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

Science.gov (United States)

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

2018-02-01

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

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.

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.

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.

Effect of dissimilatory Fe(III) reducers on bio-reduction and nickel-cobalt recovery from Sukinda chromite-overburden.

Science.gov (United States)

Esther, Jacintha; Panda, Sandeep; Behera, Sunil K; Sukla, Lala B; Pradhan, Nilotpala; Mishra, Barada K

2013-10-01

The effect of an adapted dissimilatory iron reducing bacterial consortium (DIRB) towards bio-reduction of Sukinda chromite overburden (COB) with enhanced recovery of nickel and cobalt is being reported for the first time. The remarkable ability of DIRB to utilize Fe(III) as terminal electron acceptor reducing it to Fe(II) proved beneficial for treatment of COB as compared to previous reports for nickel leaching. XRD studies showed goethite as the major iron-bearing phase in COB. Under facultative anaerobic conditions, goethite was reduced to hematite and magnetite with the exposure of nickel oxide. FESEM studies showed DIRB to be associated with COB through biofilm formation with secondary mineral precipitates of magnetite deposited as tiny globular clusters on the extra polymeric substances. The morphological and mineralogical changes in COB, post DIRB application, yielded a maximum of 68.5% nickel and 80.98% cobalt in 10 days using 8M H2SO4. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

Science.gov (United States)

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

2000-01-01

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

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

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

Science.gov (United States)

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

2005-01-01

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

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

International Nuclear Information System (INIS)

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

2016-01-01

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

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

Science.gov (United States)

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

2012-04-03

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

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

International Nuclear Information System (INIS)

Khojali, Inas Osman

1999-04-01

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

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

International Nuclear Information System (INIS)

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

2000-01-01

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

Functional Role of Infective Viral Particles on Metal Reduction

Energy Technology Data Exchange (ETDEWEB)

Coates, John D.

2014-04-01

A proposed strategy for the remediation of uranium (U) contaminated sites was based on the immobilization of U by reducing the oxidized soluble U, U(VI), to form a reduced insoluble end product, U(IV). Previous studies identified Geobacter sp., including G. sulfurreducens and G. metallireducens, as predominant U(VI)-reducing bacteria under acetate-oxidizing and U(VI)-reducing conditions. Examination of the finished genome sequence annotation of the canonical metal reducing species Geobacter sulfurreducens strain PCA and G. metallireduceans strain GS-15 as well as the draft genome sequence of G. uraniumreducens strain Rf4 identified phage related proteins. In addition, the completed genome for Anaeromyxobacter dehalogenans and the draft genome sequence of Desulfovibrio desulfuricans strain G20, two more model metal-reducing bacteria, also revealed phage related sequences. The presence of these gene sequences indicated that Geobacter spp., Anaeromyxobacter spp., and Desulfovibrio spp. are susceptible to viral infection. Furthermore, viral populations in soils and sedimentary environments in the order of 6.4×10{sup 6}–2.7×10{sup 10} VLP’s cm{sup -3} have been observed. In some cases, viral populations exceed bacterial populations in these environments suggesting that a relationship may exist between viruses and bacteria. Our preliminary screens of samples collected from the ESR FRC indicated that viral like particles were observed in significant numbers. The objective of this study was to investigate the potential functional role viruses play in metal reduction specifically Fe(III) and U(VI) reduction, the environmental parameters affecting viral infection of metal reducing bacteria, and the subsequent effects on U transport.

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.

Isolation and Biosynthetic Analysis of Haliamide, a New PKS-NRPS Hybrid Metabolite from the Marine Myxobacterium Haliangium ochraceum

Directory of Open Access Journals (Sweden)

Yuwei Sun

2016-01-01

Full Text Available Myxobacteria of marine origin are rare and hard-to-culture microorganisms, but they genetically harbor high potential to produce novel antibiotics. An extensive investigation on the secondary metabolome of the unique marine myxobacterium Haliangium ochraceum SMP-2 led to the isolation of a new polyketide-nonribosomal peptide hybrid product, haliamide (1. Its structure was elucidated by spectroscopic analyses including NMR and HR-MS. Haliamide (1 showed cytotoxicity against HeLa-S3 cells with IC50 of 12 μM. Feeding experiments were performed to identify the biosynthetic building blocks of 1, revealing one benzoate, one alanine, two propionates, one acetate and one acetate-derived terminal methylene. The biosynthetic gene cluster of haliamide (hla, 21.7 kbp was characterized through the genome mining of the producer, allowing us to establish a model for the haliamide biosynthesis. The sulfotransferase (ST-thioesterase (TE domains encoded in hlaB appears to be responsible for the terminal alkene formation via decarboxylation.

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

Science.gov (United States)

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

2015-12-01

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

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

OpenAIRE

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

1999-01-01

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

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.

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

Identification of a c-Type Cytochrome Specific for Manganese Dioxide (MnO2) Reduction in Anaeromyxobacter dehalogenans Strain 2CP-C

Science.gov (United States)

Pfiffner, S. M.; Nissen, S.; Liu, X.; Chourey, K.; Vishnivetskaya, T. A.; Hettich, R.; Loeffler, F.

2014-12-01

Anaeromyxobacter dehalogenans is a metabolically versatile Deltaproteobacterium and conserves energy from the reduction of various electron acceptors, including insoluble MnO2 and ferric oxides/oxyhydroxides (FeOOH). The goal of this study was to identify c-type cytochromes involved in electron transfer to MnO2. The characterization of deletion mutants has revealed a number of c-type cytochromes involved in electron transfer to solid metal oxides in Shewanella spp. and Geobacter spp; however, a genetic system for Anaeromyxobacter is not available. The A. dehalogenans str. 2CP-C genome encodes 68 putative c-type cytochromes, which all lack functional assignments. To identify c-type cytochromes involved in electron transfer to solid MnO2, protein expression profiles of A. dehalogenans str. 2CP-C cells grown with acetate as electron donor and MnO2, ferric citrate, FeOOH, nitrate or fumarate as electron acceptors were compared. Whole cell proteomes were analyzed after trypsin proteolysis using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Distinct c-type cytochrome expression patterns were observed with cells grown with different electron acceptors. A. dehalogenans str. 2CP-C grown with MnO2 expressed 25 out of the 68 c-type cytochromes encoded on the genome. The c-type cytochrome Adeh_1278 was only expressed in strain 2CP-C grown with MnO2. Reverse transcription PCR confirmed that the Adeh_1278 gene was transcribed in MnO2-grown cells but not in cells grown with other terminal electron acceptors. The expression of the Adeh_1278 gene correlated with Mn(IV) reduction activity. Adeh_1278 has three heme binding motifs and is predicted to be located in the periplasm. The identification of Adeh_1278 as a protein uniquely expressed when MnO2 serves as electron acceptor suggests its utility as a biomarker for MnO2 reduction. This example demonstrates the value of the LC-MS/MS approach for identifying specific proteins of interest and making functional assignments

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

Directory of Open Access Journals (Sweden)

Krishnaveni Venkidusamy

2018-03-01

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

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

Science.gov (United States)

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

2018-01-01

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

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

Science.gov (United States)

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

2008-01-01

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

Reductive immobilization of U(VI) in Fe(III) oxide-reducing subsurface sediments: Analysis of coupled microbial-geochemical processes in experimental reactive transport systems. Final Scientific/Technical Report-EMSP 73914

International Nuclear Information System (INIS)

Eric E. Roden Matilde M. Urrutia Mark O. Barnett Clifford R. Lange

2005-01-01

The purpose of this research was to provide information to DOE on microbiological and geochemical processes underlying the potential use of dissimilatory metal-reducing bacteria (DMRB) to create subsurface redox barriers for immobilization of uranium and other redox-sensitive metal/radionuclide contaminants that were released to the environment in large quantities during Cold War nuclear weapons manufacturing operations. Several fundamental scientific questions were addressed in order to understand and predict how such treatment procedures would function under in situ conditions in the subsurface. These questions revolved the coupled microbial-geochemical phenomena which are likely to occur within a redox barrier treatment zone, and on the dynamic interactions between hydrologic flux and biogeochemical process rates. First, we assembled a robust conceptual understanding and numerical framework for modeling the kinetics of microbial Fe(III) oxide reduction and associated DMRB growth in sediments. Development of this framework is a critical prerequisite for predicting the potential effectiveness of DMRB-promoted subsurface bioremediation, since Fe(III) oxides are expected to be the primary source of electron-accepting capacity for growth and maintenance of DMRB in subsurface environments. We also defined in detail the kinetics of microbial (enzymatic) versus abiotic, ferrous iron-promoted reduction of U(VI) in the presence and absence of synthetic and natural Fe(III) oxide materials. The results of these studies suggest that (i) the efficiency of dissolved U(VI) scavenging may be influenced by the kinetics of enzymatic U(VI) reduction in systems with relative short fluid residence times; (2) association of U(VI) with diverse surface sites in natural soils and sediments has the potential to limit the rate and extent of microbial U(VI) reduction, and in turn modulate the effectiveness of in situ U(VI) bioremediation; and (3) abiotic, ferrous iron (Fe(II)) drive n U

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

Science.gov (United States)

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

1992-01-01

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

Role of an organic carbon-rich soil and Fe(III) reduction in reducing the toxicity and environmental mobility of chromium(VI) at a COPR disposal site.

Science.gov (United States)

Ding, Weixuan; Stewart, Douglas I; Humphreys, Paul N; Rout, Simon P; Burke, Ian T

2016-01-15

Cr(VI) is an important contaminant found at sites where chromium ore processing residue (COPR) is deposited. No low cost treatment exists for Cr(VI) leaching from such sites. This study investigated the mechanism of interaction of alkaline Cr(VI)-containing leachate with an Fe(II)-containing organic matter rich soil beneath the waste. The soil currently contains 0.8% Cr, shown to be present as Cr(III)(OH)3 in EXAFS analysis. Lab tests confirmed that the reaction of Cr(VI) in site leachate with Fe(II) present in the soil was stoichiometrically correct for a reductive mechanism of Cr accumulation. However, the amount of Fe(II) present in the soil was insufficient to maintain long term Cr(VI) reduction at historic infiltration rates. The soil contains a population of bacteria dominated by a Mangroviflexus-like species, that is closely related to known fermentative bacteria, and a community capable of sustaining Fe(III) reduction in alkaline culture. It is therefore likely that in situ fermentative metabolism supported by organic matter in the soil produces more labile organic substrates (lactate was detected) that support microbial Fe(III) reduction. It is therefore suggested that addition of solid phase organic matter to soils adjacent to COPR may reduce the long term spread of Cr(VI) in the environment. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

Novel Insights Into Microbial Uranium Reduction and Immobilization

Science.gov (United States)

Loeffler, F. E.; Fletcher, K.; Thomas, S.; Kemner, K. M.; Boyanov, M.; Sanford, R.

2010-12-01

Many ferric iron- and manganese oxide-reducing bacteria affect the oxidation state and complexation of toxic radionuclides in subsurface environments. Relevant to uranium (U) speciation are bacteria that reduce predominantly water-soluble and mobile U(VI) to U(IV), which has reduced solubility and typically forms the uraninite (UO2) mineral. Gram-negative model organisms including Shewanella spp., Geobacter spp., and more recently Anaeromyxobacter spp. use U(VI) as growth-supporting electron acceptor; however, the biomass yields are lower than predicted based on the theoretical free energy changes associated with U(VI)-to-U(IV) reduction. Recent findings demonstrated that U(VI) reduction is not limited to Gram-negative bacteria, and members of the genus Desulfitobacterium, which are commonly found in soil and subsurface environments, share the ability to reduce U(VI). Interestingly, extended X-ray absorption fine structure (EXAFS) analysis demonstrated that the U(IV) produced in cultures of five Desulfitobacterium spp. was not UO2 but rather a phase or mineral composed of mononuclear U(IV) atoms. Since the properties of the reduced product influence U(IV) fate, knowledge of the diversity of U reduction mechanisms and the stability of the end products is desirable for controlling and predicting U fate. For example, UO2 is susceptible to reoxidation by oxidants, and oxic/anoxic interface processes are controlling the stability of the precipitated material. In other words, metal reducers that thrive at the oxic/anoxic interface are likely key players affecting long-term U fate. Anaeromyxobacter spp. are facultative microaerophiles and grow with oxygen as electron acceptor at partial pressures equal to or below 0.18 atm. Thus, Anaeromyxobacter are uniquely adapted to life at the oxic-anoxic interface where they consume oxygen and take advantage of oxidized metal species including U(VI) as electron acceptors. The application of 16S rRNA gene-targeted qPCR approaches

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

Energy Technology Data Exchange (ETDEWEB)

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

1992-04-01

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

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

International Nuclear Information System (INIS)

Grivé, Mireia; Duro, Lara; Bruno, Jordi

2014-01-01

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

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

DEFF Research Database (Denmark)

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

2011-01-01

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

Characterization of the surfaceome of the metal-reducing bacterium Desulfotomaculum reducens

Directory of Open Access Journals (Sweden)

Elena eDalla Vecchia

2014-08-01

Full Text Available Desulfotomaculum reducens strain MI-1 is a Gram-positive, sulfate-reducing bacterium also capable of reducing Fe(III. Metal reduction in Gram-positive bacteria is poorly understood. Here, we investigated Fe(III reduction with lactate, a non-fermentable substrate, as the electron donor. Lactate consumption is concomitant to Fe(III reduction, but does not support significant growth, suggesting that little energy can be conserved from this process and that it may occur fortuitously. D. reducens can reduce both soluble (Fe(III-citrate and insoluble (hydrous ferric oxide, HFO Fe(III. Because physically inaccessible HFO was not reduced, we concluded that reduction requires direct contact under these experimental conditions. This implies the presence of a surface exposed reductase capable of transferring electrons from the cell to the extracellular electron acceptor. With the goal of characterizing the role of surface proteins in D. reducens and of identifying candidate Fe(III reductases, we carried out an investigation of the surface proteome (surfaceome of D. reducens. Cell surface exposed proteins were extracted by trypsin cell shaving or by lysozyme treatment, and analyzed by liquid chromatography-tandem mass spectrometry. This investigation revealed that the surfaceome fulfills many functions, including solute transport, protein export, maturation and hydrolysis, peptidoglycan synthesis and modification, and chemotaxis. Furthermore, a few redox-active proteins were identified. Among these, three are putatively involved in Fe(III reduction, i.e., a membrane-bound hydrogenase 4Fe-4S cluster subunit (Dred_0462, a heterodisulfide reductase subunit A (Dred_0143 and a protein annotated as alkyl hydroperoxide reductase but likely functioning as a thiol-disulfide oxidoreductase (Dred_1533.

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

Science.gov (United States)

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

2016-02-01

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

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

International Nuclear Information System (INIS)

Remsungnen, T.

2002-11-01

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

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.

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

International Nuclear Information System (INIS)

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

2017-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

1998-08-01

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

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.

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

Directory of Open Access Journals (Sweden)

Xinqiang Du

2018-03-01

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

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

Science.gov (United States)

Lee, Ji-Hoon; Lee, Bong-Joo

2017-11-25

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

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

International Nuclear Information System (INIS)

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

2005-01-01

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

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

Directory of Open Access Journals (Sweden)

S. Yousef Ebrahimipur

2012-12-01

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

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

International Nuclear Information System (INIS)

Zhang Qiwei; Jiao Rongzhou; Song Chongli

1994-08-01

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

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

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

Science.gov (United States)

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

2017-12-01

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

Aggregicoccus edonensis gen. nov., sp. nov., an unusually aggregating myxobacterium isolated from a soil sample.

Science.gov (United States)

Sood, Sakshi; Awal, Ram Prasad; Wink, Joachim; Mohr, Kathrin I; Rohde, Manfred; Stadler, Marc; Kämpfer, Peter; Glaeser, Stefanie P; Schumann, Peter; Garcia, Ronald; Müller, Rolf

2015-03-01

A novel myxobacterium, MCy1366(T) (Ar1733), was isolated in 1981 from a soil sample collected from a region near Tokyo, Japan. It displayed general myxobacterial features like Gram-negative-staining, rod-shaped vegetative cells, gliding on solid surfaces, microbial lytic activity, fruiting-body-like aggregates and myxospore-like structures. The strain was mesophilic, aerobic and showed a chemoheterotrophic mode of nutrition. It was resistant to many antibiotics such as cephalosporin C, kanamycin, gentamicin, hygromycin B, polymyxin and bacitracin, and the key fatty acids of whole cell hydrolysates were iso-C15 : 0, iso-C17 : 0 and iso-C17 : 0 2-OH. The genomic DNA G+C content of the novel strain was 65.6 mol%. The 16S rRNA gene sequence showed highest similarity (97.60 %) to 'Stigmatella koreensis' strain KYC-1019 (GenBank accession no. EF112185). Phylogenetic analysis based on 16S rRNA gene sequences and MALDI-TOF MS data revealed a novel branch in the family Myxococcaceae. DNA-DNA hybridization showed only 28 % relatedness between the novel strain and the closest recognized species, Corallococcus exiguus DSM 14696(T) (97 % 16S rRNA gene sequence similarity). A recent isolate from a soil sample collected in Switzerland, MCy10622, displayed 99.9 % 16S rRNA gene sequence similarity with strain MCy1366(T) and showed almost the same characteristics. Since some morphological features like fruiting-body-like aggregates were barely reproducible in the type strain, the newly isolated strain, MCy10622, was also intensively studied. On the basis of a comprehensive taxonomic study, we propose a novel genus and species, Aggregicoccus edonensis gen. nov., sp. nov., for strains MCy1366(T) and MCy10622. The type strain of the type species is MCy1366(T) ( = DSM 27872(T) = NCCB 100468(T)). © 2015 Prof. Dr. Rolf Muller, Department of Pharmaceutical Biotechnology, Saarland University, Campus C2 3, 66123 Saarbrücken, Germany.

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

International Nuclear Information System (INIS)

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

2010-01-01

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

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

Directory of Open Access Journals (Sweden)

Endang Tri Wahyuni

2010-06-01

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

Mercury methylation coupled to iron reduction by dissimilatory iron-reducing bacteria.

Science.gov (United States)

Si, Youbin; Zou, Yan; Liu, Xiaohong; Si, Xiongyuan; Mao, Jingdong

2015-03-01

Iron reduction and mercury methylation by dissimilatory iron-reducing bacteria (DIRB), Geobacter sulfurreducens and Shewanella oneidensis, were studied, and the relationship of mercury methylation coupled to iron reduction was determined. The ability of both bacteria for reducing iron was tested, and Fe(III) reduction occurred with the highest rate when ferric oxyhydroxide was used as a terminal electron acceptor. G. sulfurreducens had proven to mediate the production of methylmercury (MeHg), and a notable increase of MeHg following the addition of inorganic Hg was observed. When the initial concentration of HgCl2 was 500nM, about 177.03nM of MeHg was determined at 8d after G. sulfurreducens inoculation. S. oneidensis was tested negligible for Hg methylation and only 12.06nM of MeHg was determined. Iron reduction could potentially influence Hg methylation rates. The increase in MeHg was consistent with high rate of iron reduction, indicating that Fe(III) reduction stimulated the formation of MeHg. Furthermore, the net MeHg concentration increased at low Fe(III) additions from 1.78 to 3.57mM, and then decreased when the added Fe(III) was high from 7.14 to 17.85mM. The mercury methylation rate was suppressed with high Fe(III) additions, which might have been attributable to mercury complexation and low availability. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

Directory of Open Access Journals (Sweden)

S. Esakki Muthu

2005-01-01

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

Secondary mineral formation associated with respiration of nontronite, NAu-1 by iron reducing bacteria

Directory of Open Access Journals (Sweden)

Furukawa Yoko

2005-10-01

Full Text Available Experimental batch and miscible-flow cultures were studied in order to determine the mechanistic pathways of microbial Fe(III respiration in ferruginous smectite clay, NAu-1. The primary purpose was to resolve if alteration of smectite and release of Fe precedes microbial respiration. Alteration of NAu-1, represented by the morphological and mineralogical changes, occurred regardless of the extent of microbial Fe(III reduction in all of our experimental systems, including those that contained heat-killed bacteria and those in which O2, rather than Fe(III, was the primary terminal electron acceptor. The solid alteration products observed under transmission electron microscopy included poorly crystalline smectite with diffuse electron diffraction signals, discrete grains of Fe-free amorphous aluminosilicate with increased Al/Si ratio, Fe-rich grains, and amorphous Si globules in the immediate vicinity of bacterial cells and extracellular polymeric substances. In reducing systems, Fe was also found as siderite. The small amount of Fe partitioned to the aqueous phase was primarily in the form of dissolved Fe(III species even in the systems in which Fe(III was the primary terminal electron acceptor for microbial respiration. From these observations, we conclude that microbial respiration of Fe(III in our laboratory systems proceeded through the following: (1 alteration of NAu-1 and concurrent release of Fe(III from the octahedral sheets of NAu-1; and (2 subsequent microbial respiration of Fe(III.

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

Isolation and identification of ferric reducing bacteria and evaluation of their roles in iron availability in two calcareous soils

Science.gov (United States)

Ghorbanzadeh, N.; Lakzian, A.; Haghnia, G. H.; Karimi, A. R.

2014-12-01

Iron is an essential element for all organisms which plays a crucial role in important biochemical processes such as respiration and photosynthesis. Iron deficiency seems to be an important problem in many calcareous soils. Biological dissimilatory Fe(III) reduction increases iron availability through reduction of Fe(III) to Fe(II). The aim of this study was to isolate, identify and evaluate some bacterial isolates for their abilities to reduce Fe(III) in two calcareous soils. Three bacterial isolates were selected and identified from paddy soils by using 16S rRNA amplification and then inoculated to sterilized and non-sterilized calcareous soils in the presence and absence of glucose. The results showed that all isolates belonged to Bacillus genus and were capable of reducing Fe(III) to Fe(II) in vitro condition. The amount of Fe(III) reduction in sterilized calcareous soils was significantly higher when inoculated with PS23 isolate and Shewanella putrefaciens ( S. putrefaciens) (as positive control) compared to PS16 and PS11 isolates. No significant difference was observed between PS11 and PS16 isolates in the presence of indigenous microbial community. The results also revealed that glucose had a significant effect on Fe(III) reduction in the examined calcareous soil samples. The amount of Fe(III) reduction increased two-fold when soil samples were treated with glucose and inoculated by S. putrefaciens and PS23 in non-sterilized soils.

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

Microbial reduction of structural iron in interstratified illite-smectite minerals by a sulfate-reducing bacterium.

Science.gov (United States)

Liu, D; Dong, H; Bishop, M E; Zhang, J; Wang, H; Xie, S; Wang, S; Huang, L; Eberl, D D

2012-03-01

Clay minerals are ubiquitous in soils, sediments, and sedimentary rocks and could coexist with sulfate-reducing bacteria (SRB) in anoxic environments, however, the interactions of clay minerals and SRB are not well understood. The objective of this study was to understand the reduction rate and capacity of structural Fe(III) in dioctahedral clay minerals by a mesophilic SRB, Desulfovibrio vulgaris and the potential role in catalyzing smectite illitization. Bioreduction experiments were performed in batch systems, where four different clay minerals (nontronite NAu-2, mixed-layer illite-smectite RAr-1 and ISCz-1, and illite IMt-1) were exposed to D. vulgaris in a non-growth medium with and without anthraquinone-2,6-disulfonate (AQDS) and sulfate. Our results demonstrated that D. vulgaris was able to reduce structural Fe(III) in these clay minerals, and AQDS enhanced the reduction rate and extent. In the presence of AQDS, sulfate had little effect on Fe(III) bioreduction. In the absence of AQDS, sulfate increased the reduction rate and capacity, suggesting that sulfide produced during sulfate reduction reacted with the phyllosilicate Fe(III). The extent of bioreduction of structural Fe(III) in the clay minerals was positively correlated with the percentage of smectite and mineral surface area of these minerals. X-ray diffraction, and scanning and transmission electron microscopy results confirmed formation of illite after bioreduction. These data collectively showed that D. vulgaris could promote smectite illitization through reduction of structural Fe(III) in clay minerals. © 2011 Blackwell Publishing Ltd.

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

Science.gov (United States)

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

2017-10-15

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

Improved Understanding of Microbial Iron and Sulfate Reduction Through a Combination of Bottom-up and Top-down Functional Proteomics Assays

Energy Technology Data Exchange (ETDEWEB)

Richardson, Ruth [Cornell Univ., Ithaca, NY (United States)

2016-02-28

Our overall goal was to improve the understanding of microbial iron and sulfate reduction by evaluating a diverse iron and sulfate reducing organisms utilizing a multi-omics approach combining “top-down” and “bottom-up” omics methodologies. We initiated one of the first combined comparative genomics, shotgun proteomics, RTqPCR, and heterologous expression studies in pursuit of our project objectives. Within the first year of this project, we created a new bioinformatics tool for ortholog identification (“SPOCS”). SPOCS is described in our publication, Curtis et al., 2013. Using this tool we were able to identify conserved orthologous groups across diverse iron and sulfate reducing microorganisms from Firmicutes, gamma-proteobacteria and delta-proteobacteria. For six iron and sulfate reducers we also performed shotgun proteomics (“bottom-up” proteomics including accurate mass and time (AMT) tag and iTRAQ approaches). Cultures include Gram (-) and Gram (+) microbes. Gram (-) were: Geobacter sulfureducens (grown on iron citrate and fumarate), Geobacter bemidjiensis (grown on iron citrate and fumarate), Shewanella oneidiensis (grown on iron citrate and fumarate) and Anaeromyxobacter dehalogenans (grown on iron citrate and fumarate). Although all cultures grew on insoluble iron, the iron precipitates interfered with protein extraction and analysis; which remains a major challenge for researchers in disparate study systems. Among the Gram (-) organisms studied, Anaeromyxobacter dehalogenans remains the most poorly characterized. Yet, it is arguably the most versatile organisms we studied. In this work we have used comparative proteomics to hypothesize which two of the dozens of predicted c-type cytochromes within Anaeromyxobacter dehalogenans may be directly involved in soluble iron reduction. Unfortunately, heterologous expression of these Anaeromyxobacter dehalogenans ctype cytochromes led to poor protein production and/or formation of inclusion bodies

Novel processes for anaerobic sulfate production from elemental sulfur by sulfate-reducing bacteria

Science.gov (United States)

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

1994-01-01

Sulfate reducers and related organisms which had previously been found to reduce Fe(III) with H2 or organic electron donors oxidized S0 to sulfate when Mn(IV) was provided as an electron acceptor. Organisms catalyzing this reaction in washed cell suspensions included Desulfovibrio desulfuricans, Desulfomicrobium baculatum. Desulfobacterium autotrophicum, Desulfuromonas acetoxidans, and Geobacter metallireducens. These organisms produced little or no sulfate from S0 with Fe(III) as a potential electron acceptor or in the absence of an electron acceptor. In detailed studies with Desulfovibrio desulfuricans, the stoichiometry of sulfate and Mn(II) production was consistent with the reaction S0 + 3 MnO2 + 4H+ ???SO42- + 3Mn(II) + 2H2O. None of the organisms evaluated could be grown with S0 as the sole electron donor and Mn(IV) as the electron acceptor. In contrast to the other sulfate reducers evaluated, Desulfobulbus propionicus produced sulfate from S0 in the absence of an electron acceptor and Fe(III) oxide stimulated sulfate production. Sulfide also accumulated in the absence of Mn(IV) or Fe(III). The stoichiometry of sulfate and sulfide production indicated that Desulfobulbus propionicus disproportionates S0 as follows: 4S0 + 4H2O???SO42- + 3HS- + 5 H+. Growth of Desulfobulbus propionicus with S0 as the electron donor and Fe(III) as a sulfide sink and/or electron acceptor was very slow. The S0 oxidation coupled to Mn(IV) reduction described here provides a potential explanation for the Mn(IV)-dependent sulfate production that previous studies have observed in anoxic marine sediments. Desulfobulbus propionicus is the first example of a pure culture known to disproportionate S0.

