to an extracellular, ultrafine-grained magnetite with characteristics similar to that found in some hot environments and that was previously thought to be of abiotic origin. Furthermore, cell suspensions of P. islandicum rapidly reduced the soluble and oxidized form of uranium, U(VI), to extracellular precipitates of the highly insoluble U(IV) mineral, uraninite (UO(2)). The reduction of U(VI) was dependent on the presence of hydrogen as the electron donor. These findings suggest that microbes may play a key role in metal deposition in hyperthermophilic environments and provide a plausible explanation for such phenomena as magnetite accumulation and formation of uranium deposits at ca. 100 degrees C.

  3. Enrichment of Functional Redox Reactive Proteins and Identification by Mass Spectrometry Results in Several Terminal Fe(III)-reducing Candidate Proteins in Shewanella oneidensis MR-1.

    Energy Technology Data Exchange (ETDEWEB)

    Elias, Dwayne A.; Yang, Feng; Mottaz, Heather M.; Beliaev, Alex S.; Lipton, Mary S.

    2007-02-01

    Identification of the proteins directly involved in microbial metal-reduction is important to understanding the biochemistry involved in heavy metal reduction/immobilization and the ultimate cleanup of DOE contaminated sites. Although previous strategies for the identification of these proteins have traditionally required laborious protein purification/characterization of metal-reducing capability, activity is often lost before the final purification step, thus creating a significant knowledge gap. In the current study, subcellular fractions of S. oneidensis MR-1 were enriched for Fe(III)-NTA reducing proteins in a single step using several orthogonal column matrices. The protein content of eluted fractions that demonstrated activity were determined by ultra high pressure liquid chromatography coupled with tandem mass spectrometry (LCMS/ MS). A comparison of the proteins identified from active fractions in all separations produced 30 proteins that may act as the terminal electron-accepting protein for Fe(III)-reduction. These include MtrA, MtrB, MtrC and OmcA as well as a number of other proteins not previously associated with Fe(III)-reduction. This is the first report of such an approach where the laborious procedures for protein purification are not required for identification of metal-reducing proteins. Such work provides the basis for a similar approach with other cultured organisms as well as analysis of sediment and groundwater samples from biostimulation efforts at contaminated sites.

  4. 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.

  5. 21 CFR 184.1751 - Sodium citrate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sodium citrate. 184.1751 Section 184.1751 Food and... Substances Affirmed as GRAS § 184.1751 Sodium citrate. (a) Sodium citrate (C6H5Na3O7·2H2O, CAS Reg. No. 68... may be prepared in an anhydrous state or may contain two moles of water per mole of sodium citrate....

  6. Acid–base equilibria of the Zn(II and Fe(III complexes with condensation products of 2-acetylpyridine and the dihydrazide of oxalic and malonic acid

    Directory of Open Access Journals (Sweden)

    DUŠAN SLADIĆ

    2009-03-01

    Full Text Available Acid–base equilibria of Zn(II and Fe(III complexes with N',N'2-bis[(1E-1-(2-pyridylethylidene]ethanedihydrazide (ligand L1 and N',N'2-bis[(1E-1-(2-pyridylethylidene]propanedihydrazide (ligand L2, i.e., [Fe(L1Cl2(H2O], [Fe(L2Cl(H2O]2+, [Zn(L1(H2O3]+ and [Zn(L2(H2O2]2+, which expressed cytotoxic activity, were investigated in aqueous media. The equilibrium constants were determined potentiometrically at 25 °C at a constant ionic strength of 0.10 mol/dm3 (Na2SO4. The results showed that at pH < 8 both the Fe(III complexes studied here have three, while [Zn(L1(H2O3]+ and [Zn(L2(H2O2]2+ have one and two titratable protons, respectively. Based on the obtained values for the equilibrium constants, protonation schemes of the examined complexes are proposed.

  7. Studies of chemical reduction of Fe(III)*EDTA in an SO{sub 2}/NO{sub x} aqueous scrubber system

    Energy Technology Data Exchange (ETDEWEB)

    Li, W.; Keener, T.C. [Univ. of Cincinnati, OH (United States). Dept. of Civil and Environmental Engineering; Mendelsohn, M.; Harkness, J.B.L.; Livengood, C.D. [Argonne National Lab., IL (United States)