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

Science.gov (United States)

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

2009-05-01

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

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

Science.gov (United States)

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

2016-03-14

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

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.

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

Science.gov (United States)

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

2018-05-23

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

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

Science.gov (United States)

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

2017-05-16

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

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

International Nuclear Information System (INIS)

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

1996-01-01

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

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

DEFF Research Database (Denmark)

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

2008-01-01

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

Estimation of redox potentials of Fe(III)- gallic acid complexes at different pH by spectrophotometric titration with ascorbate

International Nuclear Information System (INIS)

Iqbal, M.; Tasneem, Z.; Kazmi, S.A.

1993-01-01

Fe(III) is strongly chelated by Gallic acid. This equilibrium as well as the kinetics of reduction of the complex is strongly pH dependent. The complex was prepared in acetate buffers of pH 4.6, 5.0 and 5.6 and in Tris buffer of pH 7.0.The complex was reduced by ascorbate. The reduced absorbance was taken to be a measure of reaction. Nernst equation was then applied to determine the standard redox potentials of the complex taking the literature values of the redox potentials of ascorbate at different pH. The values of redox potentials of complex were found to be 0.197 V at pH 4.6. 0.181 V at pH 5.0 1.132 V at pH 5.6 and 0.092 V at pH 7.0. (author)

Organic carbon and reducing conditions lead to cadmium immobilization by secondary Fe mineral formation in a pH-neutral soil.

Science.gov (United States)

Muehe, E Marie; Adaktylou, Irini J; Obst, Martin; Zeitvogel, Fabian; Behrens, Sebastian; Planer-Friedrich, Britta; Kraemer, Ute; Kappler, Andreas

2013-01-01

Cadmium (Cd) is of environmental relevance as it enters soils via Cd-containing phosphate fertilizers and endangers human health when taken up by crops. Cd is known to associate with Fe(III) (oxyhydr)oxides in pH-neutral to slightly acidic soils, though it is not well understood how the interrelation of Fe and Cd changes under Fe(III)-reducing conditions. Therefore, we investigated how the mobility of Cd changes when a Cd-bearing soil is faced with organic carbon input and reducing conditions. Using fatty acid profiles and quantitative PCR, we found that both fermenting and Fe(III)-reducing bacteria were stimulated by organic carbon-rich conditions, leading to significant Fe(III) reduction. The reduction of Fe(III) minerals was accompanied by increasing soil pH, increasing dissolved inorganic carbon, and decreasing Cd mobility. SEM-EDX mapping of soil particles showed that a minor fraction of Cd was transferred to Ca- and S-bearing minerals, probably carbonates and sulfides. Most of the Cd, however, correlated with a secondary iron mineral phase that was formed during microbial Fe(III) mineral reduction and contained mostly Fe, suggesting an iron oxide mineral such as magnetite (Fe3O4). Our data thus provide evidence that secondary Fe(II) and Fe(II)/Fe(III) mixed minerals could be a sink for Cd in soils under reducing conditions, thus decreasing the mobility of Cd in the soil.

Detoxification of Pesticide-Containing Wastewater with FeIII, Activated Carbon and Fenton Reagent and Its Control Using Three Standardized Bacterial Inhibition Tests

Directory of Open Access Journals (Sweden)

Eduard Rott

2017-12-01

Full Text Available Discharge of toxic industrial wastewaters into biological wastewater treatment plants may result in inhibition of activated sludge bacteria (ASB. In order to find an appropriate method of detoxification, the wastewater of a pesticide-processing plant in Vietnam was treated with three different methods (FeIII, powdered activated carbon (PAC, Fenton (FeII/H2O2 analyzing the detoxification effect with the nitrification inhibition test (NIT, respiration inhibition test (RIT and luminescent bacteria test (LBT. The heterotrophic ASB were much more resistant to the wastewater than the autotrophic nitrificants. The NIT turned out to be more suitable than the RIT since the NIT was less time-consuming and more reliable. In addition, the marine Aliivibrio fischeri were more sensitive than the nitrificants indicating that a lack of inhibition in the very practical and time-efficient LBT correlates with a lack of nitrification inhibition. With 95%, the Fenton method showed the highest efficiency regarding the chemical oxygen demand (COD removal. Although similar COD removal (60–65% was found for both the FeIII and the PAC method, the inhibitory effect of the wastewater was reduced much more strongly with PAC. Both the NIT and the LBT showed that the PAC and Fenton methods led to a similar reduction in the inhibitory effect.

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

Science.gov (United States)

Khaodee, Warangkhana; Aeungmaitrepirom, Wanlapa; Tuntulani, Thawatchai

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

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.

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

Directory of Open Access Journals (Sweden)

Harsasi Setyawati

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

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.

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.

Influence of Reactive Transport on the Reduction of U(VI) in the Presence of Fe(III) and Nitrate: Implications for U(VI) Immobilization by Bioremediation/Biobarriers - Final Report

International Nuclear Information System (INIS)

B.D. Wood

2007-01-01

Subsurface contamination by metals and radionuclides represent some of the most challenging remediation problems confronting the Department of Energy (DOE) complex. In situ remediation of these contaminants by dissimilatory metal reducing bacteria (DMRB) has been proposed as a potential cost effective remediation strategy. The primary focus of this research is to determine the mechanisms by which the fluxes of electron acceptors, electron donors, and other species can be controlled to maximize the transfer of reductive equivalents to the aqueous and solid phases. The proposed research is unique in the NABIR portfolio in that it focuses on (i) the role of flow and transport in the initiation of biostimulation and the successful sequestration of metals and radionuclides [specifically U(VI)], (ii) the subsequent reductive capacity and stability of the reduced sediments produced by the biostimulation process, and (iii) the potential for altering the growth of biomass in the subsurface by the addition of specific metabolic uncoupling compounds. A scientifically-based understanding of these phenomena are critical to the ability to design successful bioremediation schemes. The laboratory research will employ Shewanella putrefaciens (CN32), a facultative DMRB that can use Fe(III) oxides as a terminal electron acceptor. Sediment-packed columns will be inoculated with this organism, and the reduction of U(VI) by the DMRB will be stimulated by the addition of a carbon and energy source in the presence of Fe(III). Separate column experiments will be conducted to independently examine: (1) the importance of the abiotic reduction of U(VI) by biogenic Fe(II); (2) the influence of the transport process on Fe(III) reduction and U(VI) immobilization, with emphasis on methods for controlling the fluxes of aqueous species to maximize uranium reduction; (3) the reductive capacity of biologically-reduced sediments (with respect to re-oxidation by convective fluxes of O2 and NO3-) and

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

Shewanella putrefaciens mtrB encodes an outer membrane protein required for Fe(III) and Mn(IV) reduction.

Science.gov (United States)

Beliaev, A S; Saffarini, D A

1998-12-01

Iron and manganese oxides or oxyhydroxides are abundant transition metals, and in aquatic environments they serve as terminal electron acceptors for a large number of bacterial species. The molecular mechanisms of anaerobic metal reduction, however, are not understood. Shewanella putrefaciens is a facultative anaerobe that uses Fe(III) and Mn(IV) as terminal electron acceptors during anaerobic respiration. Transposon mutagenesis was used to generate mutants of S. putrefaciens, and one such mutant, SR-21, was analyzed in detail. Growth and enzyme assays indicated that the mutation in SR-21 resulted in loss of Fe(III) and Mn(IV) reduction but did not affect its ability to reduce other electron acceptors used by the wild type. This deficiency was due to Tn5 inactivation of an open reading frame (ORF) designated mtrB. mtrB encodes a protein of 679 amino acids and contains a signal sequence characteristic of secreted proteins. Analysis of membrane fractions of the mutant, SR-21, and wild-type cells indicated that MtrB is located on the outer membrane of S. putrefaciens. A 5.2-kb DNA fragment that contains mtrB was isolated and completely sequenced. A second ORF, designated mtrA, was found directly upstream of mtrB. The two ORFs appear to be arranged in an operon. mtrA encodes a putative 10-heme c-type cytochrome of 333 amino acids. The N-terminal sequence of MtrA contains a potential signal sequence for secretion across the cell membrane. The amino acid sequence of MtrA exhibited 34% identity to NrfB from Escherichia coli, which is involved in formate-dependent nitrite reduction. To our knowledge, this is the first report of genes encoding proteins involved in metal reduction.

Degradation of Nitrobenzene Using Bio-Reduced Fe-Clays: Progress Towards the Development of an in-situ Groundwater Remediation Technology

Science.gov (United States)

White, M. L.; Fialips, C. I.

2008-12-01

Clay minerals are widely used in agricultural, industrial and environmental engineering applications due to their specific physical and chemical properties and their high abundance in soils in sediments. Currently however, Fe-bearing clays are not widely exploited in these applied fields. Fe-rich smectites, such as nontronite, can contain up to 20wt% of Fe2O3 as structural Fe(III) and if a suitable electron donor is available, this Fe(III) can be utilized by Fe-reducing bacteria as a terminal electron acceptor. When reduced, the overall reactivity of Fe-smectites changes, particularly where interactions with water and various organic compounds are involved. For instance, the presence of reduced Fe-smectites has been found to induce the degradation of certain organic contaminants found in groundwaters and the subsurface, e.g. chlorinated aliphatics and nitroaromatic compounds. The goal of this study is to develop an in-situ groundwater remediation technology that targets redox- sensitive organics, in the form of a permeable Bio Fe-clay barrier. To achieve this, the iron-reducing bacterium Shewanella algae BrY was first used to reduce structural FeIII in <2micron fractions of the Fe- rich smectite nontronite (NAu-2, 41.74wt% Fe2O3) and a Fe-bearing montmorrillonite (Speeton Clay, Yorkshire, UK, ~8wt% Fe2O3). S. algae BrY was able to reduce structural FeIII within these clays to maximum Fe(II)/Fe(II)+Fe(III) ratios 0.34 and 0.19 for the nontronite and Speeton Clay, respectively, in the presence and absence of the electron shuttle, AQDS (9, 10-anthraquinone-2, 6-disulfonic acid). These results are novel because the capability of S. algae BrY to reduce structural Fe(III) in smectite clays has not previously been tested. Nitrobenzene was selected as the test redox-sensitive organic compound as it is a common subsurface contaminant and is of global ecotoxicological concern. To test the capability of bio- reduced Fe-clays to transform nitrobenzene to aniline (the less

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

Science.gov (United States)

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

2014-10-01

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

Integrative analysis of Geobacter spp. and sulfate-reducing bacteria during uranium bioremediation

Directory of Open Access Journals (Sweden)

D. Lovley

2012-03-01

Full Text Available Enhancing microbial U(VI reduction with the addition of organic electron donors is a promising strategy for immobilizing uranium in contaminated groundwaters, but has yet to be optimized because of a poor understanding of the factors controlling the growth of various microbial communities during bioremediation. In previous field trials in which acetate was added to the subsurface, there were two distinct phases: an initial phase in which acetate-oxidizing, U(VI-reducing Geobacter predominated and U(VI was effectively reduced and a second phase in which acetate-oxidizing sulfate reducing bacteria (SRB predominated and U(VI reduction was poor. The interaction of Geobacter and SRB was investigated both in sediment incubations that mimicked in situ bioremediation and with in silico metabolic modeling. In sediment incubations, Geobacter grew quickly but then declined in numbers as the microbially reducible Fe(III was depleted whereas the SRB grow more slowly and reached dominance after 30–40 days. Modeling predicted a similar outcome. Additional modeling in which the relative initial percentages of the Geobacter and SRB were varied indicated that there was little to no competitive interaction between Geobacter and SRB when acetate was abundant. Further simulations suggested that the addition of Fe(III would revive the Geobacter, but have little to no effect on the SRB. This result was confirmed experimentally. The results demonstrate that it is possible to predict the impact of amendments on important components of the subsurface microbial community during groundwater bioremediation. The finding that Fe(III availability, rather than competition with SRB, is the key factor limiting the activity of Geobacter during in situ uranium bioremediation will aid in the design of improved uranium bioremediation strategies.

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.

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

NARCIS (Netherlands)

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

1982-01-01

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

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

Directory of Open Access Journals (Sweden)

S Azizi

2014-05-01

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

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

Science.gov (United States)

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

2012-03-21

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

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

Science.gov (United States)

Ngwack, Bernd; Sigg, Laura

1997-03-01

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

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

Science.gov (United States)

Suhartana; Sukmasari, Emmanuella; Azmiyawati, Choiril

2018-04-01

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

Preliminary study on the photoproduction of hydroxyl radicals in aqueous solution with Aldrich humic acid, algae and Fe(III) under high-pressure mercury lamp irradiation.

Science.gov (United States)

Liu, Xianli; Xu, Dong; Wu, Feng; Liao, Zhenhuan; Liu, Jiantong; Deng, Nansheng

2004-03-01

Under a high-pressure mercury lamp (HPML) and using an exposure time of 4 h, the photoproduction of hydroxyl radicals (*OH) could be induced in an aqueous solution containing humic acid (HA). Hydroxyl radicals were determined by high-performance liquid chromatography using benzene as a probe. The results showed that *OH photoproduction increased from 1.80 to 2.74 microM by increasing the HA concentration from 10 to 40 mg L(-1) at an exposure time of 4 h (pH 6.5). Hydroxyl radical photoproduction in aqueous solutions of HA containing algae was greater than that in the aqueous solutions of HA without algae. The photoproduction of *OH in the HA solution with Fe(III) was greater than that of the solution without Fe(III) at pH ranging from 4.0 to 8.0. The photoproduction of *OH in HA solution with algae with or without Fe(III) under a 250 W HPML was greater than that under a 125 W HPML. The photoproduction of *OH in irradiated samples was influenced by the pH. The results showed that HPML exposure for 4 h in the 4-8 pH range led to the highest *OH photoproduction at pH 4.0.

Redox Reactions of Reduced Flavin Mononucleotide (FMN), Riboflavin (RBF), and Anthraquinone-2,6-disulfonate (AQDS) with Ferrihydrite and Lepidocrocite

Energy Technology Data Exchange (ETDEWEB)

Shi, Zhi [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Zachara, John M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Shi, Liang [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Wang, Zheming [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Moore, Dean A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Kennedy, David W. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Fredrickson, Jim K. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2012-09-17

Flavins are secreted by the dissimilatory iron-reducing bacterium Shewanella and can function as endogenous electron transfer mediators (ETM). In order to assess the potential importance of flavins in Fe(III) bioreduction, we investigated the redox reaction kinetics of reduced flavins (FMNH2 and RBFH2) with ferrihydrite and lepidocrocite. The organic reductants rapidly reduced and dissolved ferrihydrite and lepidocrocite in the pH range 4-8. The rate constant k for 2-line ferrihydrite reductive dissolution by FMNH2 was 87.5 ± 3.5 M-1∙s-1 at pH 7.0 in batch reactors, and the k was similar for RBFH2. For lepidocrocite, the k was 500 ± 61 M-1∙s-1 for FMNH2, and 236 ± 22 M-1∙s-1 for RBFH2. The surface area normalized initial reaction rates (ra) were between 0.08 and 77 μmoles∙m-2∙s-1 for various conditions in stopped-flow experiments. Initial rates (ro) were first-order with respect to Fe(III) oxide concentration, and ra increased with decreasing pH. Poorly crystalline 2-line ferrihydrite yielded the highest ra, followed by more crystalline 6-line ferrihydrite, and crystalline lepidocrocite. Compared to a previous whole-cell study with Shewanella oneidensis strain MR-1, our findings suggest that ETM reduction by the Mtr pathway coupled to lactate oxidation are rate limiting, rather than heterogeneous electron transfer to the Fe(III) oxide.

Novel mode of microbial energy metabolism: organic carbon oxidation coupled to dissimilatory reduction of iron or manganese.

Science.gov (United States)

Lovley, D R; Phillips, E J

1988-06-01

A dissimilatory Fe(III)- and Mn(IV)-reducing microorganism was isolated from freshwater sediments of the Potomac River, Maryland. The isolate, designated GS-15, grew in defined anaerobic medium with acetate as the sole electron donor and Fe(III), Mn(IV), or nitrate as the sole electron acceptor. GS-15 oxidized acetate to carbon dioxide with the concomitant reduction of amorphic Fe(III) oxide to magnetite (Fe(3)O(4)). When Fe(III) citrate replaced amorphic Fe(III) oxide as the electron acceptor, GS-15 grew faster and reduced all of the added Fe(III) to Fe(II). GS-15 reduced a natural amorphic Fe(III) oxide but did not significantly reduce highly crystalline Fe(III) forms. Fe(III) was reduced optimally at pH 6.7 to 7 and at 30 to 35 degrees C. Ethanol, butyrate, and propionate could also serve as electron donors for Fe(III) reduction. A variety of other organic compounds and hydrogen could not. MnO(2) was completely reduced to Mn(II), which precipitated as rhodochrosite (MnCO(3)). Nitrate was reduced to ammonia. Oxygen could not serve as an electron acceptor, and it inhibited growth with the other electron acceptors. This is the first demonstration that microorganisms can completely oxidize organic compounds with Fe(III) or Mn(IV) as the sole electron acceptor and that oxidation of organic matter coupled to dissimilatory Fe(III) or Mn(IV) reduction can yield energy for microbial growth. GS-15 provides a model for how enzymatically catalyzed reactions can be quantitatively significant mechanisms for the reduction of iron and manganese in anaerobic environments.

SPECTROPHOTOMETRIC ASSESSMENT OF FERRIC REDUCING POWER OF THE INSTANT COFFEE

OpenAIRE

Tsiupko, T. G.; Tishchenko, E. A.; Voronova, O. B.

2016-01-01

The methods of antioxidant activity determination of foodstuffs using different indicator systems were discussed. The investigation of ferric reducing power (FRP) of coffee and its individual phenolic components such as chlorogenic (CGA), caffeic (СА), ferulic (FA), gallic (GA), vanillic (VA), protocatechuic (PCA) and uric (UA) acids as well as quercetin (Qu) and catechol (C) using the spectrophotometric method with Fe(III) - o-Phen indicator system was carried out. It was shown that the sens...

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

International Nuclear Information System (INIS)

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

1998-01-01

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

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

International Nuclear Information System (INIS)

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

1980-01-01

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

Importance of different physiological groups of iron reducing microorganisms in an acidic mining lake remediation experiment.

Science.gov (United States)

Porsch, Katharina; Meier, Jutta; Kleinsteuber, Sabine; Wendt-Potthoff, Katrin

2009-05-01

Iron- and sulfate-reducing microorganisms play an important role for alkalinity-generating processes in mining lakes with low pH. In the acidic mining lake 111 in Lusatia, Germany, a passive in situ remediation method was tested in a large scale experiment, in which microbial iron and sulfate reduction are stimulated by addition of Carbokalk (a mixture of the nonsugar compounds of sugar beets and lime) and straw. The treated surface sediment consisted of three layers of different pH and geochemical composition. The top layer was acidic and rich in Fe(III), the second and third layer both showed moderately acidic to circum-neutral pH values, but only the second was rich in organics, strongly reduced and sulfidic. Aim of the study was to elucidate the relative importance of neutrophilic heterotrophic, acidophilic heterotrophic, and acidophilic autotrophic iron-reducing microorganisms in each of the three layers. In order to distinguish between them, the effect of their respective characteristic electron donors acetate, glucose, and elemental sulfur on potential iron reduction rates was investigated. Limitation of iron reduction by the availability of Fe(III) was revealed by the addition of Fe(OH)(3). The three groups of iron-reducing microorganisms were quantified by most probable number (MPN) technique and their community composition was analyzed by cloning and sequencing of 16S rRNA genes. In the acidic surface layer, none of the three electron donors stimulated iron reduction; acetate even had an inhibiting effect. In agreement with this, no decrease of the added electron donors was observed. Iron reduction rates were low in comparison to the other layers. Iron reduction in layers 2 and 3 was enhanced by glucose and acetate, accompanied by a decrease of these electron donors. Addition of elemental sulfur did not enhance iron reduction in either layer. Layer 2 exhibited the highest iron reduction rate (4.08 mmol dm(-3) d(-1)) and the highest cell numbers in MPN

Transformation impacts of dissolved and solid phase Fe(II) on trichloroethylene (TCE) reduction in an iron-reducing bacteria (IRB) mixed column system: a mathematical model.

Science.gov (United States)

Bae, Yeunook; Kim, Dooil; Cho, Hyun-Hee; Singhal, Naresh; Park, Jae-Woo

2012-12-01

In this research, we conducted trichloroethylene (TCE) reduction in a column filled with iron and iron-reducing bacteria (IRB) and developed a mathematical model to investigate the critical reactions between active species in iron/IRB/contaminant systems. The formation of ferrous iron (Fe(II)) in this system with IRB and zero-valent iron (ZVI, Fe(0)) coated with a ferric iron (Fe(III)) crust significantly affected TCE reduction and IRB respiration in various ways. This study presents a new framework for transformation property and reducing ability of both dissolved (Fe(II)(dissolved)) and solid form ferrous iron (Fe(II)(solid)). Results showed that TCE reduction was strongly depressed by Fe(II)(solid) rather than by other inhibitors (e.g., Fe(III) and lactate), suggesting that Fe(II)(solid) might reduce IRB activation due to attachment to IRB cells. Newly exposed Fe(0) from the released Fe(II)(dissolved) was a strong contributor to TCE reduction compared to Fe(II)(solid). In addition, our research confirmed that less Fe(II)(solid) production strongly supported long-term TCE reduction because it may create an easier TCE approach to Fe(0) or increase IRB growth. Our findings will aid the understanding of the contributions of iron media (e.g., Fe(II)(solid), Fe(II)(dissolved), Fe(III), and Fe(0)) to IRB for decontamination in natural groundwater systems. Copyright © 2012 Elsevier Ltd. All rights reserved.

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

Science.gov (United States)

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

2012-02-01

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

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

Science.gov (United States)

Schönherr, Jörg; Fernández, Victoria; Schreiber, Lukas

2005-06-01

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

Sediment studies of the biological factors controlling the reduction of U(VI)

International Nuclear Information System (INIS)

Lovley, Derek R.

2004-01-01

Studies were conducted primarily with sediments, both in laboratory incubations and in a field experiment, with supporting studies with pure cultures. To our knowledge the sediment studies were the first on microbial U(VI) reduction in actual uranium-contaminated subsurface sediments, under conditions that mimic those found in situ. Important findings included: (1) U(VI) reduction is a biotic process in subsurface sediments. (2) U(VI) reduction can be stimulated most effectively with the addition of acetate. Although it had been speculated that microbial U(VI) reduction might be capable of this type of environmental remediation ever since the discovery of microbial U(VI) reduction, this had not been previously demonstrated under environmentally relevant conditions. (3) U(VI) is reduced concurrently with Fe(III) and prior to sulfate reduction. U(VI) and Fe(III) reduction proceeded concurrently, accompanied by a dramatic enrichment in organisms in the Geobacteraceae. Sulfate-reducing microorganisms do not appear to be important components of the microbial community reducing U(VI) in these subsurface sediments. (4) Nitrate has important influences on U(VI) reduction. Nitrate inhibits the reduction of metals until nitrate is depleted. Fe(III)-reducing microorganisms such as Geobacter metallireducens and Desulfitobacterium species can oxidize Fe(II) with the reduction of nitrate which is an important consideration because our previous studies have demonstrated that freshly precipitated Fe(III) oxides can reoxidize U(IV) to U(VI). The discovery that G. metallireducens can ''run backwards'' and oxidize U(IV) when nitrate is present reveals another mechanism preventing precipitation of U(IV) in the presence of nitrate as well as potential novel strategy for removing uranium from the subsurface after a site has been remediated. (5) Importance of understanding Fe(III) forms available for microbial reduction. Fe(III) is orders of magnitude more abundant than U(VI) as an

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

Science.gov (United States)

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

2010-05-01

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

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

Science.gov (United States)

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

2016-09-14

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

Comparative Proteomic Analysis of Desulfotomaculum reducens MI-1: Insights into the Metabolic Versatility of a Gram-positive Sulfate and Metal-reducing Bacterium

Directory of Open Access Journals (Sweden)

Anne Elyse Otwell

2016-02-01

Full Text Available The proteomes of the metabolically versatile and poorly characterized Gram-positive bacterium Desulfotomaculum reducens MI-1 were compared across four cultivation conditions including sulfate reduction, soluble Fe(III reduction, insoluble Fe(III reduction, and pyruvate fermentation. Collectively across conditions, we observed at high confidence ~38% of genome-encoded proteins. Here, we focus on proteins that display significant differential abundance on conditions tested. To the best of our knowledge, this is the first full-proteome study focused on a Gram-positive organism grown either on sulfate or metal-reducing conditions. Several proteins with uncharacterized function encoded within heterodisulfide reductase (hdr-containing loci were upregulated on either sulfate (Dred_0633-4, Dred_0689-90, and Dred_1325-30 or Fe(III-citrate-reducing conditions (Dred_0432-3 and Dred_1778-84. Two of these hdr-containing loci display homology to recently described flavin-based electron bifurcation (FBEB pathways (Dred_1325-30 and Dred_1778-84. Additionally, we propose that a cluster of proteins, which is homologous to a described FBEB lactate dehydrogenase (LDH complex, is performing lactate oxidation in D. reducens (Dred_0367-9. Analysis of the putative sulfate reduction machinery in D. reducens revealed that most of these proteins are constitutively expressed across cultivation conditions tested. In addition, peptides from the single multiheme c-type cytochrome (MHC in the genome were exclusively observed on the insoluble Fe(III condition, suggesting that this MHC may play a role in reduction of insoluble metals.

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

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

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.

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

International Nuclear Information System (INIS)

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

2002-01-01

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

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

Science.gov (United States)

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

2016-03-15

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

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

Concurrent nitrate and Fe(III) reduction during anaerobic biodegradation of phenols in a sandstone aquifer

DEFF Research Database (Denmark)

Broholm, Mette; Crouzet, C.; Arvin, Erik

2000-01-01

The biodegradation of phenols (similar to 5, 60, 600 mg 1(-1)) under anaerobic conditions (nitrate enriched and unamended) was studied in laboratory microcosms with sandstone material and groundwater from within an anaerobic ammonium plume in an aquifer, The aqueous phase was sampled and analyzed...... for phenols and selected redox sensitive parameters on a regular basis. An experiment with sandstone material from specific depth intervals from a vertical profile across the ammonium plume was also conducted. The miniature microcosms used in this experiment were sacrificed for sampling for phenols...... and selected redox sensitive parameters at the end of the experiment. The sandstone material was characterized with respect to oxidation and reduction potential and Fe(II) and Fe(III) speciation prior to use for all microcosms and at the end of the experiments for selected microcosms. The redox conditions...

Isolation of Geobacter species from diverse sedimentary environments

Science.gov (United States)

Coaxes, J.D.; Phillips, E.J.P.; Lonergan, D.J.; Jenter, H.; Lovley, D.R.

1996-01-01

In an attempt to better understand the microorganisms responsible for Fe(III) reduction in sedimentary environments, Fe(III)-reducing microorganisms were enriched for and isolated from freshwater aquatic sediments, a pristine deep aquifer, and a petroleum-contaminated shallow aquifer. Enrichments were initiated with acetate or toluene as the electron donor and Fe(III) as the electron acceptor. Isolations were made with acetate or benzoate. Five new strains which could obtain energy for growth by dissimilatory Fe(III) reduction were isolated. All five isolates are gram- negative strict anaerobes which grow with acetate as the electron donor and Fe(III) as the electron acceptor. Analysis of the 16S rRNA sequence of the isolated organisms demonstrated that they all belonged to the genus Geobacter in the delta subdivision of the Proteobacteria. Unlike the type strain, Geobacter metallireducens, three of the five isolates could use H2 as an electron donor fur Fe(III) reduction. The deep subsurface isolate is the first Fe(III) reducer shown to completely oxidize lactate to carbon dioxide, while one of the freshwater sediment isolates is only the second Fe(III) reducer known that can oxidize toluene. The isolation of these organisms demonstrates that Geobacter species are widely distributed in a diversity of sedimentary environments in which Fe(III) reduction is an important process.