    1996-03-01

    Ferrous*EDTA has been found to be an effective scrubbing agent for nitric oxide gas. A major process problem is oxidation of the iron to the ferric species, leading to a significant decrease in NO{sub x}-removal capability. Argonne National Laboratory discovered a class of organic compounds that, when used with ferrous*EDTA in a sodium carbonate chemistry, could maintain high levels of NO{sub x} removal. However, those antioxidant/reducing agents (A/R) are not effective in a lime-based chemistry. In recent reports, it has been found that ascorbic acid and related compounds are capable of maintaining stable NO{sub x} removals of about 50% (compared with about 15% without the agent) in a lime-based FGD chemistry with Fe(II)*EDTA. It is believed that the improved performance of Fe(II)*EDTA is due to the catalytic action of ascorbate in the Fe(III)*EDTA reduction system, where Fe(III)*EDTA is reduced by ascorbate and oxidized ascorbate is then reduced back to the ascorbate by sulfite/bisulfite anions, which come from the dissolution of SO{sub 2} in the flue gas. In the present work, the kinetics of the reduction of ferric chelate by ascorbate and reduction of oxidized ascorbate by sulfite/bisulfite anions at a typical flue-gas scrubber-system operating temperature ({approximately}55 C) have been determined.

  8. Multi-reverse flow injection analysis integrated with multi-optical sensor for simultaneous determination of Mn(II), Fe(II), Cu(II) and Fe(III) in natural waters.

    Science.gov (United States)

    Youngvises, Napaporn; Suwannasaroj, Kittigan; Jakmunee, Jaroon; AlSuhaimi, Awadh

    2017-05-01

    Multi-reverse flow injection analysis (Mr-FIA) integrated with multi-optical sensor was developed and optimized for the simultaneous determination of multi ions; Mn(II), Fe(II), Cu(II) and Fe(III) in water samples. The sample/standard solutions were propelled making use of a four channels peristaltic pump whereas 4 colorimetric reagents specific for the metal ions were separately injected in sample streams using multi-syringe pump. The color zones that formed in the individual mixing coils were then streamed into multi-channels spectrometer, which comprised of four flows through cell and four pairs of light emitting diode and photodiode, whereby signals were measured concurrently. The linearity range (along with detection limit, µgL(-1)) was 0.050-3.0(16), 0.30-2.0 (11), 0.050-1.0(12) and 0.10-1.0(50)mgL(-1), for Mn(II), Fe(II), Cu(II) and Fe(III), respectively. In the interim, the correlation coefficients were 0.9924-0.9942. The percentages relative standard deviation was less than 3. The proposed system was applied successfully to determine targeted metal ions simultaneously in natural water with high sample throughput and low reagent consumption, thus it satisfies the criteria of Green Analytical Chemistry (GAC) and its goals.

  9. Citrate impairs the micropore diffusion of phosphate into pure and C-coated goethite

    Science.gov (United States)

    Mikutta, Christian; Lang, Friederike; Kaupenjohann, Martin

    2006-02-01

    Anions of polycarboxylic low-molecular-weight organic acids (LMWOA) compete with phosphate for sorption sites of hydrous Fe and Al oxides. To test whether the sorption of LMWOA anions decreases the accessibility of micropores (citrate-induced changes in microporosity and the phosphate sorption kinetics of synthetic goethite in the presence and absence of citrate in batch systems for 3 weeks (500 μM of each ion, pH 5). We also used C-coated goethite obtained after sorption of dissolved organic matter in order to simulate organic coatings in the soil. We analyzed our samples with N 2 adsorption and electrophoretic mobility measurements. Citrate clogged the micropores of both adsorbents by up to 13% within 1 h of contact. The micropore volume decreased with increasing concentration and residence time of citrate. In the absence of citrate, phosphate diffused into micropores of the pure and C-coated goethite. The C coating (5.6 μmol C m -2) did not impair the intraparticle diffusion of phosphate. In the presence of citrate, the diffusion of phosphate into the micropores of both adsorbents was strongly impaired. We attribute this to the micropore clogging and the ligand-induced dissolution of goethite by citrate. While the diffusion limitation of phosphate by citrate was stronger when citrate was added before phosphate to pure goethite, the order of addition of both ions to C-coated goethite had only a minor effect on the intraparticle diffusion of phosphate. Micropore clogging and dissolution of microporous hydrous Fe and Al oxides may be regarded as potential strategies of plants to cope with phosphate deficiency in addition to ligand-exchange.

  10. 21 CFR 582.6625 - Potassium citrate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Potassium citrate. 582.6625 Section 582.6625 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Potassium citrate. (a) Product. Potassium citrate. (b) Conditions of use. This substance is...

  11. 21 CFR 582.1625 - Potassium citrate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Potassium citrate. 582.1625 Section 582.1625 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Additives § 582.1625 Potassium citrate. (a) Product. Potassium citrate. (b) Conditions of use....

  12. 21 CFR 582.6751 - Sodium citrate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Sodium citrate. 582.6751 Section 582.6751 Food and..., FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE Sequestrants 2 § 582.6751 Sodium citrate. (a) Product. Sodium citrate. (b) Conditions of use. This substance is generally recognized...

  13. 21 CFR 582.1751 - Sodium citrate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Sodium citrate. 582.1751 Section 582.1751 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS....1751 Sodium citrate. (a) Product. Sodium citrate. (b) Conditions of use. This substance is...

  14. 21 CFR 184.1449 - Manganese citrate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Manganese citrate. 184.1449 Section 184.1449 Food... Specific Substances Affirmed as GRAS § 184.1449 Manganese citrate. (a) Manganese citrate (Mn3(C6H5O7)2, CAS... manganese carbonate from manganese sulfate and sodium carbonate solutions. The filtered and...

  15. 21 CFR 582.5449 - Manganese citrate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Manganese citrate. 582.5449 Section 582.5449 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Supplements 1 § 582.5449 Manganese citrate. (a) Product. Manganese citrate. (b) Conditions of use....

  16. Role of microbial Fe(III) reduction and solution chemistry in aggregation and settling of suspended particles in the Mississippi River Delta plain, Louisiana, USA

    Science.gov (United States)

    Jaisi, D.P.; Ji, S.; Dong, H.; Blake, R.E.; Eberl, D.D.; Kim, J.

    2008-01-01

    River-dominated delta areas are primary sites of active biogeochemical cycling, with productivity enhanced by terrestrial inputs of nutrients. Particle aggregation in these areas primarily controls the deposition of suspended particles, yet factors that control particle aggregation and resulting sedimentation in these environments are poorly understood. This study was designed to investigate the role of microbial Fe(III) reduction and solution chemistry in aggregation of suspended particles in the Mississippi Delta. Three representative sites along the salinity gradient were selected and sediments were collected from the sediment-water interface. Based on quantitative mineralogical analyses 88-89 wt.% of all minerals in the sediments are clays, mainly smectite and illite. Consumption of SO421 and the formation of H2S and pyrite during microbial Fe(III) reduction of the non-sterile sediments by Shewanella putrefaciens CN32 in artificial pore water (APW) media suggest simultaneous sulfate and Fe(III) reduction activity. The pHPZNPC of the sediments was ??? 3.5 and their zeta potentials at the sediment-water interface pH (6.9-7.3) varied from -35 to -45 mV, suggesting that both edges and faces of clay particles have negative surface charge. Therefore, high concentrations of cations in pore water are expected to be a predominant factor in particle aggregation consistent with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Experiments on aggregation of different types of sediments in the same APW composition revealed that the sediment with low zeta potential had a high rate of aggregation. Similarly, addition of external Fe(II) (i.e. not derived from sediments) was normally found to enhance particle aggregation and deposition in all sediments, probably resulting from a decrease in surface potential of particles due to specific Fe(II) sorption. Scanning and transmission electron microscopy (SEM, TEM) images showed predominant face-to-face clay aggregation in native

  17. Isolation and Identification of Fe(Ⅲ) Reducing Bacteria from Activated Sludge and Their Reducing Characteristics%活性污泥中Fe(Ⅲ)还原微生物的分离、鉴定及还原特性

    Institute of Scientific and Technical Information of China (English)

    任丽平; 张智; 李柏林; 谭洪

    2012-01-01

    A ferric reducing microorganism strain F7 was isolated from activated sludge taken from wastewater treatment plant through dilution-plate method and ferric citrate reduction. By means of the morphology .physiology and the 16S rD-NA sequence analysis and homology comparison, strain F7 was identified as Pseudomonas putida. Different ferric citrate fluid medium concentration and different pH experiments showed that strain F7 growed well with 0.32 g/L ferric citrate, and Fe( III) reduction ratio was high with 0.16 g/L ferric citrate,and the bacteria growth and Fe( III ) reduction quantity were well with pH 6.5.%采用平板分离法和柠檬酸铁还原实验法相结合,从城市污水处理厂活性污泥中分离获得Fe(Ⅲ)还原菌F7,经形态观察、生理生化和16S rDNA序列分析及同源性比对鉴定为恶臭假单胞菌(Pseudomonas putida).在不同柠檬酸铁浓度和不同pH条件下的实验表明,柠檬酸铁浓度为0.32g/L时,菌株生长情况较好,柠檬酸铁浓度为0.16g/L时,Fe(Ⅲ)异化还原比例较高;pH6.5时,菌株生长情况较好,Fe(Ⅲ)异化还原量较多.

  18. Preparation, characterization and visible-light-driven photocatalytic activity of a novel Fe(III) porphyrin-sensitized TiO2 nanotube photocatalyst

    Science.gov (United States)

    Wei, Meng; Wan, Junmin; Hu, Zhiwen; Peng, Zhiqin; Wang, Bing; Wang, Huigang

    2017-01-01

    Iron(III) meso-tetra(4-carboxyphenyl) porphyrin (FeTCPP) loaded on the surface of TiO2 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.

  19. 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.