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

Beam-induced redox transformation of arsenic during As K-edge XAS measurements: availability of reducing or oxidizing agents and As speciation.

Science.gov (United States)

Han, Young Soo; Jeong, Hoon Young; Hyun, Sung Pil; Hayes, Kim F; Chon, Chul Min

2018-05-01

During X-ray absorption spectroscopy (XAS) measurements of arsenic (As), beam-induced redox transformation is often observed. In this study, the As species immobilized by poorly crystallized mackinawite (FeS) was assessed for the susceptibility to beam-induced redox reactions as a function of sample properties including the redox state of FeS and the solid-phase As speciation. The beam-induced oxidation of reduced As species was found to be mediated by the atmospheric O 2 and the oxidation products of FeS [e.g. Fe(III) (oxyhydr)oxides and intermediate sulfurs]. Regardless of the redox state of FeS, both arsenic sulfide and surface-complexed As(III) readily underwent the photo-oxidation upon exposure to the atmospheric O 2 during XAS measurements. With strict O 2 exclusion, however, both As(0) and arsenic sulfide were less prone to the photo-oxidation by Fe(III) (oxyhydr)oxides than NaAsO 2 and/or surface-complexed As(III). In case of unaerated As(V)-reacted FeS samples, surface-complexed As(V) was photocatalytically reduced during XAS measurements, but arsenic sulfide did not undergo the photo-reduction.

Orenia metallireducens sp. nov. Strain Z6, a Novel Metal-Reducing Member of the Phylum Firmicutes from the Deep Subsurface

Science.gov (United States)

Sanford, Robert A.; Boyanov, Maxim I.; Kemner, Kenneth M.; O'Loughlin, Edward J.; Chang, Yun-juan; Locke, Randall A.; Weber, Joseph R.; Egan, Sheila M.; Mackie, Roderick I.; Cann, Isaac; Fouke, Bruce W.

2016-01-01

ABSTRACT A novel halophilic and metal-reducing bacterium, Orenia metallireducens strain Z6, was isolated from briny groundwater extracted from a 2.02 km-deep borehole in the Illinois Basin, IL. This organism shared 96% 16S rRNA gene similarity with Orenia marismortui but demonstrated physiological properties previously unknown for this genus. In addition to exhibiting a fermentative metabolism typical of the genus Orenia, strain Z6 reduces various metal oxides [Fe(III), Mn(IV), Co(III), and Cr(VI)], using H2 as the electron donor. Strain Z6 actively reduced ferrihydrite over broad ranges of pH (6 to 9.6), salinity (0.4 to 3.5 M NaCl), and temperature (20 to 60°C). At pH 6.5, strain Z6 also reduced more crystalline iron oxides, such as lepidocrocite (γ-FeOOH), goethite (α-FeOOH), and hematite (α-Fe2O3). Analysis of X-ray absorption fine structure (XAFS) following Fe(III) reduction by strain Z6 revealed spectra from ferrous secondary mineral phases consistent with the precipitation of vivianite [Fe3(PO4)2] and siderite (FeCO3). The draft genome assembled for strain Z6 is 3.47 Mb in size and contains 3,269 protein-coding genes. Unlike the well-understood iron-reducing Shewanella and Geobacter species, this organism lacks the c-type cytochromes for typical Fe(III) reduction. Strain Z6 represents the first bacterial species in the genus Orenia (order Halanaerobiales) reported to reduce ferric iron minerals and other metal oxides. This microbe expands both the phylogenetic and physiological scopes of iron-reducing microorganisms known to inhabit the deep subsurface and suggests new mechanisms for microbial iron reduction. These distinctions from other Orenia spp. support the designation of strain Z6 as a new species, Orenia metallireducens sp. nov. IMPORTANCE A novel iron-reducing species, Orenia metallireducens sp. nov., strain Z6, was isolated from groundwater collected from a geological formation located 2.02 km below land surface in the Illinois Basin, USA

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

International Nuclear Information System (INIS)

Elrahman, Azza Mohamed

2000-01-01

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

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

International Nuclear Information System (INIS)

Gurkan, R.; Altunay, N.

2013-01-01

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

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.

Microbial Mn(IV) and Fe(III) reduction in northern Barents Sea sediments under different conditions of ice cover and organic carbon deposition

DEFF Research Database (Denmark)

Nickel, Maren; Vandieken, Verona; Brüchert, Volker

2008-01-01

station, with seasonally extended ice cover, low organic carbon content and sedimentation rate combined with relatively high concentrations of Mn and Fe(III) oxides favored dissimilatory Fe and Mn reduction (98% of anaerobic carbon oxidation) over sulfate reduction in the top 12 cm of the sediment....... In contrast, in a sediment that had not been ice covered for at least 12 months and with more organic carbon and a higher sedimentation rate, sulfate reduction was the most important anaerobic electron-accepting process (>80% of anaerobic carbon oxidation). In the upper 3 cm, microbial Fe and sulfate...

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

Science.gov (United States)

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

2006-11-01

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

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

Science.gov (United States)

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

2017-09-01

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

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

International Nuclear Information System (INIS)

Sivaraman, Gandhi; Sathiyaraja, Vijayaraj; Chellappa, Duraisamy

2014-01-01

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

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.

Purification of Anthocyanins with o-Dihydroxy Arrangement by Sorption in Cationic Resins Charged with Fe(III

Directory of Open Access Journals (Sweden)

Araceli Castañeda-Ovando

2014-01-01

Full Text Available In the present work, a new purification method of anthocyanins with o-dihydroxy arrangement is proposed. This method is based on a ligand-exchange mechanism, using a cationic exchange resin loaded with metallic ions in order to increase the affinity of the resin to the anthocyanin(s with o-dihydroxy arrangement. This method was used to purify the main anthocyanin (cyanidin-3-glucoside; Cy-3-glc from the anthocyanic methanolic extract of blue corn. The best sorption result was using Fe(III in its ion form. The purification procedure begins with the formation of a metal-anthocyanin complex (Cy-3-glc-Fe which was optimal at pH 5, followed by a NaOH 0.1 M elution process in order to eliminate anthocyanins without o-dihydroxy arrangement, sugars, and organic acids. Finally, the pure anthocyanin is obtained by adding HCl 0.1 M which breaks the metal-anthocyanin complex.

Porphyromonas endodontalis binds, reduces and grows on human hemoglobin.

Science.gov (United States)

Zerr, M; Drake, D; Johnson, W; Cox, C D

2001-08-01

Porphyromonas endodontalis is a black-pigmented, obligate anaerobic rod-shaped bacterium implicated as playing a major role in endodontic infections. We have previously shown that P. endodontalis requires the porphyrin nucleus, preferably supplied as hemoglobin, as a growth supplement. The bacteria also actively transport free iron, although this activity does not support growth in the absence of a porphyrin source. The purpose of this study was to further investigate the binding and subsequent utilization of human hemoglobin by P. endodontalis. P. endodontalis binds hemoglobin and reduces the Fe(III) porphyrin, resulting in a steady accumulation of ferrous hemoglobin. Reduction of methemoglobin was similar to the extracellular reduction of nitrobluetetrazolium in the presence of oxidizable substrate. Turbidimetric and viable cell determinations showed that P. endodontalis grew when supplied only hemoglobin. Therefore, we conclude that hemoglobin appears to serve as a sole carbon and nitrogen source, and that these bacteria reduce extracellular compounds at the expense of oxidized substrates.

Interaction of selenite with reduced Fe and/or S species: An XRD and XAS study.

Science.gov (United States)

Finck, Nicolas; Dardenne, Kathy

2016-05-01

In this study, we investigated the interaction between selenite and either Fe((II))aq or S((-II))aq in solution, and the results were used to investigate the interaction between Se((IV))aq and FeS in suspension. The reaction products were characterized by a combination of methods (SEM, XRD and XAS) and the reaction mechanisms were identified. In a first experiment, Se((IV))aq was reduced to Se((0)) by interaction with Fe((II))aq which was oxidized to Fe((III)), but the reaction was only partial. Subsequently, some Fe((III)) produced akaganeite (β-FeOOH) and the release of proton during that reaction decreased the pH. The pH decrease changed the Se speciation in solution which hindered further Se((IV)) reduction by Fe((II))aq. In a second experiment, Se((IV))aq was quantitatively reduced to Se((0)) by S((-II))aq and the reaction was fast. Two sulfide species were needed to reduce one Se((IV)), and the observed pH increase was due to a proton consumption. For both experiments, experimental results are consistent with expectations based on the oxidation reduction potential of the various species. Upon interaction with FeS, Se((IV))aq was reduced to Se((0)) and minute amounts of pyrite were detected, a consequence of partial mackinawite oxidation at surface sulfur sites. These results are of prime importance with respect to safe deep disposal of nuclear waste which contains the long-lived radionuclide (79)Se. This study shows that after release of (79)Se((IV)) upon nuclear waste matrix corrosion, selenite can be reduced in the near field to low soluble Se((0)) by interaction with Fe((II))aq and/or S((-II))aq species. Because the solubility of Se((0)) species is significantly lower than that of Se((IV)), selenium will become much less (bio)available and its migration out of deep HLW repositories may be drastically hindered. Copyright © 2016. Published by Elsevier B.V.

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

International Nuclear Information System (INIS)

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

2013-01-01

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

Ferrihydrite-associated organic matter (OM stimulates reduction by Shewanella oneidensis MR-1 and a complex microbial consortia

Directory of Open Access Journals (Sweden)

R. E. Cooper

2017-11-01

Full Text Available The formation of Fe(III oxides in natural environments occurs in the presence of natural organic matter (OM, resulting in the formation of OM–mineral complexes that form through adsorption or coprecipitation processes. Thus, microbial Fe(III reduction in natural environments most often occurs in the presence of OM–mineral complexes rather than pure Fe(III minerals. This study investigated to what extent does the content of adsorbed or coprecipitated OM on ferrihydrite influence the rate of Fe(III reduction by Shewanella oneidensis MR-1, a model Fe(III-reducing microorganism, in comparison to a microbial consortium extracted from the acidic, Fe-rich Schlöppnerbrunnen fen. We found that increased OM content led to increased rates of microbial Fe(III reduction by S. oneidensis MR-1 in contrast to earlier findings with the model organism Geobacter bremensis. Ferrihydrite–OM coprecipitates were reduced slightly faster than ferrihydrites with adsorbed OM. Surprisingly, the complex microbial consortia stimulated by a mixture of electrons donors (lactate, acetate, and glucose mimics S. oneidensis under the same experimental Fe(III-reducing conditions suggesting similar mechanisms of electron transfer whether or not the OM is adsorbed or coprecipitated to the mineral surfaces. We also followed potential shifts of the microbial community during the incubation via 16S rRNA gene sequence analyses to determine variations due to the presence of adsorbed or coprecipitated OM–ferrihydrite complexes in contrast to pure ferrihydrite. Community profile analyses showed no enrichment of typical model Fe(III-reducing bacteria, such as Shewanella or Geobacter sp., but an enrichment of fermenters (e.g., Enterobacteria during pure ferrihydrite incubations which are known to use Fe(III as an electron sink. Instead, OM–mineral complexes favored the enrichment of microbes including Desulfobacteria and Pelosinus sp., both of which can utilize lactate and

Ferrihydrite-associated organic matter (OM) stimulates reduction by Shewanella oneidensis MR-1 and a complex microbial consortia

Science.gov (United States)

Cooper, Rebecca Elizabeth; Eusterhues, Karin; Wegner, Carl-Eric; Totsche, Kai Uwe; Küsel, Kirsten

2017-11-01

The formation of Fe(III) oxides in natural environments occurs in the presence of natural organic matter (OM), resulting in the formation of OM-mineral complexes that form through adsorption or coprecipitation processes. Thus, microbial Fe(III) reduction in natural environments most often occurs in the presence of OM-mineral complexes rather than pure Fe(III) minerals. This study investigated to what extent does the content of adsorbed or coprecipitated OM on ferrihydrite influence the rate of Fe(III) reduction by Shewanella oneidensis MR-1, a model Fe(III)-reducing microorganism, in comparison to a microbial consortium extracted from the acidic, Fe-rich Schlöppnerbrunnen fen. We found that increased OM content led to increased rates of microbial Fe(III) reduction by S. oneidensis MR-1 in contrast to earlier findings with the model organism Geobacter bremensis. Ferrihydrite-OM coprecipitates were reduced slightly faster than ferrihydrites with adsorbed OM. Surprisingly, the complex microbial consortia stimulated by a mixture of electrons donors (lactate, acetate, and glucose) mimics S. oneidensis under the same experimental Fe(III)-reducing conditions suggesting similar mechanisms of electron transfer whether or not the OM is adsorbed or coprecipitated to the mineral surfaces. We also followed potential shifts of the microbial community during the incubation via 16S rRNA gene sequence analyses to determine variations due to the presence of adsorbed or coprecipitated OM-ferrihydrite complexes in contrast to pure ferrihydrite. Community profile analyses showed no enrichment of typical model Fe(III)-reducing bacteria, such as Shewanella or Geobacter sp., but an enrichment of fermenters (e.g., Enterobacteria) during pure ferrihydrite incubations which are known to use Fe(III) as an electron sink. Instead, OM-mineral complexes favored the enrichment of microbes including Desulfobacteria and Pelosinus sp., both of which can utilize lactate and acetate as an electron

Synthesis, Structural Characterization and Antimicrobial Activity of Cu(II and Fe(III Complexes Incorporating Azo-Azomethine Ligand

Directory of Open Access Journals (Sweden)

Mohammad Azam

2018-04-01

Full Text Available We are reporting a novel azo-azomethine ligand, HL and its complexes with Cu(II and Fe(III ions. The ligand and its complexes are characterized by various physico-chemical techniques using C,H,N analyses, FT-IR, 1H-NMR, ESI-MS and UV-Vis studies. TGA analyses reveal complexes are sufficiently stable and undergo two-step degradation processes. The redox behavior of the complexes was evaluated by cyclic voltammetry. Furthermore, the ligand and its complexes were tested for antimicrobial activity against bacterial and fungal strains by determining inhibition zone, minimal inhibitory concentration (MIC and minimal bactericidal concentration (MBC. The complexes showed moderate antimicrobial activity when tested against Gram +ve and Gram −ve bacterial strains. To obtain insights into the structure of ligand, DFT studies are recorded. The results obtained are quite close to the experimental results. In addition, the energy gap, chemical hardness, softness, electronegativity, electrophilic index and chemical potential were calculated using HOMO, LUMO energy value of ligand.

Reoxidation of Bioreduced Uranium Under Reducing Conditions

International Nuclear Information System (INIS)

Wan, Jiamin; Tokunaga, Tetsu K.; Brodie, Eoin; Wang, Zheming; Zheng, Zuoping; Herman, Don; Hazen, Terry C.; Firestone, Mary K.; Sutton, Steven R.

2005-01-01

Uranium mining and processing for nuclear weapons and fuel have left thousands of sites with toxic levels of this actinide in soil and ground water. An emerging strategy for remediating such environments involves using organic carbon to promote microbially-mediated reduction and precipitation of insoluble U(IV) minerals. Although previous U bioreduction studies have shown promising results, they were of short duration (up to a few months). Our longer-term (20 months) laboratory study using historically contaminated sediment has alarmingly shown that microbial reduction of U was transient even under reducing (methanogenic) conditions. Uranium was reductively immobilized during the first 100 days, but later (150 to 600 days) reoxidized and mobilized, although a microbial community capable of reducing U(VI) remained through the end of the experiment. The formation of Ca2UO2(CO3)3 complexes (caused by the elevated carbonate concentration from microbial respiration and presence of calcium) drove the U(IV)/U(VI) reduction potential to much more reducing conditions. Fe(III) and Mn(IV) were found to be likely terminal electron acceptors (TEAs) for U reoxidation. Thus, U remediation by organic carbon based reductive precipitation is not sustainable in calcareous, neutral to alkaline soils and ground waters

Controls on Fe reduction and mineral formation by a subsurface bacterium

Science.gov (United States)

Glasauer, Susan; Weidler, Peter G.; Langley, Sean; Beveridge, Terry J.

2003-04-01

The reductive dissolution of FeIII (hydr)oxides by dissimilatory iron-reducing bacteria (DIRB) could have a large impact on sediment genesis and Fe transport. If DIRB are able to reduce FeIII in minerals of high structural order to carry out anaerobic respiration, their range could encompass virtually every O 2-free environment containing FeIII and adequate conditions for cell growth. Previous studies have established that Shewanella putrefaciens CN32, a known DIRB, will reduce crystalline Fe oxides when initially grown at high densities in a nutrient-rich broth, conditions that poorly model the environments where CN32 is found. By contrast, we grew CN32 by batch culture solely in a minimal growth medium. The stringent conditions imposed by the growth method better represent the conditions that cells are likely to encounter in their natural habitat. Furthermore, the expression of reductases necessary to carry out dissimilatory Fe reduction depends on the method of growth. It was found that under anaerobic conditions CN32 reduced hydrous ferric oxide (HFO), a poorly crystalline FeIII mineral, and did not reduce suspensions containing 4 mM FeIII in the form of poorly ordered nanometer-sized goethite (α-FeOOH), well-ordered micron-sized goethite, or nanometer-sized hematite (α-Fe 2O 3) crystallites. Transmission electron microscopy (TEM) showed that all minerals but the micron-sized goethite attached extensively to the bacteria and appeared to penetrate the outer cellular membrane. In the treatment with HFO, new FeII and FeIII minerals formed during reduction of HFO-Fe in culture medium containing 4.0 mmol/L P i (soluble inorganic P), as observed by TEM with energy-dispersive X-ray spectroscopy, selected area electron diffraction, and X-ray diffraction. The minerals included magnetite (Fe 3O 4), goethite, green rust, and vivianite [Fe 3(PO 4) 2 · 8H 2O]. Vivianite appeared to be the stable end product and the mean coherence length was influenced by the rate of FeIII

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.

Voltammetric determination of total dissolved iron in coastal waters using a glassy carbon electrode modified with reduced graphene oxide, Methylene Blue and gold nanoparticles

International Nuclear Information System (INIS)

Lin, Mingyue; Zhang, Haiyun; Han, Haitao; Pan, Dawei; Su, Zhencui

2015-01-01

A nanocomposite, prepared from reduced graphene oxide (rGO), Methylene Blue (MB) and gold nanoparticles (AuNPs), was used to modify a glassy carbon electrode for the determination of total dissolved iron by differential pulse voltammetry. The use of rGO warrants a larger electrode surface and the presence of more active sites, while electron transfer is accelerated by incorporating AuNPs. MB acts as an electron mediator, as an anchor for the AuNPs (which were grown in situ), and also prevents the aggregation of rGO. The modified electrode displayed a remarkably improved sensitivity and selectivity for Fe(III). The kinetics of the electrode reaction is adsorption-controlled, and the reversible process involves one proton and one electron. The response to Fe(III) is linear in the 0.3 to 100 μM concentration range, and the detection limit is 15 nM. Possible interferences by other ions were studied. The electrode was successfully applied to the determination of total dissolved iron in real coastal waters. (author)

Periplasmic Cytochrome c(3) of Desulfovibrio vulgaris Is Directly Involved in H2-Mediated Metal but Not Sulfate Reduction

International Nuclear Information System (INIS)

Elias, Dwayne A.; Suflita, Joseph M.; McInerney, Michael J.; Krumholz, Lee R.

2004-01-01

Kinetic parameters and the role of cytochrome c3 in sulfate, Fe(III), and U(VI) reduction were investigated in Desulfovibrio vulgaris Hildenborough. While sulfate reduction followed Michaelis-Menten kinetics (Km 220 uM), loss of Fe(III) and U(VI) was first-order at all concentrations tested. Initial reduction rates of all electron acceptors were similar for cells grown with H2 and sulfate, while cultures grown using lactate and sulfate had similar rates of metal loss but lower sulfate reduction activities. The similarities in metal, but not sulfate, reduction with H2 and lactate suggest divergent pathways. Respiration assays and reduced minus oxidized spectra were carried out to determine c-type cytochrome involvement in electron acceptor reduction. c-type cytochrome oxidation was immediate with Fe(III) and U(VI) in the presence of H2, lactate, or pyruvate. Sulfidogenesis occurred with all three electron donors and effectively oxidized the c-type cytochrome in lactate or pyruvate-reduced, but not H2-reduced cells. Correspondingly, electron acceptor competition assays with lactate or pyruvate as electron donors showed that Fe(III) inhibited U(VI) reduction, and U(VI) inhibited sulfate loss. However, sulfate reduction was slowed but not halted when H2 was the electron donor in the presence of Fe(III) or U(VI). U(VI) loss was still impeded by Fe(III) when H2 was used. Hence, we propose a modified pathway for the reduction of sulfate, Fe(III), and U(VI) which helps explain why these bacteria cannot grow using these metals. We further propose that cytochrome c3 is an electron carrier involved in lactate and pyruvate oxidation and is the reductase for alternate electron acceptors with higher redox potentials than sulfate

The nature of the exchange coupling between high-spin Fe(III) heme o3 and CuBII in Escherichia coli quinol oxidase, cytochrome bo3: MCD and EPR studies.

Science.gov (United States)

Cheesman, Myles R; Oganesyan, Vasily S; Watmough, Nicholas J; Butler, Clive S; Thomson, Andrew J

2004-04-07

Fully oxidized cytochrome bo3 from Escherichia coli has been studied in its oxidized and several ligand-bound forms using electron paramagnetic resonance (EPR) and magnetic circular dichroism (MCD) spectroscopies. In each form, the spin-coupled high-spin Fe(III) heme o3 and CuB(II) ion at the active site give rise to similar fast-relaxing broad features in the dual-mode X-band EPR spectra. Simulations of dual-mode spectra are presented which show that this EPR can arise only from a dinuclear site in which the metal ions are weakly coupled by an anisotropic exchange interaction of J 1 cm-1. A variable-temperature and magnetic field (VTVF) MCD study is also presented for the cytochrome bo3 fluoride and azide derivatives. New methods are used to extract the contribution to the MCD of the spin-coupled active site in the presence of strong transitions from low-spin Fe(III) heme b. Analysis of the MCD data, independent of the EPR study, also shows that the spin-coupling within the active site is weak with J approximately 1 cm-1. These conclusions overturn a long-held view that such EPR signals in bovine cytochrome c oxidase arise from an S' = 2 ground state resulting from strong exchange coupling (J > 10(2) cm-1) within the active site.

Heterogeneous biomimetic catalysis using iron porphyrin for cyclohexane oxidation promoted by chitosan

Science.gov (United States)

Huang, Guan; Liu, Yao; Cai, Jing Li; Chen, Xiang Feng; Zhao, Shu Kai; Guo, Yong An; Wei, Su Juan; Li, Xu

2017-04-01

This study investigates how ligands modulate metalloporphyrin activity with the goal of producing a practical biomimetic catalyst for use in the chemical industry. We immobilized iron porphyrinate [iron-tetrakis-(4-sulfonatophenyl)-porphyrin; Fe(III) (TPPS)] on powdered chitosan (pd-CTS) to form an immobilized catalyst Fe(III) (TPPS)/pd-CTS, which was characterized using modern spectroscopic techniques and used for catalytic oxidation of cyclohexane with O2. Amino coordination to iron porphyrin in Fe(III) (TPPS)/pd-CTS altered the electron cloud density around the iron cation, probably by reducing the activation energy of Fe(III) (TPPS) and raising the reactivity of the iron ion catalytic center, thereby improving the catalytic efficiency. One milligram of Fe(III) (TPPS) catalyst can be reused three times for the oxidation reaction to yield an average of 22.9 mol% of cyclohexanone and cyclohexanol.

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

Science.gov (United States)

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

2013-01-01

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

Influence of Ni(II) and Fe(III) complexes of 1,2 dihydroxy 9,10 anthraquinone on the modification in calf thymus DNA upon gamma irradiation

International Nuclear Information System (INIS)

Das, Saurabh; Mandal, Parikshit C.

2009-01-01

Ionizing radiation when allowed to fall upon cells or DNA, the radicals produced modify the base-pair region of the double strands. Radiation-induced double-strand modifications in calf thymus DNA were detected using Ni(II) and Fe(III) complexes of 1,2 dihydroxy 9,10 anthraquinone (DHA). 60 Co was used as the source for γ-radiation and ethidium bromide (EB) as the fluorescent dye for detecting double-strand modifications caused in DNA. Results show that the Fe(III)-DHA complex is more efficient in modifying the base-pair region in double-stranded DNA in comparison to DHA or the Ni(II)-DHA complex

Batch adsorptive removal of Fe(III), Cu(II) and Zn(II) ions in aqueous and aqueous organic–HCl media by Dowex HYRW2-Na Polisher resin as adsorbents

OpenAIRE

Aboul-Magd, Abdul-Aleem Soliman; Al-Husain, Salwa Al-Rashed; Al-Zahrani, Salma Ahmed

2016-01-01

Of the metal ions in tap, Nile, waste and sea water samples and some ores were carried out. Removal of heavy metal ions such as Fe(III), Cd(II), Zn(II), Cu(II), Mn(II), Mg(II), and Pb(II) from water and wastewater is obligatory in order to avoid water pollution. Batch shaking adsorption experiments to evaluate the performance of nitric and hydrochloric acid solutions in the removal of metal ions by cation exchange resin at the same conditions for both, such as the effect of initial metal ion ...

Liquid-liquid extraction (LLE) of Fe(III) and Ti(IV) by bis-(2-ethyl-hexyl) phosphoric acid (D2EHPA) in sulfuric acid medium; Extracao liquido-liquido de ferro (III) e titanio (IV) pelo acido bis-(2-etil-hexil) fosforico (D2EHPA) em meio de acido sulfurico

Energy Technology Data Exchange (ETDEWEB)

Silva, Glauco Correa da; Cunha, Jose Waldemar Silva Dias da [Instituto de Engenharia Nuclear (IEN), Rio de Janeiro, RJ (Brazil). Dept. de Quimica e Materiais Nucleares; Dweck, Jo [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Escola de Quimica. Dept. de Processos Inorganicos; Afonso, Julio Carlos [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Inst. de Quimica. Dept. de Quimica Analitica]. E-mail: julio@iq.ufrj.br

2008-07-01

This work presents a study on the separation of Fe(III) and Ti(IV) from sulfuric acid leaching solutions of ilmenite (FeTiO{sub 3}) using liquid-liquid extraction with D2EHPA in n-dodecane as extracting agent. The distribution coefficients (K{sub D}) of the elements related to free acidity and concentration of Fe(III) and Ti(IV) were determined. Free acidity was changed from 3x10{sup -2} to 11.88 mol L{sup -1} and D2EHPA concentration was fixed at 1.5 mol L{sup 1}. Recovery of final products as well as recycling of wastes generated in the process were also investigated. The LLE process as a feasible alternative to obtain high-purity TiO{sub 2}. (author)

Heterogeneous biomimetic catalysis using iron porphyrin for cyclohexane oxidation promoted by chitosan

Energy Technology Data Exchange (ETDEWEB)

Huang, Guan, E-mail: huangg66@126.com; Liu, Yao; Cai, Jing Li; Chen, Xiang Feng; Zhao, Shu Kai; Guo, Yong An; Wei, Su Juan; Li, Xu

2017-04-30

Graphical abstract: A biomimetic catalyst of iron-tetrakis(4-sulfonatophenyl)porphyrin immobilized on powdered chitosan achieves efficient cyclohexane oxidation with high ketone and alcohol yields. - Highlights: • Fe (TPPS)/pd-CTS is an excellent catalyst for cyclohexane oxidation. • Amino ligation alters the electron cloud density around the iron cation. • Amino coordination likely reduces the activation energy of Fe (TPPS). • The catalyst achieved 22.9 mol% yields of cyclohexanone and cyclohexanol. - Abstract: This study investigates how ligands modulate metalloporphyrin activity with the goal of producing a practical biomimetic catalyst for use in the chemical industry. We immobilized iron porphyrinate [iron-tetrakis-(4-sulfonatophenyl)-porphyrin; Fe(III) (TPPS)] on powdered chitosan (pd-CTS) to form an immobilized catalyst Fe(III) (TPPS)/pd-CTS, which was characterized using modern spectroscopic techniques and used for catalytic oxidation of cyclohexane with O{sub 2}. Amino coordination to iron porphyrin in Fe(III) (TPPS)/pd-CTS altered the electron cloud density around the iron cation, probably by reducing the activation energy of Fe(III) (TPPS) and raising the reactivity of the iron ion catalytic center, thereby improving the catalytic efficiency. One milligram of Fe(III) (TPPS) catalyst can be reused three times for the oxidation reaction to yield an average of 22.9 mol% of cyclohexanone and cyclohexanol.