  20. Magnetic, high-field EPR studies and catalytic activity of Schiff base tetranuclear CuII2FeIII2 complexes obtained by direct synthesis.

    Science.gov (United States)

    Nesterova, Oksana V; Chygorin, Eduard N; Kokozay, Vladimir N; Bon, Volodymyr V; Omelchenko, Irina V; Shishkin, Oleg V; Titiš, Ján; Boča, Roman; Pombeiro, Armando J L; Ozarowski, Andrew

    2013-12-28

    Two novel heterometallic complexes [Cu2Fe2(HL(1))2(H2L(1))2]·10DMSO (1) and [Cu2Fe2(HL(2))2(H2L(2))2]·2DMF (2) have been prepared using the open-air reaction of copper powder, iron(II) chloride and DMSO (1) or DMF (2) solutions of the polydentate Schiff base (H4L(1), 1; H4L(2), 2) formed in situ from salicylaldehyde (1) or 5-bromo-salicylaldehyde (2) and tris(hydroxymethyl)aminomethane. Crystallographic analysis revealed that both compounds are based on the centrosymmetric tetranuclear core {Cu(II)2Fe(III)2(μ-O)6} where metal centres are joined by μ-O bridges from the deprotonated ligands forming a nonlinear chain-like arrangement. Variable-temperature (1.8-300 K) magnetic susceptibility measurements of 1 and 2 showed a decrease of the effective magnetic moment value at low temperature, indicative of antiferromagnetic coupling (JCu-Fe/hc = -10.2 cm(-1), JFe-Fe/hc = -10.5 cm(-1) in 1, JCu-Fe/hc = -10.5 cm(-1), JFe-Fe/hc = -8.93 cm(-1) in 2) between the magnetic centres in both compounds. They reveal an exceptionally high catalytic activity in the oxidation of cyclohexane with hydrogen peroxide under mild conditions, with the best observed yield/TON combined values of 36%/596 and 44%/1.1 × 10(3) for 1 and 2, respectively.

  1. Spectroscopic and thermal degradation behavior of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) complexes with thiopental sodium anesthesia drug

    Science.gov (United States)

    Refat, Moamen S.

    2013-04-01

    A new series of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) complexes have been synthesized with thiopental sodium anesthesia drug. The elemental analyses of the complexes are confined to stoichiometry of the formulas [M(TPL)3]ṡnH2O (M = Cr(III) or Fe(III); n = 6 or 5), [M(TPL)2(H2O)2]ṡnH2O (M = Mn(II), Co(II) or Ni(II); n = 0 or 4), and [M(TPL)2] (M = Cu(II) or Zn(II); n = 2 or 0) respectively, where TPL is thiopental chelating agent. Structures have been discussed and suggested upon elemental analyses, infrared, Raman, electronic, electron spin resonance, 1H NMR spectral data and magnetic studies. The X-ray powder diffraction (XRD) was performed of metal complexes. The XRD patterns indicate crystalline nature for the complexes. The measured low molar conductance values in dimethylsulfoxide indicate that the complexes are non-electrolyte nature. Spectroscopic discussion refer that coordination take place through three types: Cdbnd N (pyrimidine moiety) nitrogen and C2sbnd S (2-thiolate group) for Cr(III), Mn(II) and Fe(III), C6dbnd O (amido group) oxygen and C2sbnd S (2-thiolate group) for Co(II) and Ni(II), and Cu(II) and Zn(II) ions coordinated via Cdbnd N (pyrimidine moiety) nitrogen, C2dbnd S (2-thiolate group) and C6dbnd O (amido group) oxygen, respectively. The thermal behavior (TG/DTG/DTA) of the complexes was studied and kinetic parameters were determined by Horowitz-Metzger and Coats-Redfern methods. The thiopental and its complexes have been screened for their antimicrobial (G+ and G-) bacteria (Escherichia coli, Staphylococcus aureus, Bacillus subtilis and Pseudomonas aeruginosa) and fungi (Aspergillus flavus and Candida albicans) activities by minimum inhibitory concentration (MIC) method.

  2. Fluoride-bridged {GdIII3MIII2} (M=Cr, Fe, Ga) molecular magnetic refrigerants

    DEFF Research Database (Denmark)

    Pedersen, Kasper Steen; Lorusso, Giulia; Morales, Juan José

    2014-01-01

    -lying excited states for successful design of molecular refrigerants. Molecular coolers: Even labile fluoride complexes (see picture; Gd purple, Cr/Fe/Ga orange, F green, O red) are useful precursors for polynuclear, fluoride-bridged 3d-4f systems. Molecular geometry enforces weak exchange interactions, which...

  3. Arsenic(V) Incorporation in Vivianite during Microbial Reduction of Arsenic(V)-Bearing Biogenic Fe(III) (Oxyhydr)oxides.