Synthesis of a 3D lanthanum(III) MOFs as a multi-chemosensor to Cr(VI)-containing anion and Fe(III) cation based on a flexible ligand

Science.gov (United States)

Ma, Yang-Min; Liu, Tong; Huang, Wen-Huan

2018-02-01

Based on La(NO3)3·6H2O and 4,4‧-((5-carboxy-1,3-phenylene)bis(oxy))dibenzoic acid (H3cpbda), a 3D porous MOFs, [La(cpbda)(H2O)1.5]n (1), was synthesized by hydrothermal method and further characterized by single-crystal X-ray diffraction, power X-ray diffraction, IR spectroscopy, thermal-gravimetric analysis and fluorescence spectroscopy. Owing to its good stabilities and fluorescence property, the sensing experiments on sixteen cations and eleven anions were implemented. Moreover, the further titration processes show 1 can sensitively detect the Fe(III) cation and Cr(VI)-containing anions by quenching responses.

Insights into Nitrate-Reducing Fe(II) Oxidation Mechanisms through Analysis of Cell-Mineral Associations, Cell Encrustation, and Mineralogy in the Chemolithoautotrophic Enrichment Culture KS.

Science.gov (United States)

Nordhoff, M; Tominski, C; Halama, M; Byrne, J M; Obst, M; Kleindienst, S; Behrens, S; Kappler, A

2017-07-01

Most described nitrate-reducing Fe(II)-oxidizing bacteria (NRFeOB) are mixotrophic and depend on organic cosubstrates for growth. Encrustation of cells in Fe(III) minerals has been observed for mixotrophic NRFeOB but not for autotrophic phototrophic and microaerophilic Fe(II) oxidizers. So far, little is known about cell-mineral associations in the few existing autotrophic NRFeOB. Here, we investigate whether the designated autotrophic Fe(II)-oxidizing strain (closely related to Gallionella and Sideroxydans ) or the heterotrophic nitrate reducers that are present in the autotrophic nitrate-reducing Fe(II)-oxidizing enrichment culture KS form mineral crusts during Fe(II) oxidation under autotrophic and mixotrophic conditions. In the mixed culture, we found no significant encrustation of any of the cells both during autotrophic oxidation of 8 to 10 mM Fe(II) coupled to nitrate reduction and during cultivation under mixotrophic conditions with 8 to 10 mM Fe(II), 5 mM acetate, and 4 mM nitrate, where higher numbers of heterotrophic nitrate reducers were present. Two pure cultures of heterotrophic nitrate reducers ( Nocardioides and Rhodanobacter ) isolated from culture KS were analyzed under mixotrophic growth conditions. We found green rust formation, no cell encrustation, and only a few mineral particles on some cell surfaces with 5 mM Fe(II) and some encrustation with 10 mM Fe(II). Our findings suggest that enzymatic, autotrophic Fe(II) oxidation coupled to nitrate reduction forms poorly crystalline Fe(III) oxyhydroxides and proceeds without cellular encrustation while indirect Fe(II) oxidation via heterotrophic nitrate-reduction-derived nitrite can lead to green rust as an intermediate mineral and significant cell encrustation. The extent of encrustation caused by indirect Fe(II) oxidation by reactive nitrogen species depends on Fe(II) concentrations and is probably negligible under environmental conditions in most habitats. IMPORTANCE Most described nitrate-reducing

Insights into Nitrate-Reducing Fe(II) Oxidation Mechanisms through Analysis of Cell-Mineral Associations, Cell Encrustation, and Mineralogy in the Chemolithoautotrophic Enrichment Culture KS

Science.gov (United States)

Nordhoff, M.; Tominski, C.; Halama, M.; Byrne, J. M.; Obst, M.; Behrens, S.

2017-01-01

ABSTRACT Most described nitrate-reducing Fe(II)-oxidizing bacteria (NRFeOB) are mixotrophic and depend on organic cosubstrates for growth. Encrustation of cells in Fe(III) minerals has been observed for mixotrophic NRFeOB but not for autotrophic phototrophic and microaerophilic Fe(II) oxidizers. So far, little is known about cell-mineral associations in the few existing autotrophic NRFeOB. Here, we investigate whether the designated autotrophic Fe(II)-oxidizing strain (closely related to Gallionella and Sideroxydans) or the heterotrophic nitrate reducers that are present in the autotrophic nitrate-reducing Fe(II)-oxidizing enrichment culture KS form mineral crusts during Fe(II) oxidation under autotrophic and mixotrophic conditions. In the mixed culture, we found no significant encrustation of any of the cells both during autotrophic oxidation of 8 to 10 mM Fe(II) coupled to nitrate reduction and during cultivation under mixotrophic conditions with 8 to 10 mM Fe(II), 5 mM acetate, and 4 mM nitrate, where higher numbers of heterotrophic nitrate reducers were present. Two pure cultures of heterotrophic nitrate reducers (Nocardioides and Rhodanobacter) isolated from culture KS were analyzed under mixotrophic growth conditions. We found green rust formation, no cell encrustation, and only a few mineral particles on some cell surfaces with 5 mM Fe(II) and some encrustation with 10 mM Fe(II). Our findings suggest that enzymatic, autotrophic Fe(II) oxidation coupled to nitrate reduction forms poorly crystalline Fe(III) oxyhydroxides and proceeds without cellular encrustation while indirect Fe(II) oxidation via heterotrophic nitrate-reduction-derived nitrite can lead to green rust as an intermediate mineral and significant cell encrustation. The extent of encrustation caused by indirect Fe(II) oxidation by reactive nitrogen species depends on Fe(II) concentrations and is probably negligible under environmental conditions in most habitats. IMPORTANCE Most described nitrate-reducing

Colorimetric determination of reducing normality in the Purex process

International Nuclear Information System (INIS)

Baumann, E.W.

1983-07-01

Adjustment of the valence state of plutonium from extractable Pu(IV) to nonextractable Pu(III) in the Purex process is accomplished by addition of reductants such as Fe(II), hydroxylamine nitrate (HAN), or U(IV). To implement on-line monitoring of this reduction step for improved process control at the Savannah River Plant, a simple colorimetric method for determining excess reductant (reducing normality) was developed. The method is based on formation of a colored complex of Fe(II) with FerroZine (Hach Chemical Company). The concentration of Fe(II) is determined directly. The concentration of HAN or U(IV), in addition to Fe(II), is determined indirectly as Fe(II), produced through reduction of Fe(III). Experimental conditions for a HAN-Fe(III) reaction of known stoichiometry were established. The effect of hydrazine, which stabilizes U(IV), was also determined. Real-time measurements of color development were made that simulated on-line performance. A laboratory analytical procedure is included. 5 references, 8 figures

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.

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.

Microbial Diversity and Characteristics in Anaerobic Environments in KURT Groundwater

International Nuclear Information System (INIS)

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

2008-03-01

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

Microbial Diversity in KURT Groundwater and Biomineralization Characteristics

International Nuclear Information System (INIS)

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

2009-03-01

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

Iron-reducing bacteria accumulate ferric oxyhydroxide nanoparticle aggregates that may support planktonic growth.

Science.gov (United States)

Luef, Birgit; Fakra, Sirine C; Csencsits, Roseann; Wrighton, Kelly C; Williams, Kenneth H; Wilkins, Michael J; Downing, Kenneth H; Long, Philip E; Comolli, Luis R; Banfield, Jillian F

2013-02-01

Iron-reducing bacteria (FeRB) play key roles in anaerobic metal and carbon cycling and carry out biogeochemical transformations that can be harnessed for environmental bioremediation. A subset of FeRB require direct contact with Fe(III)-bearing minerals for dissimilatory growth, yet these bacteria must move between mineral particles. Furthermore, they proliferate in planktonic consortia during biostimulation experiments. Thus, a key question is how such organisms can sustain growth under these conditions. Here we characterized planktonic microbial communities sampled from an aquifer in Rifle, Colorado, USA, close to the peak of iron reduction following in situ acetate amendment. Samples were cryo-plunged on site and subsequently examined using correlated two- and three-dimensional cryogenic transmission electron microscopy (cryo-TEM) and scanning transmission X-ray microscopy (STXM). The outer membranes of most cells were decorated with aggregates up to 150 nm in diameter composed of ∼3 nm wide amorphous, Fe-rich nanoparticles. Fluorescent in situ hybridization of lineage-specific probes applied to rRNA of cells subsequently imaged via cryo-TEM identified Geobacter spp., a well-studied group of FeRB. STXM results at the Fe L(2,3) absorption edges indicate that nanoparticle aggregates contain a variable mixture of Fe(II)-Fe(III), and are generally enriched in Fe(III). Geobacter bemidjiensis cultivated anaerobically in the laboratory on acetate and hydrous ferric oxyhydroxides also accumulated mixed-valence nanoparticle aggregates. In field-collected samples, FeRB with a wide variety of morphologies were associated with nano-aggregates, indicating that cell surface Fe(III) accumulation may be a general mechanism by which FeRB can grow while in planktonic suspension.

The outer membrane protein Omp35 affects the reduction of Fe(III, nitrate, and fumarate by Shewanella oneidensis MR-1

Directory of Open Access Journals (Sweden)

Myers Charles R

2004-06-01

Full Text Available Abstract Background Shewanella oneidensis MR-1 uses several electron acceptors to support anaerobic respiration including insoluble species such as iron(III and manganese(IV oxides, and soluble species such as nitrate, fumarate, dimethylsulfoxide and many others. MR-1 has complex branched electron transport chains that include components in the cytoplasmic membrane, periplasm, and outer membrane (OM. Previous studies have implicated a role for anaerobically upregulated OM electron transport components in the use of insoluble electron acceptors, and have suggested that other OM components may also contribute to insoluble electron acceptor use. In this study, the role for an anaerobically upregulated 35-kDa OM protein (Omp35 in the use of anaerobic electron acceptors was explored. Results Omp35 was purified from the OM of anaerobically grown cells, the gene encoding Omp35 was identified, and an omp35 null mutant (OMP35-1 was isolated and characterized. Although OMP35-1 grew on all electron acceptors tested, a significant lag was seen when grown on fumarate, nitrate, and Fe(III. Complementation studies confirmed that the phenotype of OMP35-1 was due to the loss of Omp35. Despite its requirement for wild-type rates of electron acceptor use, analysis of Omp35 protein and predicted sequence did not identify any electron transport moieties or predicted motifs. OMP35-1 had normal levels and distribution of known electron transport components including quinones, cytochromes, and fumarate reductase. Omp35 is related to putative porins from MR-1 and S. frigidimarina as well as to the PorA porin from Neisseria meningitidis. Subcellular fraction analysis confirmed that Omp35 is an OM protein. The seven-fold anaerobic upregulation of Omp35 is mediated post-transcriptionally. Conclusion Omp35 is a putative porin in the OM of MR-1 that is markedly upregulated anaerobically by a post-transcriptional mechanism. Omp35 is required for normal rates of growth on Fe(III

The role of hydrogenotrophic iron-reducing bacteria on the corrosion process in the context of geological disposal

International Nuclear Information System (INIS)

Kerber-Schutz, Marta

2013-01-01

The nuclear industry must to demonstrate the feasibility and safety of high level nuclear waste (HLNW) disposal. The generally recognised strategy for HLNW disposal is based on a multi-barrier system made by metallic packages surrounded by geological formation. The nuclear waste repository will be water re-saturated with time, and then the metallic corrosion process will take place. The aqueous corrosion will produce dihydrogen (H 2 ) that represents a new energetic source (electron donor) for microbial development. Moreover, the formation of Fe(II,III) solid corrosion products, such as magnetite (Fe 3 O 4 ), will provide electron acceptors favoring the development of iron-reducing bacteria (IRB). The activity of hydrogenotrophic and IRB can potentially alter the protective properties of passivating oxide layers (i.e. magnetite) which could reactivate corrosion. The main objective of this study is to evaluate the role of hydrogenotrophic and IRB activities on anoxic corrosion process by using geochemical indicators. Shewanella oneidensis strain MR-1 was chosen as model organism, and both abiotic and biotic conditions were investigated. In a first setup of experiments, our results indicate that synthetic magnetite is destabilized in the presence of hydrogenotrophic IRB due to structural Fe(III) reduction coupled to H 2 oxidation. The extent of Fe(III) bioreduction is notably enhanced with the increase in the H 2 concentration in the system: 4% H 2 ≤ 10% H 2 ≤ 60% H 2 . In a second setup of experiments, our results indicate that corrosion extent changes according to the solution composition and the surface of metallic sample (iron powder and carbon steel coupon). Moreover, the solid corrosion products are different for each sample: vivianite, siderite and chukanovite are the main mineral phases identified in the experiments with iron powder, while vivianite and magnetite are identified with carbon steel coupons. Our results demonstrate that corrosion rate is

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.

Dehydrochlorination of 1,1,1-trichloroethane and pentachloroethane by microbially reduced ferruginous smectite.

Science.gov (United States)

Cervini-Silva, Javiera; Kostka, Joel E; Larson, Richard A; Stucki, Joseph W; Wu, Jun

2003-05-01

Reduction of structural Fe(III) in smectite clay minerals has been identified as a means to promote dechlorination of polychlorinated ethanes, but its environmental significance has yet to be fully assessed because Fe reduction has normally been achieved by agents uncommon in the environment (e.g., dithionite). This study reports the dehydrochlorination of pentachloroethane and 1,1,1-trichloroethane in the presence of ferruginous smectite reduced by two cultures of microorganisms, Shewanella oneidensis strain MR-1 (MR-R) and an enrichment culture from rice paddy soils (PS-R), in aqueous suspension under anoxic conditions. Microbially reduced ferruginous smectite facilitated dehydrochlorination of 1,1,1-trichloroethane to 1,1-dichloroethene with up to 60% conversion within 3 h of incubation time. In contrast, no formation of 1,1-dichloroethene was observed after incubation of 1,1,1-trichloroethane with chemically reduced ferruginous smectite for 24 h. Microbially reduced ferruginous smectite by MR-R and PS-R promoted the dehydrochlorination of pentachloroethane to tetrachloroethene by 80 and 15%, respectively, after 3 h of incubation time. The conversion of pentachloroethane to tetrachloroethene in the presence of chemically reduced ferruginous smectite after 24 h was 65%. These results indicate that structural Fe(II) in clay minerals has the potential to be an important reductant controlling the fate of organic chemicals in contaminated sediments.

Localized sulfate-reducing zones in a coastal plain aquifer

Science.gov (United States)

Brown, C.J.; Coates, J.D.; Schoonen, M.A.A.

1999-01-01

High concentrations of dissolved iron in ground water of coastal plain or alluvial aquifers contribute to the biofouling of public supply wells for which treatment and remediation is costly. Many of these aquifers, however, contain zones in which microbial sulfate reduction and the associated precipitation of iron-sulfide minerals decreases iron mobility. The principal water-bearing aquifer (Magothy Aquifer of Cretaceous age) in Suffolk County, New York, contains localized sulfate-reducing zones in and near lignite deposits, which generally are associated with clay lenses. Microbial analyses of core samples amended with [14C]-acetate indicate that microbial sulfate reduction is the predominant terminal-electron-accepting process (TEAP) in poorly permeable, lignite-rich sediments at shallow depths and near the ground water divide. The sulfate-reducing zones are characterized by abundant lignite and iron-sulfide minerals, low concentrations of Fe(III) oxyhydroxides, and by proximity to clay lenses that contain pore water with relatively high concentrations of sulfate and dissolved organic carbon. The low permeability of these zones and, hence, the long residence time of ground water within them, permit the preservation and (or) allow the formation of iron-sulfide minerals, including pyrite and marcasite. Both sulfate-reducing bacteria (SRB) and iron-reducing bacteria (IRB) are present beneath and beyond the shallow sulfate-reducing zones. A unique Fe(III)-reducing organism, MD-612, was found in core sediments from a depth of 187 m near the southern shore of Long Island. The distribution of poorly permeable, lignite-rich, sulfate-reducing zones with decreased iron concentration is varied within the principal aquifer and accounts for the observed distribution of dissolved sulfate, iron, and iron sulfides in the aquifer. Locating such zones for the placement of production wells would be difficult, however, because these zones are of limited aerial extent.

Pheromone produced by the myxobacterium Stigmatella aurantiaca.

OpenAIRE

Stephens, K; Hegeman, G D; White, D

1982-01-01

An extracellular, diffusible signaling molecule (pheromone) was produced by Stigmatella aurantiaca during fruiting body formation. The pheromone decreased the aggregation period in both the light and the dark and substituted for light in stimulating the maturation of aggregates into fruiting bodies. The cells were more sensitive to lower concentrations of pheromone in the light than in the dark, possibly explaining the stimulation of aggregation and fruiting body formation by light. The phero...

Influence of Carbon Sources and Electron Shuttles on Ferric Iron Reduction by Cellulomonas sp. Strain ES6

Energy Technology Data Exchange (ETDEWEB)

Dr Robin Gerlach; Erin K. Field; Sridhar Viamajala; Brent M. Peyton; William A. Apel; Al B. Cunningham

2011-09-01

Microbially reduced iron minerals can reductively transform a variety of contaminants including heavy metals, radionuclides, chlorinated aliphatics, and nitroaromatics. A number of Cellulomonas spp. strains, including strain ES6, isolated from aquifer samples obtained at the U.S. Department of Energy's Hanford site in Washington, have been shown to be capable of reducing Cr(VI), TNT, natural organic matter, and soluble ferric iron [Fe(III)]. This research investigated the ability of Cellulomonas sp. strain ES6 to reduce solid phase and dissolved Fe(III) utilizing different carbon sources and various electron shuttling compounds. Results suggest that Fe(III) reduction by and growth of strain ES6 was dependent upon the type of electron donor, the form of iron present, and the presence of synthetic or natural organic matter, such as anthraquinone-2,6-disulfonate (AQDS) or humic substances. This research suggests that Cellulomonas sp. strain ES6 could play a significant role in metal reduction in the Hanford subsurface and that the choice of carbon source and organic matter addition can allow for independent control of growth and iron reduction activity.

Microbial Anaerobic Ammonium Oxidation Under Iron Reducing Conditions, Alternative Electron Acceptors

Science.gov (United States)

Ruiz-Urigüen, M.; Jaffe, P. R.

2015-12-01

Autotrophic Acidimicrobiaceae-bacterium named A6 (A6), part of the Actinobacteria phylum have been linked to anaerobic ammonium (NH4+) oxidation under iron reducing conditions. These organisms obtain their energy by oxidizing NH4+ and transferring the electrons to a terminal electron acceptor (TEA). Under environmental conditions, the TEAs are iron oxides [Fe(III)], which are reduced to Fe(II), this process is known as Feammox. Our studies indicate that alternative forms of TEAs can be used by A6, e.g. iron rich clays (i.e. nontronite) and electrodes in bioelectrochemical systems such as Microbial Electrolysis Cells (MECs), which can sustain NH4+removal and A6 biomass production. Our results show that nontronite can support Feammox and promote bacterial cell production. A6 biomass increased from 4.7 x 104 to 3.9 x 105 cells/ml in 10 days. Incubations of A6 in nontronite resulted in up to 10 times more NH4+ removal and 3 times more biomass production than when ferrihydrite is used as the Fe(III) source. Additionally, Fe in nontronite can be reoxidized by aeration and A6 can reutilize it; however, Fe is still finite in the clay. In contrast, in MECs, A6 harvest electrons from NH4+ and use an anode as an unlimited TEA, as a result current is produced. We operated multiple MECs in parallel using a single external power source, as described by Call & Logan (2011). MECs were run with an applied voltage of 0.7V and different growing mediums always containing initial 5mM NH4+. Results show that current production is favored when anthraquinone-2,6-disulfonate (AQDS), an electron shuttled, is present in the medium as it facilitates the transfer of electrons from the bacterial cell to the anode. Additionally, A6 biomass increased from 1 x 104 to 9.77 x 105cells/ml in 14 days of operation. Due to Acidimicrobiaceae-bacterium A6's ability to use various TEAs, MECs represent an alternative, iron-free form, for optimized biomass production of A6 and its application in NH4

Comparative Study of Catalytic Oxidation of Ethanol to Acetaldehyde Using Fe(III Dispersed on Sb2O5 Grafted on SiO2 and on Untreated SiO2 Surfaces

Directory of Open Access Journals (Sweden)

Benvenutti Edilson V.

1998-01-01

Full Text Available Fe(III was supported on Sb(V oxide grafted on the silica gel surface and directly on the silica gel surface using ion-exchange and impregnation processes producing Fe/Sb/SiO2 and Fe/SiO2, respectively. The catalytic conversion of ethanol to acetaldehyde was much more efficient using Fe/Sb/SiO2 than Fe/SiO2 as catalyst. This higher efficiency of the former catalyst takes into account two aspects: a the new phase FeSbO4 formed when Fe/Sb/SiO2 is heat treated and, b it is higher dispersion on the matrix.

Mineral transformations associated with goethite reduction by Methanosarcina barkeri

Science.gov (United States)

Liu, D.; Wang, Hongfang; Dong, H.; Qiu, X.; Dong, X.; Cravotta, C.A.

2011-01-01

To investigate the interaction between methanogens and iron-containing minerals in anoxic environments, we conducted batch culture experiments with Methanosarcina barkeri in a phosphate-buffered basal medium (PBBM) to bioreduce structural Fe(III) in goethite with hydrogen as the sole substrate. Fe(II) and methane concentrations were monitored over the course of the bioreduction experiments with wet chemistry and gas chromatography, respectively. Subsequent mineralogical changes were characterized with X-ray diffraction (XRD) and scanning electron microscopy (SEM). In the presence of an electron shuttle anthraquinone-2,6-disulfonate (AQDS), 30% Fe(III) in goethite (weight basis) was reduced to Fe(II). In contrast, only 2% Fe(III) (weight basis) was bioreduced in the absence of AQDS. Most of the bioproduced Fe(II) was incorporated into secondary minerals including dufr??nite and vivianite. Our data implied a dufr??nite-vivianite transformation mechanism where a metastable dufr??nite transformed to a more stable vivianite over extended time in anaerobic conditions. Methanogenesis was greatly inhibited by bioreduction of goethite Fe(III). These results have important implications for the methane flux associated with Fe(III) bioreduction and ferrous iron mineral precipitation in anaerobic soils and sediments. ?? 2011 Elsevier B.V.

Coordination and Oxidation States of Iron Incorporated in Mesoporous MCM41

International Nuclear Information System (INIS)

Lazar, K.; Pal-Borbely, G.; Szegedi, A.; Beyer, H. K.

2002-01-01

Mesoporous Fe-MCM41 samples (Si/Fe=25) were synthesized and characterized under evacuation and reducing/oxidizing treatments by in situ FTIR and Moessbauer spectroscopies. Both Fe(II) and Fe(III) located in low coordination states in top layers of pore walls exhibit Lewis acidity and may participate in Fe(III) ↔ Fe(II) processes at low temperatures (570 K). Furthermore, Fe(III) ↔ Fe(II) cycles can be achieved and repeated with participation of the full amount of iron at higher temperatures (670 K). The accompanying formation of oxygen vacancies and restoration of the structure in the reverse process does not result in extended damages; the MCM41 structure retains its stability under the conditions applied.

Extração líquido-líquido de ferro(III e titânio(IV pelo ácido bis-(2-etil-hexil fosfórico (D2EHPA em meio de ácido sulfúrico Liquid-liquid extraction (LLE of Fe(III and Ti(IV by bis-(2-ethyl-hexyl phosphoric acid (D2EHPA in sulfuric acid medium

Directory of Open Access Journals (Sweden)

Glauco Corrêa da Silva

2008-01-01

Full Text Available This work presents a study on the separation of Fe(III and Ti(IV from sulfuric acid leaching solutions of ilmenite (FeTiO3 using liquid-liquid extraction with D2EHPA in n-dodecane as extracting agent. The distribution coefficients (K D of the elements related to free acidity and concentration of Fe(III and Ti(IV were determined. Free acidity was changed from 3x10-2 to 11.88 mol L-1 and D2EHPA concentration was fixed at 1.5 mol L-1. Recovery of final products as well as recycling of wastes generated in the process were also investigated. The LLE process as a feasible alternative to obtain high-purity TiO2.

Meta-Transcriptomic Analysis of a Chromate-Reducing Aquifer Microbial Community

Science.gov (United States)

Beller, H. R.; Brodie, E. L.; Han, R.; Karaoz, U.

2010-12-01

A major challenge for microbial ecology that has become more tractable in the advent of new molecular techniques is characterizing gene expression in complex microbial communities. We are using meta-transcriptomic analysis to characterize functional changes in an aquifer-derived, chromate-reducing microbial community as it transitions through various electron-accepting conditions. We inoculated anaerobic microcosms with groundwater from the Cr-contaminated Hanford 100H site and supplemented them with lactate and electron acceptors present at the site, namely, nitrate, sulfate, and Fe(III). The microcosms progressed successively through various electron-accepting conditions (e.g., denitrifying, sulfate-reducing, and ferric iron-reducing conditions, as well as nitrate-dependent, chemolithotrophic Fe(II)-oxidizing conditions). Cr(VI) was rapidly reduced initially and again upon further Cr(VI) amendments. Extensive geochemical sampling and analysis (e.g., lactate, acetate, chloride, nitrate, nitrite, sulfate, dissolved Cr(VI), total Fe(II)), RNA/DNA harvesting, and PhyloChip analyses were conducted. Methods were developed for removal of rRNA from total RNA in preparation for meta-transcriptome sequencing. To date, samples representing denitrifying and fermentative/sulfate-reducing conditions have been sequenced using 454 Titanium technology. Of the non-rRNA related reads for the denitrifying sample (which was also actively reducing chromate), ca. 8% were associated with denitrification and ca. 0.9% were associated with chromate resistance/transport, in contrast to the fermentative/sulfate-reducing sample (in which chromate had already been reduced), which had zero reads associated with either of these categories but many predicted proteins associated with sulfate-reducing bacteria. We observed sequences for key functional transcripts that were unique at the nucleotide level compared to the GenBank non-redundant database [such as L-lactate dehydrogenase (iron

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

Science.gov (United States)

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

2017-06-06

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

Kinetics of U(VI) reduction by a dissimilatory Fe(III)-reducing bacterium under non-growth conditions

International Nuclear Information System (INIS)

Truex, M.J.; Peyton, B.M.; Valentine, N.B.; Gorby, Y.A.

1997-01-01

Dissimilatory metal-reducing microorganisms may be useful in processes designed for selective removal of uranium from aqueous streams. These bacteria can use U(VI) as an electron acceptor and thereby reduce soluble U(VI) to insoluble U(IV). While significant research has been devoted to demonstrating and describing the mechanism of dissimilatory metal reduction, the reaction kinetics necessary to apply this for remediation processes have not been adequately defined. In this study, pure culture Shewanella alga strain BrY reduced U(VI) under non-growth conditions in the presence of excess lactate as the electron donor. Initial U(VI) concentrations ranged from 13 to 1,680microM. A maximum specific U(VI) reduction rate of 2.37 micromole-U(VI)/(mg-biomass h) and Monod half-saturation coefficient of 132 microM-U(VI) were calculated from measured U(VI) reduction rates. U(VI) reduction activity was sustained at 60% of this rate for at least 80 h. The initial presence of oxygen at a concentration equal to atmospheric saturation at 22 C delays but does not prevent U(VI) reduction. The rate of U(VI) reduction by BrY is comparable or better than rates reported for other metal reducing species. BrY reduces U(VI) at a rate that is 30% of its Fe(III) reduction rate

Effect of deacetylation on property of electrospun chitosan/PVA nanofibrous membrane and removal of methyl orange, Fe(III) and Cr(VI) ions.

Science.gov (United States)

Habiba, Umma; Siddique, Tawsif A; Talebian, Sepehr; Lee, Jacky Jia Li; Salleh, Areisman; Ang, Bee Chin; Afifi, Amalina M

2017-12-01

In this study, effect of degree of deacetylation on property and adsorption capacity of chitosan/polyvinyl Alcohol electrospun membrane has been investigated. Resulting nanofibers were characterized by FESEM, FTIR, XRD, TGA, tensile testing, weight loss test and adsorption test. FESEM result shows, finer nanofiber was fabricated from 42h hydrolyzed chitosan and PVA blend solution. FTIR and XRD result showed a strong interaction between chitosan and polyvinyl alcohol. Higher tensile strength was observed for the nanofiber having 42h hydrolyzed chitosan. Blend solution of chitosan/PVA having low DD chitosan had higher viscosity. The nanofibrous membrane was stable in distilled water, acidic and basic medium. The isotherm study shows that the adsorption capacity (q m ) of nanofiber containing higher DD chitosan was higher for Cr(VI). In contrary, the membrane containing chitosan with lower DD showed the higher adsorption capacity for Fe(III) and methyl orange. Moreover, the effect of DD on removal percentage of adsorbate was dependent on the initial concentration of the adsorbate. Copyright © 2017 Elsevier Ltd. All rights reserved.

Intercellular signalling in Stigmatella aurantiaca.

Science.gov (United States)

Plaga, W; Ulrich, S H

1999-12-01

The myxobacterium Stigmatella aurantiaca is a prokaryotic model used to study intercellular signalling and the genetic determination of morphogenesis. Signalling factors and genes required for the generation of the elaborate multicellular fruiting body are to be identified. Recently, the structure of stigmolone, which is the pheromone necessary for fruiting body formation, was elucidated, and genes involved in development were characterised. Progress has also been made in the genetic accessibility of S. aurantiaca.

Adrenaline and triiodothyronine modify the iron handling in the freshwater air-breathing fish Anabas testudineus Bloch: role of ferric reductase in iron acquisition.

Science.gov (United States)

Rejitha, V; Peter, M C Subhash

2013-01-15

The effects of in vivo adrenaline and triiodothyronine (T(3)) on ferric reductase (FR) activity, a membrane-bound enzyme that reduces Fe(III) to Fe(II) iron, were studied in the organs of climbing perch (Anabas testudineus Bloch). Adrenaline injection (10 ng g(-1)) for 30 min produced significant inhibition of FR activity in the liver and kidney and that suggests a role for this stress hormone in iron acquisition in this fish. Short-term T(3) injection (40 ng g(-1)) reduced FR activity in the gills of fed fish but not in the unfed fish. Similar reduction of FR activity was also obtained in the intestine and kidney of fed fish after T(3) injection. Feeding produced pronounced decline in FR activity in the spleen but T(3) challenge in fed and unfed fish increased its activity in this iron storing organ and that point to the sensitivity of FR system to feeding activity. The in vitro effects of Fe on FR activity in the gill explants of freshwater fish showed correlations of FR with Na(+), K(+)-ATPase and H(+)-ATPase activities. Substantial increase in the FR activity was found in the gill explants incubated with all the tested doses of Fe(II) iron (1.80, 3.59 and 7.18 μM) and Fe(III) iron (1.25, 2.51 and 5.02 μM) and this indicate that FR and Na pump activity are positively correlated. On the contrary, substantial reduction of gill H(+)-ATPase activity was found in the gill explants incubated with Fe(II) iron and Fe(III) iron indicating that perch gills may not require a high acidic microenvironment for the reduction of Fe(III) iron. Accumulation of iron in the gill explants after Fe(III) iron incubation implies a direct relationship between Fe acquisition and FR activity in this tissue. The inverse correlation between FR activity and H(+)-ATPase activity in Fe(II) or Fe(III) loaded gills and the significant positive correlations of FR activity with total [Fe] content in the Fe(III) loaded gills substantiate that FR which shows sensitivity to sodium and proton pumps

Pyrite oxidation at circumneutral pH

Science.gov (United States)

Moses, Carl O.; Herman, Janet S.

1991-02-01

Previous studies of pyrite oxidation kinetics have concentrated primarily on the reaction at low pH, where Fe(III) has been assumed to be the dominant oxidant. Studies at circumneutral pH, necessitated by effective pH buffering in some pyrite oxidation systems, have often implicitly assumed that the dominant oxidant must be dissolved oxygen (DO), owing to the diminished solubility of Fe(III). In fact, Fe(III)(aq) is an effective pyrite oxidant at circumneutral pH, but the reaction cannot be sustained in the absence of DO. The purpose of this experimental study was to ascertain the relative roles of Fe(III) and DO in pyrite oxidation at circumneutral pH. The rate of pyrite oxidation was first-order with respect to the ratio of surface area to solution volume. Direct determinations of both Fe(II) (aq)> and Fe(III) (aq) demonstrated a dramatic loss of Fe(II) from the solution phase in excess of the loss for which oxidation alone could account. Based on rate data, we have concluded that Fe(II) is adsorbed onto the pyrite surface. Furthermore, Fe(II) is preferred as an adsorbate to Fe(III), which we attribute to both electrostatic and acid-base selectivity. We also found that the rate of pyrite oxidation by either Fe(III) (aq) or DO is reduced in the presence of aqueous Fe(II), which leads us to conclude that, under most natural conditions, neither Fe(III) (aq) nor DO directly attacks the pyrite surface. The present evidence suggests a mechanism for pyrite oxidation that involves adsorbed Fe( II ) giving up electrons to DO and the resulting Fe(III) rapidly accepting electrons from the pyrite. The adsorbed Fe is, thus, cyclically oxidized and reduced, while it acts as a conduit for electrons traveling from pyrite to DO. Oxygen is transferred from the hydration sphere of the adsorbed Fe to pyrite S. The cycle of adsorbed Fe oxidation and reduction and the successive addition of oxygen to pyrite S continues until a stable sulfoxy species dissociates from the surface. Prior

Study of the oxidation-reduction kinetics involved in the Np(V) + Fe(II) in equilibrium Np(IV) + Fe(III) system in nitric acid solutions

International Nuclear Information System (INIS)

Jao, Y.

1975-08-01

Ferrous nitrate-hydrazine is one of the more attractive alternate reactants to the currently used reagent, ferrous sulfamate, for partitioning plutonium from neptunium and uranium. An understanding of the kinetics of the reduction of Np(VI) to Np(IV) by ferrous nitrate-hydrazine is needed before a satisfactory evaluation of the feasibility of this reductant in actinide element separations can be made. The purpose of this work was to study the kinetics and mechanisms of the reduction of Np(V) by Fe(II) and the oxidation of Np(IV) by Fe(III) in 1-2 M nitric acid solutions. The acid concentration range was chosen to include that typically used in the separation of plutonium from neptunium and uranium by solvent extraction with tributylphosphate. The forward and reverse rate constants, hydrogen ion dependence, temperature dependence, ionic strength effects and nitrate ion influence were determined. The proposed reaction mechanisms involve protonation of the NpO 2 + ions and hydroxyoxygenation of Np 4 + ions. (LK)

Microbial iron reduction related to metal speciation in mine waste at the former uranium mine in Ranstad

International Nuclear Information System (INIS)

Nejad, F.T.

1998-02-01

Mining activities in Ranstad uranium mine started in 1965 and ended in 1969. In 1988 the final restoration was discussed, and it was proposed to water-fill the open pit and cover the waste disposal area using the 'dry method'. Today the open pit has become a lake. Also some alum shale was placed on the land surface where it has been weathered by oxygen and water during 30 years. In 1994 it was observed that the color of the lake turned over to brown-red. Further studies showed increasing iron concentration in the lake and around the tailings area. For estimation of microbial iron reduction in the lake, three iron reducing bacteria were isolated from the water-filled open pit. For the enrichment process, water samples were inoculated in an anoxic enrichment medium. The isolates were able to reduce Fe(III) oxyhydroxide by oxidation of lactate as energy source. Growth of these strains was determined by production of a black precipitation of iron sulfide and was confirmed by estimation of total number of cells. Fe(III) reduction was monitored by measuring the accumulation of Fe(II) over time. Comparison of the 16S rRNA gene sequences of strains Tran-l, Tran-2, and Tran-3 with the EMBL data base showed 98.6% identity with Shewanella putrefaciens, 98.7% identity with Shewanella alga and 98.2% identity with Aeromonas salmonicida, respectively. S. putrefaciens strains have been isolated from many different environments, many of which are suboxic or anoxic. In addition to growing aerobically, S. putrefaciens can use Fe(III) as terminal electron acceptor under anaerobic conditions. To distinguish if the Fe(III) and/or organic compounds presence in weathered alum shale can be utilized by iron reducing bacteria isolated from the lake, reduction of Fe(III) coupled to the oxidation of organic compounds in sterile and non-sterile weathered alum shale was studied. The reduction of Fe(III) coupled to growth of bacteria on sterile and non-sterile shale was observed. Furthermore

Application Of Bacterial Iron Reduction For The Removal Of Iron Impurities From Industrial Silica Sand And Kaolin

Science.gov (United States)

Zegeye, A.; Yahaya, S.; Fialips, C. I.; White, M.; Manning, D. A.; Gray, N.

2008-12-01

Biogeochemical evidence exists to support the potential importance of crystalline or amorphous Fe minerals as electron acceptor for Fe reducing bacteria in soils and subsurface sediments. This microbial metabolic activity can be exploited as alternative method in different industrial applications. For instance, the removal of ferric iron impurities from minerals for the glass and paper industries currently rely on physical and chemical treatments having substantial economical and environmental disadvantages. The ability to remove iron by other means, such as bacterial iron reduction, may reduce costs, allow lower grade material to be mined, and improve the efficiency of mineral processing. Kaolin clay and silica sand are used in a wide range of industrial applications, particularly in paper, ceramics and glass manufacturing. Depending on the geological conditions of deposition, they are often associated with iron (hydr)oxides that are either adsorbed to the mineral surfaces or admixed as separate iron bearing minerals. In this study, we have examined the Fe(III) removal efficiency from kaolin and silica sand by a series of iron- reducing bacteria from the Shewanella species (S. alga BrY, S. oneidensis MR-1, S. putrefaciens CN32 and S. putrefaciens ATCC 8071) in the presence of anthraquinone 2,6 disulfonate (AQDS). We have also investigated the effectiveness of a natural organic matter, extracted with the silica sand, as a substitute to AQDS for enhancing Fe(III) reduction kinetics. The microbial reduction of Fe(III) was achieved using batch cultures under non-growth conditions. The rate and the extent of Fe(III) reduction was monitored as a function of the initial Fe(III) content, Shewanella species and temperature. The bacterially- treated minerals were analyzed by transmission electron microscopy (TEM) and X-ray diffraction (XRD) to observe any textural and mineralogical transformation. The whiteness and ISO brightness of the kaolin was also measured by

Microbial iron reduction related to metal speciation in mine waste at the former uranium mine in Ranstad

Energy Technology Data Exchange (ETDEWEB)

Nejad, F.T. [Goeteborg Univ. (Sweden). Dept. of General and Marine Microbiology

1998-02-01

Mining activities in Ranstad uranium mine started in 1965 and ended in 1969. In 1988 the final restoration was discussed, and it was proposed to water-fill the open pit and cover the waste disposal area using the `dry method`. Today the open pit has become a lake. Also some alum shale was placed on the land surface where it has been weathered by oxygen and water during 30 years. In 1994 it was observed that the color of the lake turned over to brown-red. Further studies showed increasing iron concentration in the lake and around the tailings area. For estimation of microbial iron reduction in the lake, three iron reducing bacteria were isolated from the water-filled open pit. For the enrichment process, water samples were inoculated in an anoxic enrichment medium. The isolates were able to reduce Fe(III) oxyhydroxide by oxidation of lactate as energy source. Growth of these strains was determined by production of a black precipitation of iron sulfide and was confirmed by estimation of total number of cells. Fe(III) reduction was monitored by measuring the accumulation of Fe(II) over time. Comparison of the 16S rRNA gene sequences of strains Tran-l, Tran-2, and Tran-3 with the EMBL data base showed 98.6% identity with Shewanella putrefaciens, 98.7% identity with Shewanella alga and 98.2% identity with Aeromonas salmonicida, respectively. S. putrefaciens strains have been isolated from many different environments, many of which are suboxic or anoxic. In addition to growing aerobically, S. putrefaciens can use Fe(III) as terminal electron acceptor under anaerobic conditions. To distinguish if the Fe(III) and/or organic compounds presence in weathered alum shale can be utilized by iron reducing bacteria isolated from the lake, reduction of Fe(III) coupled to the oxidation of organic compounds in sterile and non-sterile weathered alum shale was studied. The reduction of Fe(III) coupled to growth of bacteria on sterile and non-sterile shale was observed. Furthermore

Microbial effects on the release and attenuation of arsenic in the shallow subsurface of a natural geochemical anomaly

International Nuclear Information System (INIS)

Drahota, Petr; Falteisek, Lukáš; Redlich, Aleš; Rohovec, Jan; Matoušek, Tomáš; Čepička, Ivan

2013-01-01

Critical factors leading to arsenic release and attenuation from the shallow subsurface were studied with multidisciplinary approach in the natural gold–arsenic geochemical anomaly at Mokrsko (Czech Republic). The results show that microbial reduction promotes arsenic release from Fe(III) (hydr)oxides and Fe(III) arsenates, thereby enhancing dissolved arsenic in the shallow groundwater at average concentration of 7.76 mg/L. In the organic-rich aggregates and wood particles, however, microbial sulfate reduction triggers the formation of realgar deposits, leading to accumulation of As in the distinct organic-rich patches of the shallow subsurface. We conclude that precipitation of realgar in the shallow subsurface of soil/sediment depends on specific and non-trivial combination of water and rock chemistry, microbial community composition and spatial organisation of the subsurface zone, where speciation in saturated environments varied on a centimeter scale from reduced (decomposed wood, H 2 S and realgar present) to oxidized (goethite and arsenate minerals are present). Highlights: •Very high As(III) concentrations were detected in the shallow groundwater. •Arsenic is bound to Fe(III) (hydr)oxides, Fe(III) arsenates and newly-formed realgar. •Reductive dissolution of Fe(III) and As(V) minerals by bacteria leads to mobilization of arsenic. •Precipitation of realgar is constrained to anaerobic domains around and within organic particles. -- Microbial reduction of Fe(III) and As(V) minerals leads to mobilization of As and induces a mineralogical transition toward realgar formation

Reductive Dissolution of Goethite and Hematite by Reduced Flavins

Energy Technology Data Exchange (ETDEWEB)

Shi, Zhi; Zachara, John M.; Wang, Zheming; Shi, Liang; Fredrickson, Jim K.

2013-10-02

The abiotic reductive dissolution of goethite and hematite by the reduced forms of flavin mononucleotide (FMNH2) and riboflavin (RBFH2), electron transfer mediators (ETM) secreted by the dissimilatory iron-reducing bacterium Shewanella, was investigated under stringent anaerobic conditions. In contrast to the rapid redox reaction rate observed for ferrihydrite and lepidocrocite (Shi et al., 2012), the reductive dissolution of crystalline goethite and hematite was slower, with the extent of reaction limited by the thermodynamic driving force at circumneutral pH. Both the initial reaction rate and reaction extent increased with decreasing pH. On a unit surface area basis, goethite was less reactive than hematite between pH 4.0 and 7.0. AH2DS, the reduced form of the well-studied synthetic ETM anthraquinone-2,6-disulfonate (AQDS), yielded higher rates than FMNH2 under most reaction conditions, despite the fact that FMNH2 was a more effective reductant than AH2DS for ferryhydrite and lepidocrocite. Two additional model compounds, methyl viologen and benzyl viologen, were investigated under similar reaction conditions to explore the relationship between reaction rate and thermodynamic properties. Relevant kinetic data from the literature were also included in the analysis to span a broad range of half-cell potentials. Other conditions being equal, the surface area normalized initial reaction rate (ra) increased as the redox potential of the reductant became more negative. A non-linear, parabolic relationship was observed between log ra and the redox potential for eight reducants at pH 7.0, as predicted by Marcus theory for electron transfer. When pH and reductant concentration were fixed, log ra was positively correlated to the redox potential of four Fe(III) oxides over a wide pH range, following a non-linear parabolic relationship as well.

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.

Investigation of iron(III) reduction and trace metal interferences in the determination of dissolved iron in seawater using flow injection with luminol chemiluminescence detection

Energy Technology Data Exchange (ETDEWEB)

Ussher, Simon J. [School of Earth, Ocean and Environmental Sciences (SEOES), University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom); Milne, Angela [School of Earth, Ocean and Environmental Sciences (SEOES), University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom); Department of Oceanography, Florida State University, Tallahassee, FL 32306-4320 (United States); Landing, William M. [Department of Oceanography, Florida State University, Tallahassee, FL 32306-4320 (United States); Attiq-ur-Rehman, Kakar [Department of Chemistry, University of Balochistan, Quetta (Pakistan); Seguret, Marie J.M.; Holland, Toby [School of Earth, Ocean and Environmental Sciences (SEOES), University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom); Achterberg, Eric P. [National Oceanography Centre, University of Southampton, European Way, Southampton SO14 3ZH (United Kingdom); Nabi, Abdul [Department of Chemistry, University of Balochistan, Quetta (Pakistan); Worsfold, Paul J., E-mail: pworsfold@plymouth.ac.uk [School of Earth, Ocean and Environmental Sciences (SEOES), University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom)

2009-10-12

A detailed investigation into the performance of two flow injection-chemiluminescence (FI-CL) manifolds (with and without a preconcentration column) for the determination of sub-nanomolar dissolved iron (Fe(II) + Fe(III)), following the reduction of Fe(III) by sulphite, in seawater is described. Kinetic experiments were conducted to examine the efficiency of reduction of inorganic Fe(III) with sulphite under different conditions and a rigorous study of the potential interference caused by other transition metals present in seawater was conducted. Using 100 {mu}M concentrations of sulphite a reduction time of 4 h was sufficient to quantitatively reduce Fe(III) in seawater. Under optimal conditions, cobalt(II) and vanadium(IV)/(III) were the major positive interferences and strategies for their removal are reported. Specifically, cobalt(II) was masked by the addition of dimethylglyoxime to the luminol solution and vanadium(IV) was removed by passing the sample through an 8-hydroxyquinoline column in a low pH carrier stream. Manganese(II) also interfered by suppression of the CL response but this was not significant at typical open ocean concentrations.

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

Directory of Open Access Journals (Sweden)

Krupińska Izabela

2017-09-01

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

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

Science.gov (United States)

Krupińska, Izabela

2017-09-01

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

Desulfuromonas svalbardensis sp. nov. and Desulfuromusa ferrireducens sp. nov., psychrophilic, Fe(III)-reducing bacteria isolated from Arctic sediments, Svalbard

DEFF Research Database (Denmark)

Vandieken, Verona; Mussmann, Marc; Niemann, Helge

2006-01-01

Two psychrophilic, Gram-negative, rod-shaped, motile bacteria (strains 112T and 102T) that conserved energy from dissimilatory Fe(III) reduction concomitant with acetate oxidation were isolated from permanently cold Arctic marine sediments. Both strains grew at temperatures down to -2 degrees C...

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...

Complete genome sequence of the myxobacterium Sorangium cellulosum

DEFF Research Database (Denmark)

Schneiker, S; Perlova, O; Kaiser, O

2007-01-01

The genus Sorangium synthesizes approximately half of the secondary metabolites isolated from myxobacteria, including the anti-cancer metabolite epothilone. We report the complete genome sequence of the model Sorangium strain S. cellulosum Soce56, which produces several natural products and has...... morphological and physiological properties typical of the genus. The circular genome, comprising 13,033,779 base pairs, is the largest bacterial genome sequenced to date. No global synteny with the genome of Myxococcus xanthus is apparent, revealing an unanticipated level of divergence between...... these myxobacteria. A large percentage of the genome is devoted to regulation, particularly post-translational phosphorylation, which probably supports the strain's complex, social lifestyle. This regulatory network includes the highest number of eukaryotic protein kinase-like kinases discovered in any organism...

Environmental Factors Affecting Ammonium Oxidation Under Iron Reducing Conditions

Science.gov (United States)

Jaffe, P. R.; Huang, S.; Ruiz-Urigüen, M.

2014-12-01

Ammonium (NH4+) oxidation coupled to iron (Fe) reduction in the absence of oxygen and nitrate/nitrite (NO3-/NO2-) has been reported by several investigators and referred to as Feammox. Feammox is a biological reaction, where Fe(III) is the electron acceptor, which is reduced to Fe(II), and NH4+ is the electron donor, which is oxidized to NO2-. Through a 180-day anaerobic incubation experiment, and using PCR-DGGE, 454-pyosequecing and qPCR analysis, we have shown that an Acidimicrobiaceae bacterium A6, a previously unreported species in the Acidimicrobiaceae family, might be either responsible or plays a key role in the Feammox process, We have enriched these Feammox bacteria (65.8% in terms of cell numbers) in a membrane reactor, and isolated the pure Acidimicrobiaceae bacterium A6 strain in an autotrophic medium. In samples collected and then incubated from a series of local wetland-, upland-, as well as storm-water detention pond-sediments, Feammox activity was only detected in acidic soil environments that contain Fe oxides. Using primers we developed for this purpose, Acidimicrobiaceae bacterium A6 was detected in all incubations where Feammox was observed. Anaerobic incubations of Feammox enrichment cultures adjusted to different pH, revealed that the optimal pH for Feammox is 4 ~ 5, and the reaction does not proceed when pH > 7. Feammox was still proceeding at pH as low as 2. In Feammox culture amended with different Fe(III) sources, Feammox reaction proceeded only when Fe oxides (ferrihydrite or goethite ) were supplied, whereas samples incubated with ferric chloride or ferric citrate showed no measurable NH4+ oxidation. Furthermore, we have also determined from incubation experiments conducted with a temperature gradient (10 ~ 35℃), that the Feammox process was active when the temperature is above 15℃, and the optimal temperature is 20℃. Incubations of enrichment culture with 79% Feammox bacteria appeared to remove circa 8% more NH4+ at 20ºC than at

Microbial Communities in Contaminated Sediments, Associated with Bioremediation of Uranium to Submicromolar Levels▿

Science.gov (United States)

Cardenas, Erick; Wu, Wei-Min; Leigh, Mary Beth; Carley, Jack; Carroll, Sue; Gentry, Terry; Luo, Jian; Watson, David; Gu, Baohua; Ginder-Vogel, Matthew; Kitanidis, Peter K.; Jardine, Philip M.; Zhou, Jizhong; Criddle, Craig S.; Marsh, Terence L.; Tiedje, James M.

2008-01-01

Microbial enumeration, 16S rRNA gene clone libraries, and chemical analysis were used to evaluate the in situ biological reduction and immobilization of uranium(VI) in a long-term experiment (more than 2 years) conducted at a highly uranium-contaminated site (up to 60 mg/liter and 800 mg/kg solids) of the U.S. Department of Energy in Oak Ridge, TN. Bioreduction was achieved by conditioning groundwater above ground and then stimulating growth of denitrifying, Fe(III)-reducing, and sulfate-reducing bacteria in situ through weekly injection of ethanol into the subsurface. After nearly 2 years of intermittent injection of ethanol, aqueous U levels fell below the U.S. Environmental Protection Agency maximum contaminant level for drinking water and groundwater (reducers were detected, including Desulfovibrio, Geobacter, Anaeromyxobacter, Desulfosporosinus, and Acidovorax spp. The predominant sulfate-reducing bacterial species were Desulfovibrio spp., while the iron reducers were represented by Ferribacterium spp. and Geothrix spp. Diversity-based clustering revealed differences between treated and untreated zones and also within samples of the treated area. Spatial differences in community structure within the treatment zone were likely related to the hydraulic pathway and to electron donor metabolism during biostimulation. PMID:18456853

Surface Analysis of Marine Sulphate-Reducing Bacteria Exo polymers on Steel During Bio corrosion Using X-ray Photoelectron Spectroscopy

International Nuclear Information System (INIS)

Fathul Karim Sahrani; Madzlan Abd. Aziz; Zaharah Ibrahim; Adibah Yahya

2008-01-01

The aim of this study was to determine the surface chemistry during bio corrosion process on growth and on the production of exo polymeric substances (EPS) in batch cultures of mix-strains of marine sulphate-reducing bacteria (SRB) isolated from Malaysian Shipyard and Engineering Harbours, Pasir Gudang. The EPS and precipitates were analyzed by x-ray photoelectron spectroscopy (XPS). The XPS results indicate that Fe(2p 3/2 ) spectrum for iron sulphide can be fitted with Fe(II) and Fe(III) components, both corresponding to Fe-S bond types. The absence of oxide oxygen in the O(1s) spectrum and Fe(III)-O bond types in the Fe(2p 3/2 ) spectrum supports the conclusion that iron sulphides are composed of both ferric and ferrous iron coordinated with mono sulphide and disulphide. (author)

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

Science.gov (United States)

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

2016-10-15

Iron electrocoagulation (Fe-EC) is a low-cost process in which Fe(II) generated from an Fe(0) anode reacts with dissolved O2 to form (1) Fe(III) precipitates with an affinity for bacterial cell walls and (2) bactericidal reactive oxidants. Previous work suggests that Fe-EC is a promising treatment option for groundwater containing arsenic and bacterial contamination. However, the mechanisms of bacteria attenuation and the impact of major groundwater ions are not well understood. In this work, using the model indicator Escherichia coli (E. coli), we show that physical removal via enmeshment in EC precipitate flocs is the primary process of bacteria attenuation in the presence of HCO3(-), which significantly inhibits inactivation, possibly due to a reduction in the lifetime of reactive oxidants. We demonstrate that the adhesion of EC precipitates to cell walls, which results in bacteria encapsulation in flocs, is driven primarily by interactions between EC precipitates and phosphate functional groups on bacteria surfaces. In single solute electrolytes, both P (0.4 mM) and Ca/Mg (1-13 mM) inhibited the adhesion of EC precipitates to bacterial cell walls, whereas Si (0.4 mM) and ionic strength (2-200 mM) did not impact E. coli attenuation. Interestingly, P (0.4 mM) did not affect E. coli attenuation in electrolytes containing Ca/Mg, consistent with bivalent cation bridging between bacterial phosphate groups and inorganic P sorbed to EC precipitates. Finally, we found that EC precipitate adhesion is largely independent of cell wall composition, consistent with comparable densities of phosphate functional groups on Gram-positive and Gram-negative cells. Our results are critical to predict the performance of Fe-EC to eliminate bacterial contaminants from waters with diverse chemical compositions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Hexavalent chromium removal by chitosan modified-bioreduced nontronite

Science.gov (United States)

Singh, Rajesh; Dong, Hailiang; Zeng, Qiang; Zhang, Li; Rengasamy, Karthikeyan

2017-08-01

Recent efforts have focused on structural Fe(II) in chemically or biologically reduced clay minerals to immobilize Cr(VI) from aqueous solution, but the coulombic repulsion between the negatively charged clay surface and the polyanionic form of Cr(VI), e.g., dichromate, can hinder the effectiveness of this process. The purpose of this study was to investigate the efficiency and mechanism of Cr(VI) removal by a charge-reversed nontronite (NAu-2), an Fe-rich smectite. Chitosan, a linear polysaccharide derived from chitin found in soil and groundwater, was used to reverse the charge of NAu-2. Intercalation of chitosan into NAu-2 interlayer increased the basal d-spacing of NAu-2 from 1.23 nm to 1.83 nm and zeta potential from -27.17 to +34.13 mV, with the amount of increase depending on chitosan/NAu-2 ratio. Structural Fe(III) in chitosan-exchanged NAu-2 was then biologically reduced by an iron-reducing bacterium Shewanella putrefaciens CN32 in bicarbonate buffer with lactate as the sole electron donor, with and without electron shuttle, AQDS. Without AQDS, the extent of Fe(III) reduction increased from the lowest (∼9%) for the chitosan-free NAu-2 to the highest (∼12%) for the highest chitosan loaded NAu-2 (3:1 ratio). This enhancement of Fe(III) reduction was likely due to the attachment of negatively charged bacterial cells to charge-reversed (e.g., positively charged) NAu-2 surfaces, facilitating the electron transfer between cells and structural Fe(III). With AQDS, Fe(III) reduction extent doubled relative to those without AQDS, but the enhancement effect was similar across all chitosan loadings, suggesting that AQDS was more important than chitosan in enhancing Fe(III) bioreduction. Chitosan-exchanged, biologically reduced NAu-2 was then utilized for removing Cr(VI) in batch experiments with three consecutive spikes of 50 μM Cr. With the first Cr spike, the rate of Cr(VI) removal by charged-reversed NAu-2 that was bioreduced without and with AQDS was ∼1

Influence of Oxygen and Nitrate on Fe (Hydr)oxide Mineral Transformation and Soil Microbial Communities during Redox Cycling.