    Science.gov (United States)

    Muehe, E Marie; Morin, Guillaume; Scheer, Lukas; Pape, Pierre Le; Esteve, Imène; Daus, Birgit; Kappler, Andreas

    2016-03-01

    The dissolution of arsenic-bearing iron(III) (oxyhydr)oxides during combined microbial iron(III) and arsenate(V) reduction is thought to be the main mechanism responsible for arsenic mobilization in reducing environments. Besides its mobilization during bioreduction, arsenic is often resequestered by newly forming secondary iron(II)-bearing mineral phases. In phosphate-bearing environments, iron(II) inputs generally lead to vivianite precipitation. In fact, in a previous study we observed that during bioreduction of arsenate(V)-bearing biogenic iron(III) (oxyhydr)oxides in phosphate-containing growth media, arsenate(V) was immobilized by the newly forming secondary iron(II) and iron(II)/iron(III)mineral phases, including vivianite. In the present study, changes in arsenic redox state and binding environment in these experiments were analyzed. We found that arsenate(V) partly replaced phosphate in vivianite, thus forming a vivianite-symplesite solid solution identified as Fe3(PO4)1.7(AsO4)0.3·8H2O. Our data suggests that in order to predict the fate of arsenic during the bioreduction of abiogenic and biogenic iron(III) (oxyhydr)oxides in arsenic-contaminated environments, the formation of symplesite-vivianite minerals needs to be considered. Indeed, such mineral phases could contribute to a delayed and slow release of arsenic in phosphate-bearing surface and groundwater environments.

  4. Changes in physiological activity of algae Desmodesmus quadricauda after active bioaccumulation of newly prepared and characterized Fe(III) complexes with pyridine-3-carboxamide (pca) by living algal cells.

    Science.gov (United States)

    Fargasová, Agáta; Ondrejkovicová, Iveta; Kramarová, Zuzana; Fáberová, Zuzana

    2010-08-01

    The study characterized five iron(III) complexes with heterocyclic N-donor ligand pyridine-3-carboxamide (pca) [FeCl(3)(pca)(3)], [Fe(H(2)O)(2)(pca)(3)](ClO(4))(3), [Fe(2)O(ac)(2)(pca)(6)]Cl(2).3H(2)O, [Fe(NO(3))(3)(pca)(3)].3H(2)O, [Fe(Cl(2)ac)(3)(pca)(3)] (ac=acetate, Cl(2)ac=dichloroacetate) and their effects on biomass, chlorophylls (a, b), photosynthetic oxygen production and iron biosorption in algae Desmodesmus quadricauda. The effects of Fe(III) complexes were compared with control and those of FeCl(3).6H(2)O. While pca coordination to iron atom through the nitrogen atom of its heterocyclic ring mostly increased iron inhibitory effect on algal biomass and chlorophylls production, oxygen production was enhanced. The exceptions were observed only for [Fe(2)O(ac)(2)(pca)(6)]Cl(2).3H(2)O complex effect on biomass and oxygen production and [Fe(H(2)O)(2)(pca)(3)](ClO(4))(3) complex effect on chlorophylls production. Complexation increased iron biosorption in algal biomass and iron accumulated amount in algae was 2.8-20 times higher than that from FeCl(3).6H(2)O with maximal accumulation from dimeric complex [Fe(2)O(ac)(2)(pca)(6)]Cl(2).3H(2)O.

  5. Binding of the Trace Elements: Cu(II) and Fe(III) to the Native and Modified Nutritive Potato Starches Studied by EPR

    Science.gov (United States)

    Śmigielska, H.; Lewandowicz, G.; Goslar, J.; Hoffmann, S. K.

    2006-08-01

    The Cu(II) and Fe(III) ions have been adsorbed by four potato starches of different degrees of oxidation (different numbers of COOH groups replacing host CH2OH groups): native (no oxidized), white (pudding) with oxidation degree of 0.04%, gelating (0.1%), and LUBOX starch (0.5%). Concentration of the ions in starches was determined from atomic absorption and EPR spectrum intensity. For small concentration of the adsorbed ions (below 4 mg/g) nearly all ions are adsorbed from the solution. EPR shows that adsorbed copper(II) ions are chemically bonded to the starch molecules (preferably) at COOH sites and uniformly dispersed in the starch structure. The complexes are typical of octahedral or square-quadratic coordination with spin-Hamiltonian parameters gǁ=2.373, g⊥= 2.080, Aǁ=12.1 mT, A⊥=1.0 mT. For higher concentrations the Cu(II) displays a tendency to clustering. Iron(III) ions are introduced into starch in a form of clusters mainly, even for the smallest concentration. The highest concentrations of both Cu(II) and Fe(III) were observed in LUBOX starch having the highest degree of oxidation.