Science.gov (United States)

Mejia, Jacqueline; Roden, Eric E; Ginder-Vogel, Matthew

2016-04-05

Oscillations between reducing and oxidizing conditions are observed at the interface of anaerobic/oxic and anaerobic/anoxic environments, and are often stimulated by an alternating flux of electron donors (e.g., organic carbon) and electron acceptors (e.g., O2 and NO3(-)). In iron (Fe) rich soils and sediments, these oscillations may stimulate the growth of both Fe-reducing bacteria (FeRB) and Fe-oxidizing bacteria (FeOB), and their metabolism may induce cycling between Fe(II) and Fe(III), promoting the transformation of Fe (hydr)oxide minerals. Here, we examine the mineralogical evolution of lepidocrocite and ferrihydrite, and the adaptation of a natural microbial community to alternating Fe-reducing (anaerobic with addition of glucose) and Fe-oxidizing (with addition of nitrate or air) conditions. The growth of FeRB (e.g., Geobacter) is stimulated under anaerobic conditions in the presence of glucose. However, the abundance of these organisms depends on the availability of Fe(III) (hydr)oxides. Redox cycling with nitrate results in decreased Fe(II) oxidation thereby decreasing the availability of Fe(III) for FeRB. Additionally, magnetite is detected as the main product of both lepidocrocite and ferrihydrite reduction. In contrast, introduction of air results in increased Fe(II) oxidation, increasing the availability of Fe(III) and the abundance of Geobacter. In the lepidocrocite reactors, Fe(II) oxidation by dissolved O2 promotes the formation of ferrihydrite and lepidocrocite, whereas in the ferrihydrite reactors we observe a decrease in magnetite stoichiometry (e.g., oxidation). Understanding Fe (hydr)oxide transformation under environmentally relevant redox cycling conditions provides insight into nutrient availability and transport, contaminant mobility, and microbial metabolism in soils and sediments.

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.

Effects of ferric iron reduction and regeneration on nitrous oxide and methane emissions in a rice soil.

Science.gov (United States)

Huang, Bin; Yu, Kewei; Gambrell, Robert P

2009-01-01

A laboratory soil slurry experiment and an outdoor pot experiment were conducted to study effects of ferric iron (Fe(III)) reduction and regeneration on nitrous oxide (N(2)O) and methane (CH(4)) emissions in a rice (Oryza sativa L.) soil. The anoxic slurry experiment showed that enhancing microbial Fe(III) reduction by ferrihydrite amendment (40 mol Fe g(-1)) transitionally stimulated N(2)O production and lowered CH(4) production by 16% during an initial 33-day incubation. Increased regeneration of Fe(III) through a 4-day aeration period in the Fe-amended slurry compared to the control slurry reduced CH(4) emission by 30% in the subsequent 15-day anaerobic incubation. The pot experiment showed that ferrihydrite amendment (63 micromol Fe g(-1)) stimulated N(2)O fluxes in the days following flooding. The Fe amendment suppression on CH(4) emission was obscured in the early season but became significant upon reflooding in the mid- and late-seasons. As a result, seasonal CH(4) emission in Fe-amended pots was 26% lower than the control with a single 2-day drainage and 69% lower with a double 2-day drainage. The reduction in CH(4) emission upon reflooding from the Fe-amended pots was mainly attributed to the increased Fe(III) regeneration during drainage showing a mechanism of Fe(III) regeneration in mitigating CH(4) emission by short-term drainage in flooded soils.

Complete genome sequences of Desulfosporosinus orientis DSM765(T), Desulfosporosinus youngiae DSM17734(T), Desulfosporosinus meridiei DSM13257(T), and Desulfosporosinus acidiphilus DSM22704(T)

OpenAIRE

Pester, M.; Brambilla, E.; Alazard, Didier; Rattei, T.; Weinmaier, T.; Han, J.; Lucas, S.; Lapidus, A.; Cheng, J. F.; Goodwin, L.; Pitluck, S.; Peters, L.; Ovchinnikova, G.; Teshima, H.; Detter, J. C.

2012-01-01

Desulfosporosinus species are sulfate-reducing bacteria belonging to the Firmicutes. Their genomes will give insights into the genetic repertoire and evolution of sulfate reducers typically thriving in terrestrial environments and able to degrade toluene (Desulfosporosinus youngiae), to reduce Fe(III) (Desulfosporosinus meridiei, Desulfosporosinus orientis), and to grow under acidic conditions (Desulfosporosinus acidiphilus).

Binding of molecular oxygen by an artificial heme analogue: investigation on the formation of an Fe–tetracarbene superoxo complex

KAUST Repository

Anneser, Markus R.

2016-02-26

The dioxygen reactivity of a cyclic iron(II) tetra–NHC-complex (NHC: N-heterocyclic carbene) is investigated. Divergent oxidation behavior is observed depending on the choice of the solvent (acetonitrile or acetone). In the first case, exposure to molecular oxygen leads to an oxygen free Fe(III) whereas in the latter case an oxide bridged Fe(III) dimer is formed. In acetone, an Fe(III)-superoxide can be trapped, isolated and characterized as intermediate at low temperatures. An Fe(III)–O–Fe(III) dimer is formed from the Fe(III) superoxide in acetone upon warming and the molecular structure has been revealed by single crystal X-ray diffraction. It is shown that the oxidation of the Fe(II) complex in both solvents is a reversible process. For the regeneration of the initial Fe(II) complex both organic and inorganic reducing agents can be used.

Thermal, spectral, magnetic and biological studies of thiosemicarbazones complexes with metal ions: Cu(II), Co(II), Ni(II), Fe(III), Zn(II), Mn(II) and UO2(VI)

International Nuclear Information System (INIS)

Mashaly, M.M.; Seleem, H.S.; El-Behairy, M.A.; Habib, H.A.

2004-01-01

Thiosemicarbazones ligands, isatin-3-thiosemicarbazone(HIT) and N-acetylisatin-3-thiosemicarbazone (HAIT), which have tridentate ONN coordinating sites were prepared. The complexes of both ligands with Cu(II), Co(II), Ni(II), Fe(III), Zn(II), Mn(II) and UO 2 (VI) ions were isolated. The ligands and their metal complexes were characterized by elemental analysis, IR, UV-Vis and mass spectra, also by conductance, magnetic moment and TG-DSC measurements. All the transition metal complexes have octahedral configurations, except Cu-complexes which have planar geometry and the UO 2 (VI) complexes which have coordination number 8 and may acquire the distorted dodecahedral geometry. Thermal studies explored the possibility of obtaining new complexes. Inversion from octahedral to square-planar configuration occurred upon heating the parent Ni-HIAT complex to form the corresponding pyrolytic product. The antifungal activity against the tested organisms showed that some metal complexes enhanced the activity with respect to the parent ligands. (author)

Microbial metal reduction by members of the genus Shewanella: novel strategies for anaerobic respiration

International Nuclear Information System (INIS)

Dichristina, Thomas; Bates, David J.; Burns, Justin L.; Dale, Jason R.; Payne, Amanda N.

2006-01-01

Metal-reducing members of the genus Shewanella are important components of the microbial community residing in redox-stratified freshwater and marine environments. Metal-reducing gram-negative bacteria such as Shewanella, however, are presented with a unique physiological challenge: they are required to respire anaerobically on terminal electron acceptors which are either highly insoluble (Fe(III)- and Mn(IV)-oxides) and reduced to soluble end-products or highly soluble (U(VI) and Tc(VII)) and reduced to insoluble end-products. To overcome physiological problems associated with metal solubility, metal-respiring Shewanella are postulated to employ a variety of novel respiratory strategies not found in other gram-negative bacteria which respire on soluble electron acceptors such as O2, NO3 and SO4. The following chapter highlights the latest findings on the molecular mechanism of Fe(III), U(VI) and Tc(VII) reduction by Shewanella, with particular emphasis on electron transport chain physiology.

Importance of c-Type cytochromes for U(VI reduction by Geobacter sulfurreducens

Directory of Open Access Journals (Sweden)

Leang Ching

2007-03-01

Full Text Available Abstract Background In order to study the mechanism of U(VI reduction, the effect of deleting c-type cytochrome genes on the capacity of Geobacter sulfurreducens to reduce U(VI with acetate serving as the electron donor was investigated. Results The ability of several c-type cytochrome deficient mutants to reduce U(VI was lower than that of the wild type strain. Elimination of two confirmed outer membrane cytochromes and two putative outer membrane cytochromes significantly decreased (ca. 50–60% the ability of G. sulfurreducens to reduce U(VI. Involvement in U(VI reduction did not appear to be a general property of outer membrane cytochromes, as elimination of two other confirmed outer membrane cytochromes, OmcB and OmcC, had very little impact on U(VI reduction. Among the periplasmic cytochromes, only MacA, proposed to transfer electrons from the inner membrane to the periplasm, appeared to play a significant role in U(VI reduction. A subpopulation of both wild type and U(VI reduction-impaired cells, 24–30%, accumulated amorphous uranium in the periplasm. Comparison of uranium-accumulating cells demonstrated a similar amount of periplasmic uranium accumulation in U(VI reduction-impaired and wild type G. sulfurreducens. Assessment of the ability of the various suspensions to reduce Fe(III revealed no correlation between the impact of cytochrome deletion on U(VI reduction and reduction of Fe(III hydroxide and chelated Fe(III. Conclusion This study indicates that c-type cytochromes are involved in U(VI reduction by Geobacter sulfurreducens. The data provide new evidence for extracellular uranium reduction by G. sulfurreducens but do not rule out the possibility of periplasmic uranium reduction. Occurrence of U(VI reduction at the cell surface is supported by the significant impact of elimination of outer membrane cytochromes on U(VI reduction and the lack of correlation between periplasmic uranium accumulation and the capacity for uranium

Adsorption of hydrogen gas and redox processes in clays.

Science.gov (United States)

Didier, Mathilde; Leone, Laura; Greneche, Jean-Marc; Giffaut, Eric; Charlet, Laurent

2012-03-20

In order to assess the adsorption properties of hydrogen gas and reactivity of adsorbed hydrogen, we measured H(2)(g) adsorption on Na synthetic montmorillonite-type clays and Callovo-Oxfordian (COx) clayrock using gas chromatography. Synthetic montmorillonites with increasing structural Fe(III) substitution (0 wt %, 3.2 wt %, and 6.4 wt % Fe) were used. Fe in the synthetic montmorillonites is principally present as structural Fe(III) ions. We studied the concomitant reduction of structural Fe(III) in the clays using (57)Fe Mössbauer spectrometry. The COx, which mainly contains smectite/illite and calcite minerals, is also studied together with the pure clay fraction of this clayrock. Experiments were performed with dry clay samples which were reacted with hydrogen gas at 90 and 120 °C for 30 to 45 days at a hydrogen partial pressure close to 0.45 bar. Results indicate that up to 0.11 wt % of hydrogen is adsorbed on the clays at 90 °C under 0.45 bar of relative pressure. (57)Fe Mössbauer spectrometry shows that up to 6% of the total structural Fe(III) initially present in these synthetic clays is reduced upon adsorption of hydrogen gas. No reduction is observed with the COx sample in the present experimental conditions.

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-12-15

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

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

International Nuclear Information System (INIS)

Prado, F.R.

1989-01-01

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

Effect of the tether on the Mg(II), Ca(II), Cu(II) and Fe(III) stability constants and pM values of chelating agents related to EDDHA.

Science.gov (United States)

Sierra, Miguel A; Gómez-Gallego, Mar; Alcázar, Roberto; Lucena, Juan J; Yunta, Felipe; García-Marco, Sonia

2004-11-07

The effect of the length and the structure of the tether on the chelating ability of EDDHA-like chelates have not been established. In this work, PDDHA (propylenediamine-N,N'-bis(o-hydroxyphenyl)acetic acid), BDDHA (butylenediamine-N,N'-bis(o-hydroxyphenyl)acetic acid) and XDDHA (p-xylylenediamine-N,N'-bis(o-hydroxyphenyl)acetic acid) have been obtained and their chemical behaviour has been studied and compared with that of EDDHA following our methodology. The purity of the chelating agents, and their protonation, Ca(II), Mg(II), Fe(III) and Cu(II) stability constants and pM values have been determined. The stability constants and pM values indicate that EDDHA forms the most stable chelates followed by PDDHA. However, the differences among the pFe values are small when a nutrient solution is used, and in these conditions the XDDHA/Fe(III) chelate is the most stable. The results obtained in this work indicate that all the chelating agents studied can be used as iron chlorosis correctors and they can be applied to soil/plant systems.

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.

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.

Interactions between magnetite and humic substances: redox reactions and dissolution processes.

Science.gov (United States)

Sundman, Anneli; Byrne, James M; Bauer, Iris; Menguy, Nicolas; Kappler, Andreas

2017-10-19

Humic substances (HS) are redox-active compounds that are ubiquitous in the environment and can serve as electron shuttles during microbial Fe(III) reduction thus reducing a variety of Fe(III) minerals. However, not much is known about redox reactions between HS and the mixed-valent mineral magnetite (Fe 3 O 4 ) that can potentially lead to changes in Fe(II)/Fe(III) stoichiometry and even dissolve the magnetite. To address this knowledge gap, we incubated non-reduced (native) and reduced HS with four types of magnetite that varied in particle size and solid-phase Fe(II)/Fe(III) stoichiometry. We followed dissolved and solid-phase Fe(II) and Fe(III) concentrations over time to quantify redox reactions between HS and magnetite. Magnetite redox reactions and dissolution processes with HS varied depending on the initial magnetite and HS properties. The interaction between biogenic magnetite and reduced HS resulted in dissolution of the solid magnetite mineral, as well as an overall reduction of the magnetite. In contrast, a slight oxidation and no dissolution was observed when native and reduced HS interacted with 500 nm magnetite. This variability in the solubility and electron accepting and donating capacity of the different types of magnetite is likely an effect of differences in their reduction potential that is correlated to the magnetite Fe(II)/Fe(III) stoichiometry, particle size, and crystallinity. Our study suggests that redox-active HS play an important role for Fe redox speciation within minerals such as magnetite and thereby influence the reactivity of these Fe minerals and their role in biogeochemical Fe cycling. Furthermore, such processes are also likely to have an effect on the fate of other elements bound to the surface of Fe minerals.

Immobilization of radionuclides and heavy metals through anaerobic bio-oxidation of Fe(II)

International Nuclear Information System (INIS)

Lack, J.G.; Chaudhuri, S.K.; Kelly, S.D.; Kemner, K.M.; O'Connor, S.M.; Coates, J.D.

2002-01-01

Adsorption of heavy metals and radionuclides (HMR) onto iron and manganese oxides has long been recognized as an important reaction for the immobilization of these compounds. However, in environments containing elevated concentrations of these HMR the adsorptive capacity of the iron and manganese oxides may well be exceeded, and the HMR can migrate as soluble compounds in aqueous systems. Here we demonstrate the potential of a bioremediative strategy for HMR stabilization in reducing environments based on the recently described anaerobic nitrate-dependent Fe(II) oxidation by Dechlorosoma species. Bio-oxidation of 10 mM Fe(II) and precipitation of Fe(III) oxides by these organisms resulted in rapid adsorption and removal of 55 μM uranium and 81 μM cobalt from solution. The adsorptive capacity of the biogenic Fe(III) oxides was lower than that of abiotically produced Fe(III) oxides (100 μM for both metals), which may have been a result of steric hindrance by the microbial cells on the iron oxide surfaces. The binding capacity of the biogenic oxides for different heavy metals was indirectly correlated to the atomic radius of the bound element. X-ray absorption spectroscopy indicated that the uranium was bound to the biogenically produced Fe(III) oxides as U(VI) and that the U(VI) formed bidentate and tridentate inner-sphere complexes with the Fe(III) oxide surfaces. Dechlorosoma suillum oxidation was specific for Fe(II), and the organism did not enzymatically oxidize U(IV) or Co(II). Small amounts (less than 2.5 μM) of Cr(III) were reoxidized by D. suillum; however, this appeared to be inversely dependent on the initial concentration of the Cr(III). The results of this study demonstrate the potential of this novel approach for stabilization and immobilization of HMR in the environment.

Assessment of heavy metal tolerance and hexavalent chromium reducing potential of Corynebacterium paurometabolum SKPD 1204 isolated from chromite mine seepage

Directory of Open Access Journals (Sweden)

Amal Kanti Paul

2016-07-01

Full Text Available Corynebacterium paurometabolum SKPD 1204 (MTCC 8730, a heavy metal tolerant and chromate reducing bacterium isolated from chromite mine seepage of Odisha, India has been evaluated for chromate reduction under batch culture. The isolate was found to tolerate metals like Co(II, Cu(II, Ni(II, Mn(II, Zn(II, Fe(III and Hg(II along with Cr(VI and was resistant to different antibiotics as evaluated by disc-diffusion method. The isolate, SKPD 1204 was found to reduce 62.5% of 2 mM Cr(VI in Vogel Bonner broth within 8 days of incubation. Chromate reduction capability of SKPD 1204 decreased with increase in Cr(VI concentration, but increased with increase in cell density and attained its maximum at 1010 cells/mL. Chromate reducing efficiency of SKPD 1204 was promoted in the presence of glycerol and glucose, while the highest reduction was recorded at pH 7.0 and 35 °C. The reduction process was inhibited by divalent cations Zn(II, Cd(II, Cu(II, and Ni(II, but not by Mn(II. Anions like nitrate, phosphate, sulphate and sulphite was found to be inhibitory to the process of Cr(VI reduction. Similarly, sodium fluoride, carbonyl cyanide m-chlorophenylhydrazone, sodium azide and N, N,-Di cyclohexyl carboiimide were inhibitory to chromate reduction, while 2,4-dinitrophenol appeared to be neither promotive nor inhibitory to the process.

[Effects of iron on azoreduction by Shewanella decolorationis S12].

Science.gov (United States)

Chen, Xing-Juan; Xu, Mei-Ying; Sun, Guo-Ping

2010-01-01

The effects of soluble and insoluble Fe(III) on anaerobic azoreduction by Shewanella decolorationis S12 were examined in a series of experiments. Results showed that the effects of iron on anaerobic azoreduction depended on the solubility and concentration of the compounds. Azoreduction was inhibited by insoluble Fe(III) and 0.05-2 mmol/L Fe2 O3 all decelerated the azoreduction activity of 0.2 mmol/L amaranth, but the increase in the concentrations of Fe2O3 did not cause an increasing inhibition. Soluble Fe(III) of which concentration less than 0.4 mmol/L enhanced azoreduction activity of 0.2 mmol/L amaranth but there was no linear relationship between the concentration of soluble Fe(III) and azoreduction activity. Soluble Fe(III) of which concentration more than 1 mmol/L inhibited azoreduction activity of 0.2 mmol/L amaranth and an increasing concentration resulted in an increased inhibition. The inhibition was strengthened under the conditions of limited electron donor. On the other hand, soluble Fe(III) and Fe(II) could relieve the inhibition of azoreduction by dicumarol which blocked quinone cycle. It suggests that in addition to quinone cycle, there is a Fe(III) Fe(II) cycle shuttling electrons in cytoplasmic and periplasmic environment. That is the reason why low concentration of soluble Fe(III) or Fe (II) can enhance azoreduction of S. decolorationis S12. It also indicates that insoluble Fe(III) and high concentration of soluble Fe(III) do compete with azo dye for electrons once it acts as electron acceptor. Thus, when iron and azo dye coexisted, iron could serve as an electron transfer agent or electron competitive inhibitor for anaerobic azoreduction under different conditions. High efficiency of azoreduction can be achieved through controlling the solubility and concentration of irons.

The Complex Conductivity Signature of Geobacter Species in Geological Media

Science.gov (United States)

Brown, I.; Atekwana, E. A.; Sarkisova, S.; Achang, M.

2013-12-01

The Complex Conductivity (CC) technique is a promising biogeophysical approach for sensing microbially-induced changes in geological media because of its low-invasive character and sufficient sensitivity to enhanced microbial activity in the near subsurface. Geobacter species have been shown to play important roles in the bioremediation of groundwater contaminated with petroleum and landfill leachate. This capability is based on the ability of Geobacter species to reduce Fe(III) by transferring of electrons from the reduced equivalents to Fe(III) rich minerals through respiration chain and special metallic-like conductors - pili. Only the cultivation of Geobacter species on Fe(III) oxides specifically express pili biosynthesis. Moreover, mutants that cannot produce pili are unable to reduce Fe(III) oxides. However, little is known about the contribution of these molecular conductors (nanowires) to the generation of complex conductivity signatures in geological media. Here, we present the results about the modulation of CC signatures in geological media by Geobacter sulfurreducens (G.s.). Cultures of wild strain G.s. and its pilA(-) mutant were anaerobically cultivated in the presence of the pair of such donors and acceptors of electrons: acetate - fumarate, and acetate - magnetite under anaerobic conditions. Each culture was injected in CC sample holders filled either with N2-CO2 mix (planktonic variant) or with this gases mix and glass beads, d=1 mm, (porous medium variant). Both strains of G.s. proliferated well in a medium supplemented with acetate-fumarate. However, pilA(-) mutant did not multiply in a medium supplemented with ox-red pair yeast extract - magnetite. This observation confirmed that only wild pilA(+) strain is capable of the dissimilatory reduction of Fe(III) within magnetite molecule. The measurement of CC responses from planktonic culture of G.s. wild strain grown with acetate-fumarate did not show linear correlation with their magnitudes but

Biotransformation of uranium and transition metal citrate complexes by clostridia

International Nuclear Information System (INIS)

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

2002-01-01

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

Biogenic uraninite precipitation and its reoxidation by iron(III) (hydr)oxides: A reaction modeling approach

Science.gov (United States)

Spycher, Nicolas F.; Issarangkun, Montarat; Stewart, Brandy D.; Sevinç Şengör, S.; Belding, Eileen; Ginn, Tim R.; Peyton, Brent M.; Sani, Rajesh K.

2011-08-01

One option for immobilizing uranium present in subsurface contaminated groundwater is in situ bioremediation, whereby dissimilatory metal-reducing bacteria and/or sulfate-reducing bacteria are stimulated to catalyze the reduction of soluble U(VI) and precipitate it as uraninite (UO 2). This is typically accomplished by amending groundwater with an organic electron donor. It has been shown, however, that once the electron donor is entirely consumed, Fe(III) (hydr)oxides can reoxidize biogenically produced UO 2, thus potentially impeding cleanup efforts. On the basis of published experiments showing that such reoxidation takes place even under highly reducing conditions (e.g., sulfate-reducing conditions), thermodynamic and kinetic constraints affecting this reoxidation are examined using multicomponent biogeochemical simulations, with particular focus on the role of sulfide and Fe(II) in solution. The solubility of UO 2 and Fe(III) (hydr)oxides are presented, and the effect of nanoscale particle size on stability is discussed. Thermodynamically, sulfide is preferentially oxidized by Fe(III) (hydr)oxides, compared to biogenic UO 2, and for this reason the relative rates of sulfide and UO 2 oxidation play a key role on whether or not UO 2 reoxidizes. The amount of Fe(II) in solution is another important factor, with the precipitation of Fe(II) minerals lowering the Fe +2 activity in solution and increasing the potential for both sulfide and UO 2 reoxidation. The greater (and unintuitive) UO 2 reoxidation by hematite compared to ferrihydrite previously reported in some experiments can be explained by the exhaustion of this mineral from reaction with sulfide. Simulations also confirm previous studies suggesting that carbonate produced by the degradation of organic electron donors used for bioreduction may significantly increase the potential for UO 2 reoxidation through formation of uranyl carbonate aqueous complexes.

Reductive and sorptive properties of sulfate green rust (GRSO4)

DEFF Research Database (Denmark)

Nedel, Sorin

The Fe(II), Fe(III) hydroxide containing sulfate in its structure, called sulfate green rust (GRSO4), can effectively reduce and convert contaminants to less mobile and less toxic forms. However, the ability of GRSO4 to remove positively charged species from solution, via sorption, is very limited...

Batch adsorptive removal of Fe(III, Cu(II and Zn(II ions in aqueous and aqueous organic–HCl media by Dowex HYRW2-Na Polisher resin as adsorbents

Directory of Open Access Journals (Sweden)

Abdul-Aleem Soliman Aboul-Magd

2016-09-01

Full Text Available Of the metal ions in tap, Nile, waste and sea water samples and some ores were carried out. Removal of heavy metal ions such as Fe(III, Cd(II, Zn(II, Cu(II, Mn(II, Mg(II, and Pb(II from water and wastewater is obligatory in order to avoid water pollution. Batch shaking adsorption experiments to evaluate the performance of nitric and hydrochloric acid solutions in the removal of metal ions by cation exchange resin at the same conditions for both, such as the effect of initial metal ion concentration, different proportions of some organic solvents, H+-ion concentrations and reaction temperature on the partition coefficients. The metal adsorption for the cation exchanger was found to be significant in different media for both nitric and hydrochloric acids, i.e., the adsorption up take of metal ions presented in this work is very significant depending on the characteristics of ions and on the external concentrations of solute. The presence of low ionic strength or low concentration of acids does have a significant adsorption of metal ions on ion-exchange resin. The results show that the ion exchanger could be employed for the preconcentration, separation and the determination.

Interactions of trivalent and tetravalent heavy metal-siderophore complexes with pseudomonas fluorescens

International Nuclear Information System (INIS)

Yoshida, T.; Ozaki, T.; Ohnuki, T.; Francis, A.J.

2004-01-01

We investigated the interactions of the Fe(III)-, Eu(III)-, and Hf(IV)-desferrioxamine B (DFO) complexes with the Gram-negative aerobic bacterium Pseudomonas fluorescens. Potentiometric titration of 1:1 Fe(III)-, Eu(III)-, and Hf(IV)-DFO complexes showed that Hf(IV) formed a strong complex with DFO whose stability was comparable to that of the Fe(III)-DFO complex, while Eu(III) formed a weaker one. DFO in a growth medium was not degraded by P. fluorescens. Contact of P. fluorescens cells with the Fe(III)-, Eu(III)-, and Hf(IV)-DFO complexes at pH 4-9 revealed that there was negligible adsorption of Hf(IV) and Fe(III), whereas Eu(III) was dissociated from DFO and was readily adsorbed by the cells. These results suggest that Fe(III) and Hf(IV) form stable complexes with DFO and are not adsorbed by P. fluorescens cells. Europium(III) forms a weaker complex with DFO than Fe(III) and Hf(IV) do and its DFO complex is readily dissociated in the presence of the cells. (orig.)