  6. SERS and DFT investigation of 1-(2-pyridylazo)-2-naphthol and its metal complexes with Al(III), Mn(II), Fe(III), Cu(II), Zn(II) and Pb(II)

    Science.gov (United States)

    Szabó, László; Herman, Krisztian; Mircescu, Nicoleta E.; Fălămaş, Alexandra; Leopold, Loredana F.; Leopold, Nicolae; Buzumurgă, Claudia; Chiş, Vasile

    The development of surface-enhanced Raman scattering (SERS) as a prospective analytical methodology for detection of metal ions was shown in recent years by several studies on metal complexes. In this work, 1-(2-pyridylazo)-2-naphthol (PAN) and its Al(III), Mn(II), Fe(III), Cu(II), Zn(II) and Pb(II) complexes were studied by FTIR, FT-Raman and surface enhanced Raman spectroscopies. Molecular geometry optimization, molecular electrostatic potential (MEP) distribution and vibrational frequencies calculations were performed using the hybrid B3LYP exchange-correlation functional for the PAN molecule and its bidentate complexes. The calculated MEP distributions indicated the atoms with highest electronegativity, the adsorption to the silver surface occurring through these atoms. Based on experimental and theoretical data we were able to identify unique and representative features, useful for the identification of each PAN-metal complex.

  7. Heat capacity and magnetic phase transition of two-dimensional metal-assembled complex, K[{l_brace}Mn{sup III}(3-MeOsalen){r_brace}{sub 2}Fe{sup III}(China){sub 6}

    Energy Technology Data Exchange (ETDEWEB)

    Miyazaki, Yuji [Research Center for Molecular Thermodynamics, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043 (Japan)]. E-mail: miyazaki@chem.sci.osaka-u.ac.jp; Wang, Qi [Research Center for Molecular Thermodynamics, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043 (Japan); Department of Chemistry, Zhejiang University, Hangzhou 310027 (China); Yu, Qing-sen [Research Center for Molecular Thermodynamics, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043 (Japan); Department of Chemistry, Zhejiang University, Hangzhou 310027 (China); Matsumoto, Tetsuya [Research Center for Molecular Thermodynamics, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043 (Japan); Miyasaka, Hitoshi [Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, Minami-ohsawa 1-1, Hachioji, Tokyo 192-0397 (Japan); Matsumoto, Naohide [Department of Chemistry, Faculty of Science, Kumamoto University, 2-39-1 Kurokami, Kumamoto 860-8555 (Japan); Sorai, Michio [Research Center for Molecular Thermodynamics, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043 (Japan)

    2005-06-15

    Heat capacities of the two-dimensional metal-assembled complex, K[{l_brace}Mn{sup III}(3-MeOsalen){r_brace}{sub 2}Fe{sup III}(China){sub 6}] [3-MeOsalen N,N'-ethylenebis(3-methoxysalicylideneaminato) dianion], were measured at the temperatures from 0.5 to 300 K by adiabatic calorimetry. An antiferromagnetic phase transition was observed at T {sub N} = 8.29 K. Above T {sub N}, a heat capacity tail arising from the short-range-order effect of the spins was found, which is characteristic of two-dimensional magnets. The magnetic enthalpy and entropy were evaluated to be {delta}H = 373 J mol{sup -1} and {delta}S = 31.3 J K{sup -1} mol{sup -1}, respectively. The experimental magnetic entropy is in good agreement with {delta}S = R ln (5 x 5 x 2) (=32.5 J K{sup -1} mol{sup -1}; R being the gas constant), which is expected for the metal complex with two Mn(III) ions in high spin state (spin quantum number S = 2) and one Fe(III) ion in low spin state (S = 1/2). The spin wave analysis suggests that the complex shows three-dimensional antiferromagnetic order below T {sub N}. The heat capacity tail above T {sub N} was decreased by grinding and pressurizing the crystal. This mechanochemical effect would originate in the increase of lattice defects and imperfections in the crystal lattice, leading to decrease of the magnetic heat capacity and hence the magnetic enthalpy and entropy.