Comparison of lactate, formate, and propionate as hydrogen donors for the reductive dehalogenation of trichloroethene in a continuous-flow column

Science.gov (United States)

Azizian, Mohammad F.; Marshall, Ian P. G.; Behrens, Sebastian; Spormann, Alfred M.; Semprini, Lewis

2010-04-01

A continuous-flow column study was conducted to analyze the reductive dehalogenation of trichloroethene (TCE) with aquifer material with high content of iron oxides. The column was bioaugmented with the Point Mugu (PM) culture, which is a mixed microbial enrichment culture capable of completely transforming TCE to ethene (ETH). We determined whether lactate, formate, or propionate fermentation resulted in more effective dehalogenation. Reductive dehalogenation, fermentation, and sulfate, Fe(III), and Mn(IV) reduction were all exhibited within the column. Different steady-states of dehalogenation were achieved based on the concentration of substrates added, with effective transformation to ETH obtained when ample electron donor equivalents were provided. Most of the metabolic reducing equivalents were channeled to sulfate, Fe(III), and Mn(IV) reduction. When similar electron reducing equivalents were added, the most effective dehalogenation was achieved with formate, with 14% of the electron equivalents going towards dehalogenation reactions, compared to 6.5% for lactate and 9.6% for propionate. Effective dehalogenation was maintained over 1000 days of column operation. Over 90% of electron equivalents added could be accounted for by the different electron accepting processes in the column, with 50% associated with soluble and precipitated Fe(II) and Mn(II). Bulk Fe(III) and Mn(IV) reduction was rather associated with lactate and propionate addition than formate addition. Sulfate reduction was a competing electron acceptor reaction with all three electron donors. DNA was extracted from solid coupon samples obtained during the course of the experiment and analyzed using 16S rRNA gene clone libraries and quantitative PCR. Lactate and propionate addition resulted in a significant increase in Geobacter, Spirochaetes, and Desulfitobacterium phylotypes relative to " Dehalococcoides" when compared to formate addition. Results from the molecular biological analyses support

Surface complexation modeling of the effects of phosphate on uranium(VI) adsorption

Energy Technology Data Exchange (ETDEWEB)

Romero-Gonzalez, M.R.; Cheng, T.; Barnett, M.O. [Auburn Univ., AL (United States). Dept. of Civil Engeneering; Roden, E.E. [Wisconsin Univ., Madison, WI (United States). Dept. of Geology and Geophysics

2007-07-01

Previous published data for the adsorption of U(VI) and/or phosphate onto amorphous Fe(III) oxides (hydrous ferric oxide, HFO) and crystalline Fe(III) oxides (goethite) was examined. These data were then used to test the ability of a commonly-used surface complexation model (SCM) to describe the adsorption of U(VI) and phosphate onto pure amorphous and crystalline Fe(III) oxides and synthetic goethite-coated sand, a surrogate for a natural Fe(III)-coated material, using the component additivity (CA) approach. Our modeling results show that this model was able to describe U(VI) adsorption onto both amorphous and crystalline Fe(III) oxides and also goethite-coated sand quite well in the absence of phosphate. However, because phosphate adsorption exhibits a stronger dependence on Fe(III) oxide type than U(VI) adsorption, we could not use this model to consistently describe phosphate adsorption onto both amorphous and crystalline Fe(III) oxides and goethite-coated sand. However, the effects of phosphate on U(VI) adsorption could be incorporated into the model to describe U(VI) adsorption to both amorphous and crystalline Fe(III) oxides and goethite-coated sand, at least for an initial approximation. These results illustrate both the potential and limitations of using surface complexation models developed from pure systems to describe metal/radionuclide adsorption under more complex conditions. (orig.)

Surface complexation modeling of the effects of phosphate on uranium(VI) adsorption

International Nuclear Information System (INIS)

Romero-Gonzalez, M.R.; Cheng, T.; Barnett, M.O.; Roden, E.E.

2007-01-01

Previous published data for the adsorption of U(VI) and/or phosphate onto amorphous Fe(III) oxides (hydrous ferric oxide, HFO) and crystalline Fe(III) oxides (goethite) was examined. These data were then used to test the ability of a commonly-used surface complexation model (SCM) to describe the adsorption of U(VI) and phosphate onto pure amorphous and crystalline Fe(III) oxides and synthetic goethite-coated sand, a surrogate for a natural Fe(III)-coated material, using the component additivity (CA) approach. Our modeling results show that this model was able to describe U(VI) adsorption onto both amorphous and crystalline Fe(III) oxides and also goethite-coated sand quite well in the absence of phosphate. However, because phosphate adsorption exhibits a stronger dependence on Fe(III) oxide type than U(VI) adsorption, we could not use this model to consistently describe phosphate adsorption onto both amorphous and crystalline Fe(III) oxides and goethite-coated sand. However, the effects of phosphate on U(VI) adsorption could be incorporated into the model to describe U(VI) adsorption to both amorphous and crystalline Fe(III) oxides and goethite-coated sand, at least for an initial approximation. These results illustrate both the potential and limitations of using surface complexation models developed from pure systems to describe metal/radionuclide adsorption under more complex conditions. (orig.)

Photocatalytic Reduction of Hexavalent Chromium Induced by Photolysis of Ferric/tartrate Complex

Energy Technology Data Exchange (ETDEWEB)

Feng, Xianghua; Ding, Shimin; Zhang, Lixian [Yangtze Normal Univ., Fuling (China)

2012-11-15

Photocatalytic reduction of hexavalent chromium (Cr(VI)) in ferric-tartrate system under irradiation of visible light was investigated. Effects of light resources, initial pH value and initial concentration of various reactants on Cr(VI) photocatalytic reduction were studied. Photoreaction kinetics was discussed and a possible photochemical pathway was proposed. The results indicate that Fe(III)-tartrate system is able to rapidly and effectively photocatalytically reduce Cr(VI) utilizing visible light. Initial pH variations results in the concentration changes of Fe(III)-tartrate complex in this system, and pH at 3.0 is optimal for Cr(VI) photocatalytic reduction. Efficiency of Cr(VI) photocatalytic reduction increases with increasing initial concentrations of Cr(VI), Fe(III) and tartrate. Kinetics analysis indicates that initial Fe(III) concentration affects Cr(VI) photoreduction most significantly.

Photocatalytic Reduction of Hexavalent Chromium Induced by Photolysis of Ferric/tartrate Complex

International Nuclear Information System (INIS)

Feng, Xianghua; Ding, Shimin; Zhang, Lixian

2012-01-01

Photocatalytic reduction of hexavalent chromium (Cr(VI)) in ferric-tartrate system under irradiation of visible light was investigated. Effects of light resources, initial pH value and initial concentration of various reactants on Cr(VI) photocatalytic reduction were studied. Photoreaction kinetics was discussed and a possible photochemical pathway was proposed. The results indicate that Fe(III)-tartrate system is able to rapidly and effectively photocatalytically reduce Cr(VI) utilizing visible light. Initial pH variations results in the concentration changes of Fe(III)-tartrate complex in this system, and pH at 3.0 is optimal for Cr(VI) photocatalytic reduction. Efficiency of Cr(VI) photocatalytic reduction increases with increasing initial concentrations of Cr(VI), Fe(III) and tartrate. Kinetics analysis indicates that initial Fe(III) concentration affects Cr(VI) photoreduction most significantly

Vivianite Precipitation and Phosphate Sorption following Iron Reduction in Anoxic Soils

DEFF Research Database (Denmark)

Heiberg, Lisa; Bender Koch, Christian; Kjærgaard, Charlotte

2012-01-01

, the Fe(II) production reached its maximum and 34% of the citrate–bicarbonate–dithionite extractable Fe (FeCBD) was reduced to Fe(II) in the sandy soil. The peat soil showed a much faster reduction of Fe(III) and the maximum reduction of 89% of FeCBD was reached after 200 d. Neoformation...

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Electrochemical study of FeIII(Fc2Ph2P)Cl revealed ferrocenebased two-electron quasi-reversible oxidation at 0.72 V indicating no observable coupling of the ferrocene moieties. The higher oxidation state of Fe(III) reduces the electron releasing tendency of the porphyrin ring and thus make the ferrocene oxidation difficult.

Vertical variability of arsenic concentrations under the control of iron-sulfur-arsenic interactions in reducing aquifer systems

Science.gov (United States)

Pi, Kunfu; Wang, Yanxin; Postma, Dieke; Ma, Teng; Su, Chunli; Xie, Xianjun

2018-06-01

High spatial variability of arsenic (As) concentration in geogenic As-contaminated groundwater has been commonly observed worldwide, but the underlying reasons remain not well understood. Selecting a sulfate-containing, As-affected aquifer at the Datong Basin, northern China as the study area and combining hydrogeochemical investigation and sediment extraction with reactive transport modeling, this work elucidated the roles of Fe-S-As interactions in regulating the vertical variation of As concentration in the groundwater. Dissolved As concentration varied between 0.05 and 18 μmol/L, but generally increased in the depth of 20-25 m and then decreased in 25-30 m. The high-As groundwater contained low Fe(II) (groundwater devoid of sulfate reduction. The reductive dissolution of As-bearing Fe(III) oxides coupled to the degradation of organic matter with an estimated maximum rate of 0.22 mmol C/L/yr, mainly accounted for the depth-dependent increase of As concentration in the upper part of the shallow aquifer (groundwater but also probably co-precipitated As to prompt As decrease in the depth of 25-30 m. Arsenite adsorbed on remaining Fe(III) oxides and newly-formed Fe(II) sulfides is another important pool of As in the aquifer, which varies in response to the extents of Fe(III)-oxide and sulfate reduction and consequently alters As distribution coefficient between the solid and the aqueous phases. This study highlights the importance of coupled geochemical cycling of Fe, S and As for As mobilization and reveals how it regulates As partitioning between groundwater and sediments.

Characterization of Co(III) EDTA-Reducing Bacteria in Metal- and Radionuclide-Contaminated Groundwater

Energy Technology Data Exchange (ETDEWEB)

Gao, Weimin [Arizona State University; Gentry, Terry J [ORNL; Mehlhorn, Tonia L [ORNL; Carroll, Sue L [ORNL; Jardine, Philip M [ORNL; Zhou, Jizhong [University of Oklahoma, Norman

2010-01-01

The Waste Area Grouping 5 (WAG5) site at Oak Ridge National Laboratory has a potential to be a field site for evaluating the effectiveness of various bioremediation approaches and strategies. The site has been well studied in terms of its geological and geochemical properties over the past decade. However, despite the importance of microorganisms in bioremediation processes, the microbiological populations at the WAG5 site and their potential in bioremediation have not been similarly evaluated. In this study, we initiated research to characterize the microbial populations in WAG5 groundwater. Approximately 100 isolates from WAG5 groundwater were isolated and selected based on colony morphology. Fifty-five unique isolates were identified by BOX-PCR and subjected to further characterization. 16S rRNA sequences indicated that these isolates belong to seventeen bacterial genera including Alcaligenes (1 isolate), Aquamonas (1), Aquaspirillum (1), Bacillus (10), Brevundimonas (5), Caulobacter (7), Dechloromonas (2), Janibacter (1), Janthinobacterium (2), Lactobacillus (1), Paenibacillus (4), Pseudomonas (9), Rhodoferax (1), Sphingomonas (1), Stenotrophomonas (6), Variovorax (2), and Zoogloea (1). Metal respiration assays identified several isolates, which phylogenically belong or are close to Caulobacter, Stenotrophomonas, Bacillus, Paenibacillus and Pseudomonas, capable of reducing Co(III)EDTA- to Co(II)EDTA{sup 2-} using the defined M1 medium under anaerobic conditions. In addition, using WAG5 groundwater directly as the inoculants, we found that organisms associated with WAG5 groundwater can reduce both Fe(III) and Co(III) under anaerobic conditions. Further assays were then performed to determine the optimal conditions for Co(III) reduction. These assays indicated that addition of various electron donors including ethanol, lactate, methanol, pyruvate, and acetate resulted in metal reduction. These experiments will provide useful background information for future

Anaerobic degradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA).

Science.gov (United States)

Finneran, K T; Lovley, D R

2001-05-01

The potential for anaerobic degradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) was investigated in laboratory incubations of sediments from a petroleum-contaminated aquifer and in aquatic sediments. The addition of humic substances (HS) stimulated the anaerobic degradation of MTBE in aquifer sediments in which Fe(III) was available as an electron acceptor. This is attributed to the fact that HS and other extracellular quinones can stimulate the activity of Fe(III)-reducing microorganisms by acting as an electron shuttle between Fe(III)-reducing microorganisms and insoluble Fe(III) oxides. MTBE was not degraded in aquifer sediments without Fe(III) and HS. [14C]-MTBE added to aquatic sediments adapted for anaerobic MTBE degradation was converted to 14CO2 in the presence or absence of HS or the HS analog, anthraquione-2,6-disulfonate. Unamended aquatic sediments produced 14CH4 as well as 14CO2 from [14C]-MTBE. The aquatic sediments also rapidly consumed TBA under anaerobic conditions and converted [14C]-TBA to 14CH4 and 14CO2. An adaptation period of ca. 250-300 days was required prior to the most rapid anaerobic MTBE degradation in both sediment types, whereas TBA was metabolized in the aquatic sediments without a lag. These results demonstrate that, under the appropriate conditions, MTBE and TBA can be degraded in the absence of oxygen. This suggests that it may be possible to design strategies for the anaerobic remediation of MTBE in petroleum-contaminated subsurface environments.

Complete Genome Sequence of the Fruiting Myxobacterium Melittangium boletus DSM 14713.

Science.gov (United States)

Treuner-Lange, Anke; Bruckskotten, Marc; Rupp, Oliver; Goesmann, Alexander; Søgaard-Andersen, Lotte

2017-11-09

The formation of spore-filled fruiting bodies in response to starvation represents a hallmark of many members of the order Myxococcales Here, we present the complete 9.9-Mb genome of the fruiting type strain Melittangium boletus DSM 14713, the first member of this genus to have its genome sequenced. Copyright © 2017 Treuner-Lange et al.

Indolenine meso-substituted dibenzotetraaza[14]annulene and its coordination chemistry toward the transition metal ions Mn(III), Fe(III), Co(II), Ni(II), Cu(II), and Pd(II).

Science.gov (United States)

Khaledi, Hamid; Olmstead, Marilyn M; Ali, Hapipah Mohd; Thomas, Noel F

2013-02-18

A new dibenzotetraaza[14]annulene bearing two 3,3-dimethylindolenine fragments at the meso positions (LH(2)), has been synthesized through a nontemplate method. X-ray crystallography shows that the whole molecule is planar. The basicity of the indolenine ring permits the macrocycle to be protonated external to the core and form LH(4)(2+)·2Cl(-). Yet another structural modification having strong C-H···π interactions was found in the chloroform solvate of LH(2). The latter two modifications are accompanied by a degree of nonplanar distortion. The antiaromatic core of the macrocycle can accommodate a number of metal ions, Mn(III), Fe(III), Co(II), Ni(II) and Cu(II), to form complexes of [Mn(L)Br], [Mn(L)Cl], [Fe(LH(2))Cl(2)](+)·Cl(-), [Co(L)], [Ni(L)], and [Cu(L)]. In addition, the reaction of LH(2) with the larger Pd(II) ion leads to the formation of [Pd(2)(LH(2))(2)(OAc)(4)] wherein the macrocycle acts as a semiflexible ditopic ligand to coordinate pairs of metal ions via its indolenine N atoms into dinuclear metallocycles. The compounds LH(2), [Co(L)], and [Ni(L)] are isostructural and feature close π-stacking as well as linear chain arrangements in the case of the metal complexes. Variable temperature magnetic susceptibility measurements showed thermally induced paramagnetism in [Ni(L)].

Fe(II)-regulated moderate pre-oxidation of Microcystis aeruginosa and formation of size-controlled algae flocs for efficient flotation of algae cell and organic matter.

Science.gov (United States)

Qi, Jing; Lan, Huachun; Liu, Ruiping; Liu, Huijuan; Qu, Jiuhui

2018-06-15

The coagulation/flocculation/flotation (C/F/F) process is becoming a popular method for algae-laden water treatment. However, the efficiency of flotation is highly dependent on the ability of the preceding coagulation/flocculation process to form flocculated algae flocs. This study aims to improve the Microcystis aeruginosa flotation efficiency from algae cell and organic matter aspects by applying Fe(II)-regulated pretreatment enhanced Al coagulation process. The ability of the C/F/F process to remove cyanobacterial cells can be enhanced from 8% to 99% at a Fe(II) dose of 30 μM. The Al dose needed can be reduced by more than half while achieving successful flotation. The introduced Fe(II) after KMnO 4 can not only realize moderate pre-oxidation of cyanobacterial cells, but also form in-situ Fe(III). The DOC value can also be decreased significantly due to the formation of in-situ Fe(III), which is more efficient in dissolved organic matter (DOM) removal compared with pre-formed Fe(III). In addition, the gradually hydrolyzed in-situ Fe(III) can facilitate the hydrolysis of Al as a dual-coagulant and promote the clustering and cross-linking of Al hydrolyzates, which can enhance the formation of size-controlled algae flocs. Finally, the size-controlled algae flocs can be effectively floated by the bubbles released in the flotation process due to the efficient collision and attachment between flocs and bubbles. Therefore, the efficient flotation of algae cell and organic matter can be realized by the Fe(II) regulated moderate pre-oxidation of M. aeruginosa and formation of size-controlled algae flocs. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

Science.gov (United States)

Chen, Chunmei; Thompson, Aaron

2018-01-16

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

Synthesis, characterization, spectroscopic and catalytic oxidation studies of Fe(III), Ni(II), Co(III), V(IV) and U(VI) Schiff base complexes with N, O donor ligands derived from 2,3-diaminopyridine

Energy Technology Data Exchange (ETDEWEB)

Zabardasti, Abedien; Shangaie, Sayed Asad [Lorestan Univ., Khorramabad (Iran, Islamic Republic of). Dept. of Chemistry

2016-10-15

Fifteen new complexes of transition metals were designed using three Schiff base ligands and aldol condensation of 2,3-diaminopyridine with 5-R-2-hydroxybenzaldehyde (R = F, Cl, Br) in the 1:2 molar ratio. The tetradentate ligands N,N{sup '}-bis(5-R-2-hydroxybenzaldehyde) pyridine were acquired with the common formula H{sub 2}[(5-R-sal){sub 2}py] and characterized by IR, UV-Vis spectra, {sup 1}H-NMR and elemental analysis. These ligands produce 1:1 complexes M[(5-R-sal){sub 2}py] with Fe(III), Ni(II), Co(III), V(IV) and U(VI) metal ions. The electronic property and nature of complexes were identified by IR, UV-Vis spectra, elemental analysis, X-ray crystallography and cyclic voltammetric methods. The catalytic activity of complexes for epoxidation of styrene with UHP as primary oxidant at minimal temperature (10 C) has been planned. The spectral data of the ligands and their complexes are deliberate in connection with the structural changes which happen due to complex preparation. The electrochemical outcome has good conformability with what suggested for electronic interaction among metal center and ligand by the UV-Vis and IR measurements.

Transformation of vivianite by anaerobic nitrate-reducing iron-oxidizing bacteria.

Science.gov (United States)

Miot, J; Benzerara, K; Morin, G; Bernard, S; Beyssac, O; Larquet, E; Kappler, A; Guyot, F

2009-06-01

In phosphate-rich environments, vivianite (Fe(II)(3)(PO(4))(2), 8H(2)O) is an important sink for dissolved Fe(II) and is considered as a very stable mineral due to its low solubility at neutral pH. In the present study, we report the mineralogical transformation of vivianite in cultures of the nitrate-reducing iron-oxidizing bacterial strain BoFeN1 in the presence of dissolved Fe(II). Vivianite was first transformed into a greenish phase consisting mostly of an amorphous mixed valence Fe-phosphate. This precipitate became progressively orange and the final product of iron oxidation consisted of an amorphous Fe(III)-phosphate. The sub-micrometer analysis by scanning transmission X-ray microscopy of the iron redox state in samples collected at different stages of the culture indicated that iron was progressively oxidized at the contact of the bacteria and at a distance from the cells in extracellular minerals. Iron oxidation in the extracellular minerals was delayed by a few days compared with cell-associated Fe-minerals. This led to strong differences of Fe redox in between these two types of minerals and finally to local heterogeneities of redox within the sample. In the absence of dissolved Fe(II), vivianite was not significantly transformed by BoFeN1. Whereas Fe(II) oxidation at the cell contact is most probably directly catalyzed by the bacteria, vivianite transformation at a distance from the cells might result from oxidation by nitrite. In addition, processes leading to the export of Fe(III) from bacterial oxidation sites to extracellular minerals are discussed including some involving colloids observed by cryo-transmission electron microscopy in the culture medium.

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

Directory of Open Access Journals (Sweden)

La Harimu

2010-06-01

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

Potential function of added minerals as nucleation sites and effect of humic substances on mineral formation by the nitrate-reducing Fe(II)-oxidizer Acidovorax sp. BoFeN1.

Science.gov (United States)

Dippon, Urs; Pantke, Claudia; Porsch, Katharina; Larese-Casanova, Phil; Kappler, Andreas

2012-06-19

The mobility of toxic metals and the transformation of organic pollutants in the environment are influenced and in many cases even controlled by iron minerals. Therefore knowing the factors influencing iron mineral formation and transformation by Fe(II)-oxidizing and Fe(III)-reducing bacteria is crucial for understanding the fate of contaminants and for the development of remediation technologies. In this study we followed mineral formation by the nitrate-reducing Fe(II)-oxidizing strain Acidovorax sp. BoFeN1 in the presence of the crystalline Fe(III) (oxyhydr)oxides goethite, magnetite and hematite added as potential nucleation sites. Mössbauer spectroscopy analysis of minerals precipitated by BoFeN1 in (57)Fe(II)-spiked microbial growth medium showed that goethite was formed in the absence of mineral additions as well as in the presence of goethite or hematite. The presence of magnetite minerals during Fe(II) oxidation induced the formation of magnetite in addition to goethite, while the addition of humic substances along with magnetite also led to goethite but no magnetite. This study showed that mineral formation not only depends on the aqueous geochemical conditions but can also be affected by the presence of mineral nucleation sites that initiate precipitation of the same underlying mineral phases.

Kinetics of abiotic nitrous oxide production via oxidation of hydroxylamine by particulate metals in seawater

Science.gov (United States)

Cavazos, A. R.; Taillefert, M.; Glass, J. B.

2016-12-01

The oceans are a significant of nitrous oxide (N2O) to the atmosphere. Current models of global oceanic N2­O flux focus on microbial N2O cycling and often ignore abiotic reactions, such as the thermodynamically favorable oxidation of the nitrification intermediate hydroxylamine (NH2OH) by Mn(IV) or Fe(III). At circumneutral pH, NH2OH oxidation is more thermodynamically favorable via Mn(IV) than Fe(III) reduction. We characterized the kinetics of NH2OH oxidation in synthetic ocean water at pH 5.1-8.8 using microsensor electrodes to measure real-time N2O production. N2O production rates and yield were greater when NH2OH was oxidized by Mn(IV) than Fe(III). Accordingly, the reduction of Mn(IV) was first order with respect to NH2OH whereas the reduction of Fe(III) was zero order with respect to NH2OH. Interestingly, the order of the reaction with respect to Mn(IV) appears to be negative whereas the reaction is second order with respect to Fe(III). The inverse order with respect to Mn(IV) may be due to the aggregation of particles in seawater, which decreases their surface area and changes their reactivity. Finally, the reaction is first order with respect to protons with Fe(III) as the oxidant but zero order with Mn(IV). The stronger effect of the pH on the reaction with Fe(III) as the oxidant compared to Mn(IV) reflects the stoichiometry of these two reactions, as each mole of N2O produced by Fe(III) reduction consumes eight protons while each mole of N2O produced with Mn(IV) as the oxidant requires only four protons. Our data show that abiotic NH2OH oxidation by Mn(IV) or Fe(III) particles may represent a significant source of N2O in seawater. These findings suggest that abiotic N2O production in marine waters may be significant in areas of the oceans where particulate metals originating from aerosols, dust, or rivers may react with NH2OH released from ammonia-oxidizing microorganisms.

Identification of Genes Involved in Biofilm Formation and Respiration via Mini-Himar Transposon Mutagenesis of Geobacter sulfurreducens▿ †

Science.gov (United States)

Rollefson, Janet B.; Levar, Caleb E.; Bond, Daniel R.

2009-01-01

Electron transfer from cells to metals and electrodes by the Fe(III)-reducing anaerobe Geobacter sulfurreducens requires proper expression of redox proteins and attachment mechanisms to interface bacteria with surfaces and neighboring cells. We hypothesized that transposon mutagenesis would complement targeted knockout studies in Geobacter spp. and identify novel genes involved in this process. Escherichia coli mating strains and plasmids were used to develop a conjugation protocol and deliver mini-Himar transposons, creating a library of over 8,000 mutants that was anaerobically arrayed and screened for a range of phenotypes, including auxotrophy for amino acids, inability to reduce Fe(III) citrate, and attachment to surfaces. Following protocol validation, mutants with strong phenotypes were further characterized in a three-electrode system to simultaneously quantify attachment, biofilm development, and respiratory parameters, revealing mutants defective in Fe(III) reduction but unaffected in electron transfer to electrodes (such as an insertion in GSU1330, a putative metal export protein) or defective in electrode reduction but demonstrating wild-type biofilm formation (due to an insertion upstream of the NHL domain protein GSU2505). An insertion in a putative ATP-dependent transporter (GSU1501) eliminated electrode colonization but not Fe(III) citrate reduction. A more complex phenotype was demonstrated by a mutant containing an insertion in a transglutaminase domain protein (GSU3361), which suddenly ceased to respire when biofilms reached approximately 50% of the wild-type levels. As most insertions were not in cytochromes but rather in transporters, two-component signaling proteins, and proteins of unknown function, this collection illustrates how biofilm formation and electron transfer are separate but complementary phenotypes, controlled by multiple loci not commonly studied in Geobacter spp. PMID:19395486

Functional environmental proteomics: elucidating the role of a c-type cytochrome abundant during uranium bioremediation.

Science.gov (United States)

Yun, Jiae; Malvankar, Nikhil S; Ueki, Toshiyuki; Lovley, Derek R

2016-02-01

Studies with pure cultures of dissimilatory metal-reducing microorganisms have demonstrated that outer-surface c-type cytochromes are important electron transfer agents for the reduction of metals, but previous environmental proteomic studies have typically not recovered cytochrome sequences from subsurface environments in which metal reduction is important. Gel-separation, heme-staining and mass spectrometry of proteins in groundwater from in situ uranium bioremediation experiments identified a putative c-type cytochrome, designated Geobacter subsurface c-type cytochrome A (GscA), encoded within the genome of strain M18, a Geobacter isolate previously recovered from the site. Homologs of GscA were identified in the genomes of other Geobacter isolates in the phylogenetic cluster known as subsurface clade 1, which predominates in a diversity of Fe(III)-reducing subsurface environments. Most of the gscA sequences recovered from groundwater genomic DNA clustered in a tight phylogenetic group closely related to strain M18. GscA was most abundant in groundwater samples in which Geobacter sp. predominated. Expression of gscA in a strain of Geobacter sulfurreducens that lacked the gene for the c-type cytochrome OmcS, thought to facilitate electron transfer from conductive pili to Fe(III) oxide, restored the capacity for Fe(III) oxide reduction. Atomic force microscopy provided evidence that GscA was associated with the pili. These results demonstrate that a c-type cytochrome with an apparent function similar to that of OmcS is abundant when Geobacter sp. are abundant in the subsurface, providing insight into the mechanisms for the growth of subsurface Geobacter sp. on Fe(III) oxide and suggesting an approach for functional analysis of other Geobacter proteins found in the subsurface.