  8. Superparamagnetic nanomaterial Fe3O4-TiO2 for the removal of As(V) and As(III) from aqueous solutions.

    Science.gov (United States)

    Beduk, Fatma

    2016-01-01

    A magnetically separable nanomaterial Fe3O4-TiO2 was synthesized and characterized which was subsequently used for the removal of arsenic (V) from aqueous solutions. The surface morphology, magnetic properties, crystalline structure, thermal stability and Brunauer-Emmet-Teller surface area of the synthesized Fe3O4-TiO2 nanoparticles (NPs) are characterized by scanning electron microscope and high-resolution transmission electron microscope, vibrating sample magnetometry, X-ray diffractometer, thermogravimetric analysis and multi point function surface area analyzer. The saturation magnetization of Fe3O4-TiO2 NPs was determined to be 50.97 emu/g, which makes them superparamagnetic. The surface area of Fe3O4-TiO2 NPs was as much as 94.9 m(2)/g. The main factors affecting adsorption efficiency, such as solution pH, reaction time, initial As(V) concentration and adsorbent concentration are investigated. When the adsorption isotherms were analyzed by the Langmuir, Freundlich and Dubinin-Radushkevich models, equilibrium data were found to be well represented by Freundlich isotherm, and adsorption on Fe3O4-TiO2 NPs fitted well with pseudo-second-order kinetic model. The maximum adsorption capacity of As(V) on Fe3O4-TiO2 NPs, calculated by the Freundlich model was determined at 11.434 µg/g. 1.0 g/L of Fe3O4-TiO2 NPs was efficient for complete removal of 100 µg/L As(V) in 1 h. Fe3O4-TiO2 NPs was also effective for 93% removal of 100 µg/L As(III). Matrix effect was determined using As(V)-contaminated well water. Successfull results were obtained for purification of real well water containing 137.12 µg/L As(V). Results show that Fe3O4-TiO2 NPs are promising adsorbents with an advantage of magnetic separation.

  9. Ultraviolet photochemical reaction of [Fe(III)(C2O4)3](3-) in aqueous solutions studied by femtosecond time-resolved X-ray absorption spectroscopy using an X-ray free electron laser.

    Science.gov (United States)

    Ogi, Y; Obara, Y; Katayama, T; Suzuki, Y-I; Liu, S Y; Bartlett, N C-M; Kurahashi, N; Karashima, S; Togashi, T; Inubushi, Y; Ogawa, K; Owada, S; Rubešová, M; Yabashi, M; Misawa, K; Slavíček, P; Suzuki, T

    2015-05-01

    Time-resolved X-ray absorption spectroscopy was performed for aqueous ammonium iron(III) oxalate trihydrate solutions using an X-ray free electron laser and a synchronized ultraviolet laser. The spectral and time resolutions of the experiment were 1.3 eV and 200 fs, respectively. A femtosecond 268 nm pulse was employed to excite [Fe(III)(C2O4)3](3-) in solution from the high-spin ground electronic state to ligand-to-metal charge transfer state(s), and the subsequent dynamics were studied by observing the time-evolution of the X-ray absorption spectrum near the Fe K-edge. Upon 268 nm photoexcitation, the Fe K-edge underwent a red-shift by more than 4 eV within 140 fs; however, the magnitude of the redshift subsequently diminished within 3 ps. The Fe K-edge of the photoproduct remained lower in energy than that of [Fe(III)(C2O4)3](3-). The observed red-shift of the Fe K-edge and the spectral feature of the product indicate that Fe(III) is upon excitation immediately photoreduced to Fe(II), followed by ligand dissociation from Fe(II). Based on a comparison of the X-ray absorption spectra with density functional theory calculations, we propose that the dissociation proceeds in two steps, forming first [(CO2 (•))Fe(II)(C2O4)2](3-) and subsequently [Fe(II)(C2O4)2](2-).

  10. Ultraviolet photochemical reaction of [Fe(III(C2O43]3− in aqueous solutions studied by femtosecond time-resolved X-ray absorption spectroscopy using an X-ray free electron laser

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    Y. Ogi

    2015-05-01

    Full Text Available Time-resolved X-ray absorption spectroscopy was performed for aqueous ammonium iron(III oxalate trihydrate solutions using an X-ray free electron laser and a synchronized ultraviolet laser. The spectral and time resolutions of the experiment were 1.3 eV and 200 fs, respectively. A femtosecond 268 nm pulse was employed to excite [Fe(III(C2O43]3− in solution from the high-spin ground electronic state to ligand-to-metal charge transfer state(s, and the subsequent dynamics were studied by observing the time-evolution of the X-ray absorption spectrum near the Fe K-edge. Upon 268 nm photoexcitation, the Fe K-edge underwent a red-shift by more than 4 eV within 140 fs; however, the magnitude of the redshift subsequently diminished within 3 ps. The Fe K-edge of the photoproduct remained lower in energy than that of [Fe(III(C2O43]3−. The observed red-shift of the Fe K-edge and the spectral feature of the product indicate that Fe(III is upon excitation immediately photoreduced to Fe(II, followed by ligand dissociation from Fe(II. Based on a comparison of the X-ray absorption spectra with density functional theory calculations, we propose that the dissociation proceeds in two steps, forming first [(CO2•Fe(II(C2O42]3− and subsequently [Fe(II(C2O42]2−.

  11. Synthesis and magnetic properties of Co1-xZnxFe2O4 (x=0÷1) nanopowders by thermal decomposition of Co(II), Zn(II) and Fe(III) carboxylates

    Science.gov (United States)

    Stefanescu, Mircea; Bozdog, Marius; Muntean, Cornelia; Stefanescu, Oana; Vlase, Titus

    2015-11-01

    Nanoparticles of cobalt-zinc ferrite Co1-xZnxFe2O4 with x varying from 0 to 1.0 were prepared by a new method, the thermal decomposition of carboxylates of Fe(III), Co(II) and Zn(II). The obtained carboxylate precursor was characterized by thermal analysis and FT-IR spectroscopy. The precursor was annealed at 350, 600 and 1000 °C. It was found that the spinel cobalt-zinc ferrite was formed starting at 350 °C, but in mixture with simple oxides γ-Fe2O3, Co3O4 and ZnO. At 1000 °C Co1-xZnxFe2O4 was formed quantitatively as a single, well-crystallized phase. The saturation magnetization of the samples annealed at 1000 °C decreased significantly with increasing Zn2+ content from 83.93 emu/g (x=0) to 4.92 emu/g (x=1.0). At 350 and 600 °C the saturation magnetization had the same trend, even if there were contributions of other magnetic phases. Obtaining of spinel ferrite was evidenced by X-ray diffractometry and FT-IR spectrometry. Powder morphology was determined by scanning electron microscopy. Magnetic properties of the synthesized ferrites were investigated employing a conventional induction method.

  12. Influence of Halogen Substituents on the Catalytic Oxidation of 2,4,6-Halogenated Phenols by Fe(III-Tetrakis(p-hydroxyphenyl porphyrins and Potassium Monopersulfate

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    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.

  13. Valence-delocalization of the mixed-valence oxo-centered trinuclear iron propionates [Fe{2/III}FeIIO(C2H5CO2)6(py)3] npy; n=0, 1.5

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    Nakamoto, Tadahiro; Katada, Motomi; Kawata, Satoshi; Kitagawa, Susumu; Sano, Hirotoshi; Konno, Michiko

    1994-12-01

    Mixed-valence trinuclear iron propionates [Fe{2/III}FeIIO(C2H5CO2)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. Mössbauer 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.

  14. 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

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    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

  15. MOF catalysis of Fe(II)-to-Fe(III) reaction for an ultrafast and one-step generation of the Fe2O3@MOF composite and uranium(vi) reduction by iron(ii) under ambient conditions.

    Science.gov (United States)

    Xiong, Yang Yang; Li, Jian Qiang; Yan, Chang Sheng; Gao, Heng Ya; Zhou, Jian Ping; Gong, Le Le; Luo, Ming Biao; Zhang, Le; Meng, Pan Pan; Luo, Feng

    2016-08-07

    Herein, we demonstrate that Zn-MOF-74 enables the ultrafast and one-step generation of the Fe2O3@MOF composite once Zn-MOF-74 contacts with FeSO4 solution. This unique reaction can be further applied in catalysis of U(vi) reduction by Fe(ii) under ambient conditions. The results provide a highly renovated strategy for U(vi) reduction by Fe(ii) just under ambient conditions, which completely subvert all established methods about U(vi) reduction by Fe(ii) in which O2- and CO2-free conditions are absolutely required.

  16. Adsorption of N/S heterocycles in the flexible metal-organic framework MIL-53(Fe(III)) studied by in situ energy dispersive X-ray diffraction.

    Science.gov (United States)

    Van de Voorde, Ben; Munn, Alexis S; Guillou, Nathalie; Millange, Franck; De Vos, Dirk E; Walton, Richard I

    2013-06-14

    The adsorption of N/S-containing heterocyclic organic molecules in the flexible iron(III) terephthalate MIL-53, Fe(III)(OH)(0.6)F(0.4)(O2C-C6H4-CO2)·(H2O), from the liquid phase was studied with in situ energy dispersive X-ray diffraction (EDXRD), in order to follow the adsorption-induced expansion of the structure. For comparison with the diffraction data, liquid phase adsorption isotherms were recorded for uptake of benzothiophene, benzothiazole and indole in isopropanol and in heptane. The solvent not only influences pore opening but is also a competing guest. The in situ EDXRD experiments allow the kinetics of guest uptake and the competition with solvent to be monitored directly. Indole uptake is limited; this adsorbate is barely capable of opening the closed, either hydrated or dehydrated, MIL-53(Fe) structure, or of penetrating the isopropanol-containing material in the concentration range under study. When isopropanol is used as a solvent, the guest molecules benzothiophene and benzothiazole must be present at a certain threshold concentration before substantial adsorption into the metal-organic framework takes place, eventually resulting in full opening of the structure. The fully expanded structures of benzothiophene or benzothiazole loaded MIL-53(Fe