One electron reduction of 1,2 dihydroxy 9,10 anthraquinone and its transition metal complexes in aqueous-isopropanol-acetone mixed solvent: a steady state-state and pulse radiolysis study

International Nuclear Information System (INIS)

Das, Saurabh; Mandal, Parikshit C.; Rath, Madhab C.; Mukherjee, Tulsi

1998-01-01

One electron reduction of 1,2 dihydroxy 9,10 anthraquinone and its Cu(II) and Ni(II) and Fe(III) complexes have been studied in aqueous-isopropanol-acetone solvent. Results indicate that the reducing ketyl radical generated reacts with the ligand forming semiquinones which undergoes a disproportionation reaction. Formation and decay rates of semiquinones was calculated using pulse radiolysis. (author)

Spectrophotometric Determination of 6-Propyl-2-Thiouracil in Pharmaceutical Formulations Based on Prussian Blue Complex Formation: An Undergraduate Instrumental Analysis Laboratory Experiment

Science.gov (United States)

Zakrzewski, Robert; Skowron, Monika; Ciesielski, Witold; Rembisz, Zaneta

2016-01-01

The laboratory experiment challenges students to determine 6-propyl-2-thiouracil (PTU) based on Prussian blue complex formation. Prussian blue is formed by ferricyanide and Fe(II) ions which are generated in situ from Fe(III) ions reduced by PTU. The absorbance of this product was measured at a wavelength of 840 nm, after a reaction time of 30…

Linking specific heterotrophic bacterial populations to bioreduction of uranium and nitrate using stable isotope probing in contaminated subsurface sediments

International Nuclear Information System (INIS)

Akob, Denise M.; Kerkhof, Lee; Kusel, Kirsten; Watson, David B.; Palumbo, Anthony Vito; Kostka, Joel

2011-01-01

Shifts in terminal electron-accepting processes during biostimulation of uranium-contaminated sediments were linked to the composition of stimulated microbial populations using DNA-based stable isotope probing. Nitrate reduction preceded U(VI) and Fe(III) reduction in [ 13 C]ethanol-amended microcosms. The predominant, active denitrifying microbial groups were identified as members of the Betaproteobacteria, whereas Actinobacteria dominated under metal-reducing conditions.

Synthesis, investigation and spectroscopic characterization of piroxicam ternary complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with glycine and DL-phenylalanine

Science.gov (United States)

Mohamed, Gehad G.; El-Gamel, Nadia E. A.

2004-11-01

The ternary piroxicam (Pir; 4-hydroxy-2-methyl- N-(2-pyridyl)-2H-1,2-benzothiazine-3-carboxamide 1,1-dioxide) complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with various amino acids (AA) such as glycine (Gly) or DL-phenylalanine (PhA) were prepared and characterized by elemental analyses, molar conductance, IR, UV-Vis, magnetic moment, diffuse reflectance and X-ray powder diffraction. The UV-Vis spectra of Pir and the effect of metal chelation on the different interligand transitions are discussed in detailed manner. IR and UV-Vis spectra confirm that Pir behaves as a neutral bidentate ligand coordinated to the metal ions via the pyridine- N and carbonyl group of the amide moiety. Gly molecule acted as a uninegatively monodentate ligand and coordinate to the metal ions through its carboxylic group, in addition PhA acted as a uninegatively bidentate ligand and coordinate to the metal ions through its carboxylic and amino groups. All the chelates have octahedral geometrical structures while Cu(II)- and Zn(II)-ternary chelates with PhA have square planar geometrical structures. The molar conductance data reveal that most of these chelates are non electrolytes, while Fe(III)-Pir-Gly, Co(II)-, Ni(II)-, Cu(II)- and Zn(II)-Pir-PhA cheletes were 1:1 electrolytes. X-ray powder diffraction is used as a new tool to estimate the crystallinity of chelates as well as to elucidate their geometrical structures.

Microbial production of isotopically light iron(II) in a modern chemically precipitated sediment and implications for isotopic variations in ancient rocks

Science.gov (United States)

Tangalos, G.E.; Beard, B.L.; Johnson, C.M.; Alpers, Charles N.; Shelobolina, E.S.; Xu, H.; Konishi, H.; Roden, E.E.

2012-01-01

The inventories and Fe isotope composition of aqueous Fe(II) and solid-phase Fe compounds were quantified in neutral-pH, chemically precipitated sediments downstream of the Iron Mountain acid mine drainage site in northern California, USA. The sediments contain high concentrations of amorphous Fe(III) oxyhydroxides [Fe(III)am] that allow dissimilatory iron reduction (DIR) to predominate over Fe–S interactions in Fe redox transformation, as indicated by the very low abundance of Cr(II)-extractable reduced inorganic sulfur compared with dilute HCl-extractable Fe. δ56Fe values for bulk HCl- and HF-extractable Fe were ≈ 0. These near-zero bulk δ56Fe values, together with the very low abundance of dissolved Fe in the overlying water column, suggest that the pyrite Fe source had near-zero δ56Fe values, and that complete oxidation of Fe(II) took place prior to deposition of the Fe(III) oxide-rich sediment. Sediment core analyses and incubation experiments demonstrated the production of millimolar quantities of isotopically light (δ56Fe ≈ -1.5 to -0.5‰) aqueous Fe(II) coupled to partial reduction of Fe(III)am by DIR. Trends in the Fe isotope composition of solid-associated Fe(II) and residual Fe(III)am are consistent with experiments with synthetic Fe(III) oxides, and collectively suggest an equilibrium Fe isotope fractionation between aqueous Fe(II) and Fe(III)am of approximately -2‰. These Fe(III) oxide-rich sediments provide a model for early diagenetic processes that are likely to have taken place in Archean and Paleoproterozoic marine sediments that served as precursors for banded iron formations. Our results suggest pathways whereby DIR could have led to the formation of large quantities of low-δ56Fe minerals during BIF genesis.

Stability of bacterial carotenoids in the presence of iron in a model of the gastric compartment - comparison with dietary reference carotenoids.

Science.gov (United States)

Sy, Charlotte; Dangles, Olivier; Borel, Patrick; Caris-Veyrat, Catherine

2015-04-15

Recently isolated spore-forming pigmented marine bacteria, Bacillus indicus HU36 and Bacillus firmus GB1 are sources of carotenoids (∼fifteen distinct yellow and orange pigments and ∼thirteen distinct pink pigments, respectively). They are glycosides of oxygenated lycopene derivatives (apo-lycopenoids) and are assumed to be more heat- and gastric-stable than common carotenoids. In this study, the oxidation by O2 of the bacterial carotenoids was initiated by free iron (Fe(II) and Fe(III)) or by heme iron (metmyoglobin) in a mildly acidic aqueous solution mimicking the gastro-intestinal compartment and compared to the oxidation of the common dietary carotenoids β-carotene, lycopene and astaxanthin. Under these conditions, all bacterial carotenoids appear more stable in the presence of heme iron vs. free iron. Carotenoid autoxidation initiated by Fe(II) is relatively fast and likely involves reactive oxygen-iron species derived from Fe(II) and O2. By contrast, the corresponding reaction with Fe(III) is kinetically blocked by the slow preliminary reduction of Fe(III) into Fe(II) by the carotenoids. The stability of carotenoids toward autoxidation increases as follows: β-carotenecarotenoids react more quickly than reference carotenoids with Fe(III), but much more slowly than the reference carotenoids with Fe(II). This reaction is correlated with the structure of the carotenoids, which can have opposite effects in a micellar system: bacterial carotenoids with electro-attracting terminal groups have a lower reducing capacity than β-carotene and lycopene. However, their polar head favours their location close to the interface of micelles, in closer contact with oxidative species. Kinetic analyses of the iron-induced autoxidation of astaxanthin and HU36 carotenoids has been performed and gives insights in the underlying mechanisms. Copyright © 2015 Elsevier Inc. All rights reserved.

Microbial community composition during anaerobic mineralization of tert-butyl alcohol (TBA) in fuel-contaminated aquifer material.

Science.gov (United States)

Wei, Na; Finneran, Kevin T

2011-04-01

Anaerobic mineralization of tert-butyl alcohol (TBA) and methyl tert-butyl ether (MTBE) were studied in sediment incubations prepared with fuel-contaminated aquifer material. Microbial community compositions in all incubations were characterized by amplified ribosomal DNA restriction analysis (ARDRA). The aquifer material mineralized 42.3±9.9% of [U-(14)C]-TBA to 14CO2 without electron acceptor amendment. Fe(III), sulfate, and Fe(III) plus anthraquinone-2,6-disulfonate addition also promoted U-[14C]-TBA mineralization at levels similar to those of the unamended controls. Nitrate actually inhibited TBA mineralization relative to unamended controls. In contrast to TBA, [U-(14)C]-MTBE was not significantly mineralized in 400 days regardless of electron acceptor amendment. Microbial community analysis indicated that the abundance of one dominant clone group correlated closely with anaerobic TBA mineralization. The clone was phylogenetically distinct from known aerobic TBA-degrading microorganisms, Fe(III)- or sulfate-reducing bacteria. It was most closely associated with organisms belonging to the alphaproteobacteria. Microbial communities were different in MTBE and TBA amended incubations. Shannon indices and Simpson indices (statistical community comparison tools) both demonstrated that microbial community diversity decreased in incubations actively mineralizing TBA, with distinct "dominant" clones developing. These data contribute to our understanding of anaerobic microbial transformation of fuel oxygenates in contaminated aquifer material and the organisms that may catalyze the reactions.

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

Science.gov (United States)

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

2018-02-01

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

Evaluation of the influence of UV/IR radiation on iron release from ferritin

International Nuclear Information System (INIS)

Gritzkov, M.; Kochev, V.; Vladimirova, L

2010-01-01

In the present work the influence of UV/IR radiation on the iron-releasing process from ferritin is investigated. The ferritins are a family of iron-storing proteins playing a key role in the biochemical reactions between iron and oxygen-processes of exclusive importance for the existence of all living organisms. The iron is stored within the ferritin core in the form of insoluble crystals containing Fe(III). Therefore for its release, the mineral matrix has to be decomposed, usually through a reduction of Fe(III) to Fe(II). Our study considers the action of UV/IR radiation on the structure of the protein molecule. Eventual changes in the ferritin conformation under the irradiation could result in the change of channel forming regions responsible for the iron efflux. This can be assess by the quantity of Fe (II) obtained in a subsequent mobilization procedure evoked by exogenous reducing agents. In our case the content of the reduced iron is determined electrochemically by the method of potentiometric titration. As already was shown, this method promises to become highly useful for quantitative evaluation of released Fe 2+ . (Author)

Survey of Microbial Diversity in Flood Areas during Thailand 2011 Flood Crisis Using High-Throughput Tagged Amplicon Pyrosequencing.

Science.gov (United States)

Mhuantong, Wuttichai; Wongwilaiwalin, Sarunyou; Laothanachareon, Thanaporn; Eurwilaichitr, Lily; Tangphatsornruang, Sithichoke; Boonchayaanant, Benjaporn; Limpiyakorn, Tawan; Pattaragulwanit, Kobchai; Punmatharith, Thantip; McEvoy, John; Khan, Eakalak; Rachakornkij, Manaskorn; Champreda, Verawat

2015-01-01

The Thailand flood crisis in 2011 was one of the largest recorded floods in modern history, causing enormous damage to the economy and ecological habitats of the country. In this study, bacterial and fungal diversity in sediments and waters collected from ten flood areas in Bangkok and its suburbs, covering residential and agricultural areas, were analyzed using high-throughput 454 pyrosequencing of 16S rRNA gene and internal transcribed spacer sequences. Analysis of microbial community showed differences in taxa distribution in water and sediment with variations in the diversity of saprophytic microbes and sulfate/nitrate reducers among sampling locations, suggesting differences in microbial activity in the habitats. Overall, Proteobacteria represented a major bacterial group in waters, while this group co-existed with Firmicutes, Bacteroidetes, and Actinobacteria in sediments. Anaeromyxobacter, Steroidobacter, and Geobacter were the dominant bacterial genera in sediments, while Sulfuricurvum, Thiovirga, and Hydrogenophaga predominated in waters. For fungi in sediments, Ascomycota, Glomeromycota, and Basidiomycota, particularly in genera Philipsia, Rozella, and Acaulospora, were most frequently detected. Chytridiomycota and Ascomycota were the major fungal phyla, and Rhizophlyctis and Mortierella were the most frequently detected fungal genera in water. Diversity of sulfate-reducing bacteria, related to odor problems, was further investigated using analysis of the dsrB gene which indicated the presence of sulfate-reducing bacteria of families Desulfobacteraceae, Desulfobulbaceae, Syntrobacteraceae, and Desulfoarculaceae in the flood sediments. The work provides an insight into the diversity and function of microbes related to biological processes in flood areas.

The limited role of aquifer heterogeneity on metal reduction in an Atlantic coastal plain determined by push-pull tests

International Nuclear Information System (INIS)

Mailloux, Brian J.; Devlin, Stephanie; Fuller, Mark E.; Onstott, T.C.; De Flaun, Mary F.; Choi, K.-H.; Green-Blum, Maria; Swift, Donald J.P.; McCarthy, John; Dong Hailiang

2007-01-01

Sixty push-pull experiments were conducted to determine the factors controlling Fe(III) and Mn(IV) reduction in a well-characterized, shallow, coastal plain aquifer near Oyster, VA, USA. The five multi-level samplers each equipped with 12 ports sampled a heterogeneous portion of the aquifer from 4.4 to 8m-bgs. Each multi-level sampler (MLS) was injected with groundwater that contained NO 3 - and Br - along with: (1) just groundwater (control treatment), (2) humics, (3) lactate (conducted twice) and (4) lactate plus humics. Microbially mediated Fe(III) reduction caused the aqueous Fe Tot concentrations to increase at every depth in the lactate treatment with significant increases within 1 day even while NO 3 - was present. Little change in the Fe Tot concentrations were observed in the control and humics treatment. Humics may have acted as an electron shuttle to increase Fe(III) reduction in the lactate plus humics treatment. The amount of Mn(IV) reduction was significantly lower than that of Fe(III) reduction. Geochemical modeling indicated that gas formation, sorption on reactive surfaces, and mineral precipitation were important processes and that Fe(III) and SO 4 2- reduction were co-occurring. Conditions were favorable for the precipitation of Fe-carbonates, Fe-sulfides and Fe-silicates. In the lactate treatment protist concentrations increased then decreased and planktonic cell concentrations steadily increased, whereas no change was observed in the control treatment. Correlations of Fe(III) reduction with physical and chemical heterogeneity were weak, probably as a result of the abundance of Fe(III) bearing minerals relative to electron donor abundance and that the push-pull test sampled a representative elemental volume that encompassed the microbial diversity within the aquifer. This work indicates that stimulating metal reduction in aquifer systems is a feasible method for remediating heterogeneous subsurface sites contaminated with metals and

Iron species determination by task-specific ionic liquid-based in situ solvent formation dispersive liquid-liquid microextraction combined with flame atomic absorption spectrometry.

Science.gov (United States)

Sadeghi, Susan; Ashoori, Vahid

2017-10-01

The task-specific ionic liquid (TSIL) of 1-ethyl-3-methylimidazolium bromide functionalized with 8-hydroxyquinoline was used as a chelating agent and extracting solvent for dispersive liquid-liquid microextraction and subsequent determination of Fe(III) by flame atomic absorption spectrometry. The in situ solvent formation of TSIL using KPF 6 provided the desired water-immiscible ionic liquid. The total Fe concentration could be determined after pre-oxidation of Fe(II) to Fe(III). Various factors affecting the proposed extraction procedure were optimized. The proposed analytical conditions were: sample pH 5, TSIL amount 0.3% (w/v), KPF 6 amount 0.15% (w/v), anti-sticking 0.1% (w/v) and salt concentration 5% (w/v). Under optimal conditions, the linear dynamic ranges for Fe(III) and total Fe were 20-80 and 20-110 ng mL -1 , respectively, with a detection limit of 6.9 ng mL -1 for Fe(III) and relative standard deviation of 2.2%. The proposed method was successfully applied to the determination of trace Fe(III) in water (underground, tap, refined water and artificial sea water) and beverage (apple, tomato, and tea) samples. The developed method offers advantages such as simplicity, ease of operation, and extraction of Fe(III) from aqueous solutions without the use of organic solvent. It was successfully applied for iron speciation in different real samples. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

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

Directory of Open Access Journals (Sweden)

Ming-Hui Zhao

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

Effects of nitrate on the stability of uranium in a bioreduced region of the subsurface

International Nuclear Information System (INIS)

Wu, Weimin; Carley, Jack M.; Green, Stefan; Luo, Jian; Kelly, Shelly D.; Van Nostrand, Joy; Lowe, Kenneth Alan; Mehlhorn, Tonia L.; Carroll, Sue L.; Boonchayanant, Benjaporn; Loeffler, Frank E.; Jardine, Philip M.; Criddle, Craig

2010-01-01

The effects of nitrate on the stability of reduced, immobilized uranium were evaluated in field experiments at a U.S. Department of Energy site in Oak Ridge, TN. Nitrate (2.0 mM) was injected into a reduced region of the subsurface containing high levels of previously immobilized U(IV). The nitrate was reduced to nitrite, ammonium, and nitrogen gas; sulfide levels decreased; and Fe(II) levels increased then deceased. Uranium remobilization occurred concomitant with nitrite formation, suggesting nitrate-dependent, iron-accelerated oxidation of U(IV). Bromide tracer results indicated changes in subsurface flowpaths likely due to gas formation and/or precipitate. Desorption-adsorption of uranium by the iron-rich sediment impacted uranium mobilization and sequestration. After rereduction of the subsurface through ethanol additions, background groundwater containing high levels of nitrate was allowed to enter the reduced test zone. Aqueous uranium concentrations increased then decreased. Clone library analyses of sediment samples revealed the presence of denitrifying bacteria that can oxidize elemental sulfur, H 2 S, Fe(II), and U(IV) (e.g., Thiobacillus spp.), and a decrease in relative abundance of bacteria that can reduce Fe(III) and sulfate. XANES analyses of sediment samples confirmed changes in uranium oxidation state. Addition of ethanol restored reduced conditions and triggered a short-term increase in Fe(II) and aqueous uranium, likely due to reductive dissolution of Fe(III) oxides and release of sorbed U(VI). After two months of intermittent ethanol addition, sulfide levels increased, and aqueous uranium concentrations gradually decreased to <0.1 μM.

The binding of aluminum to mugineic acid and related compounds as studied by potentiometric titration.

Science.gov (United States)

Yoshimura, Etsuro; Kohdr, Hicham; Mori, Satoshi; Hider, Robert C

2011-08-01

The phytosiderophores, mugineic acid (MA) and epi-hydroxymugineic acid (HMA), together with a related compound, nicotianamine (NA), were investigated for their ability to bind Al(III). Potentiometric titration analysis demonstrated that MA and HMA bind Al(III), in contrast to NA which does not under normal physiological conditions. With MA and HMA, in addition to the Al complex (AlL), the protonated (AlLH) and deprotonated (AlLH(-1)) complexes were identified from an analysis of titration curves, where L denotes the phytosiderophore form in which all the carboxylate functions are ionized. The equilibrium formation constants of the Al(III) phytosiderophore complexes are much smaller than those of the corresponding Fe(III) complexes. The higher selectivity of phytosiderophores for Fe(III) over Al(III) facilitates Fe(III) acquisition in alkaline conditions where free Al(III) levels are higher than free Fe(III) levels.

Nitrogen loss from anaerobic ammonium oxidation coupled to Iron(III) reduction in a riparian zone.

Science.gov (United States)

Ding, Bangjing; Li, Zhengkui; Qin, Yunbin

2017-12-01

Anaerobic ammonium oxidation coupled to iron(III) reduction (termed Feammox) is a recently discovered pathway of nitrogen cycling. However, little is known about the pathways of N transformation via Feammox process in riparian zones. In this study, evidence for Feammox in riparian zones with or without vegetation cover was demonstrated using isotope tracing technique and high-throughput sequencing technology. The results showed that Feammox could occur in riparian zones, and demonstrated that N 2 directly from Feammox was dominant Feammox pathway. The Feammox rates in vegetated soil samples was 0.32-0.37 mg N kg -1 d -1 , which is higher than that in un-vegetated soil samples (0.20 mg N kg -1 d -1 ). Moreover, the growth of vegetation led to a 4.99-6.41% increase in the abundance of iron reducing bacteria (Anaeromyxobacter, Pseudomonas and Geobacter) and iron reducing bacteria play an essential role in Feammox process. An estimated loss of 23.7-43.9 kg N ha -1 year -1 was associated with Feammox in the examined riparian zone. Overall, the co-occurrence of ammonium oxidation and iron reduction suggest that Feammox can play an essential role in the pathway of nitrogen removal in riparian zones. Copyright © 2017 Elsevier Ltd. All rights reserved.

Iron(III) species formed during iron(II) oxidation and iron-core formation in bacterioferritin of Escherichia coli

International Nuclear Information System (INIS)

Hawkins, C.; Treffry, A.; Mackey, J.; Williams, J.M.; Andrews, S.C.; Guest, J.R.; Harrison, P.M.

1996-01-01

This paper describes a preliminary investigation of the mechanisms of Fe(II) oxidation and storage of Fe(III) in the bacterioferritin of Escherichia coli (EcBFR). Using Moessbauer spectroscopy to examine the initial oxidation of iron by EcBFR it is confirmed that this ferritin exhibits 'ferroxidase' activity and is shown that dimeric and monomeric iron species are produced as intermediates. The characteristics of ferroxidase activity in EcBFR is compare d with those of human H-chain ferritin (HuHF) and discuss the different Moessbauer parameters of their dimeric iron with reference to the structures of their di-metal sites. In addition, it is presented preliminary findings suggesting that after an initial 'burst', the rate of oxidation is greatly reduced, possibly due to blockage of the ferroxidase centre by bound iron. A new component, not found in HuHF and probably representing a small cluster of Fe(III) atoms, is reported

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

Science.gov (United States)

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

2017-07-17

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

The pyruvate kinase of Stigmatella aurantiaca is an indole binding protein and essential for development.

Science.gov (United States)

Stamm, Irmela; Lottspeich, Friedrich; Plaga, Wulf

2005-06-01

Myxospore formation of the myxobacterium Stigmatella aurantiaca can be uncoupled from the cooperative development i.e. fruiting body formation, by low concentrations of indole. Two putative indole receptor proteins were isolated by their capacity to bind indole and identified as pyruvate kinase (PK) and aldehyde dehydrogenase. The PK activity of Stigmatella crude extracts was stimulated by indole. Cloning of the PK gene (pykA) and the construction of a pykA disruption mutant strikingly revealed that PK is essential for multicellular development: Fruiting body formation was abolished in the mutant strain and indole-induced spore formation was delayed. The developmental defects could be complemented by insertion of the pykA gene at the mtaB locus of the Stigmatella genome excluding any polar effects of the pykA disruption.

Purification of cold-shock-like proteins from Stigmatella aurantiaca - molecular cloning and characterization of the cspA gene.

Science.gov (United States)

Stamm, I; Leclerque, A; Plaga, W

1999-09-01

Prominent low-molecular-weight proteins were isolated from vegetative cells of the myxobacterium Stigmatella aurantiaca and were found to be members of the cold-shock protein family. A first gene of this family (cspA) was cloned and sequenced. It encodes a protein of 68 amino acid residues that displays up to 71% sequence identity with other bacterial cold-shock(-like) proteins. A cysteine residue within the RNP-2 motif is a peculiarity of Stigmatella CspA. A cspA::(Deltatrp-lacZ) fusion gene construct was introduced into Stigmatella by electroporation, a method that has not been used previously for this strain. Analysis of the resultant transformants revealed that cspA transcription occurs at high levels during vegetative growth at 20 and 32 degrees C, and during fruiting body formation.

Intercellular signaling in Stigmatella aurantiaca: purification and characterization of stigmolone, a myxobacterial pheromone.

Science.gov (United States)

Plaga, W; Stamm, I; Schairer, H U

1998-09-15

The myxobacterium Stigmatella aurantiaca passes through a life cycle that involves formation of a multicellular fruiting body as the most complex stage. An early step in this differentiation process depends on a signal factor secreted by the cells when nutrients become limited. The formation of a fruiting body from a small cell population can be accelerated by addition of this secreted material. The bioactive compound was found to be steam volatile. It was purified to homogeneity by steam distillation followed by reversed-phase and normal-phase HPLC. The pheromone was named stigmolone, in accordance with the structure 2,5, 8-trimethyl-8-hydroxy-nonan-4-one, as determined by NMR and mass spectrometry. Stigmolone represents a structurally unique and highly bioactive prokaryotic pheromone that is effective in the bioassay at 1 nM concentration.

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

NARCIS (Netherlands)

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

2016-01-01

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

Microbial reduction of uranium(VI) in sediments of different lithologies collected from Sellafield

International Nuclear Information System (INIS)

Newsome, Laura; Morris, Katherine; Trivedi, Divyesh; Atherton, Nick; Lloyd, Jonathan R.

2014-01-01

Highlights: • U(VI) (aq) mobility can be controlled by stimulating biogeochemical interactions. • Indigenous microbes in varied sediments reduced U(VI) to insoluble U(IV). • Sediment cell numbers and amount of bioavailable Fe(III) could limit this process. - Abstract: The presence of uranium in groundwater at nuclear sites can be controlled by microbial processes. Here we describe the results from stimulating microbial reduction of U(VI) in sediment samples obtained from a nuclear-licensed site in the UK. A variety of different lithology sediments were selected to represent the heterogeneity of the subsurface at a site underlain by glacial outwash deposits and sandstone. The natural sediment microbial communities were stimulated via the addition of an acetate/lactate electron donor mix and were monitored for changes in geochemistry and molecular ecology. Most sediments facilitated the removal of 12 ppm U(VI) during the onset of Fe(III)-reducing conditions; this was reflected by an increase in the proportion of known Fe(III)- and U(VI)-reducing species. However U(VI) remained in solution in two sediments and Fe(III)-reducing conditions did not develop. Sequential extractions, addition of an Fe(III)-enrichment culture and most probable number enumerations revealed that a lack of bioavailable iron or low cell numbers of Fe(III)-reducing bacteria may be responsible. These results highlight the potential for stimulation of microbial U(VI)-reduction to be used as a bioremediation strategy at UK nuclear sites, and they emphasise the importance of both site-specific and borehole-specific investigations to be completed prior to implementation

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

Science.gov (United States)

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

2011-07-01

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

Diversity and function of the microbial community on anodes of sediment microbial fuel cells fueled by root exudates

Energy Technology Data Exchange (ETDEWEB)

Cabezas da Rosa, Angela

2010-11-26

Anode microbial communities are essential for current production in microbial fuel cells. Anode reducing bacteria are capable of using the anode as final electron acceptor in their respiratory chain. The electrons delivered to the anode travel through a circuit to the cathode where they reduce oxygen to water generating an electric current. A novel type of sediment microbial fuel cell (SMFC) harvest energy from photosynthetically derived compounds released through the roots. Nothing is known about anode microbial communities of this type of microbial fuel cell. This work consists of three parts. The first part focuses on the study of bacterial and archaeal community compositions on anodes of SMFCs fueled by rice root exudates. By using terminal restriction fragment length polymorphism (T-RFLP), a profiling technique, and cloning / sequencing of 16S rRNA, we determined that the support type used for the plant (vermiculite, potting soil or rice field soil) is an important factor determining the composition of the microbial community. Finally, by comparing microbial communities of current producing anodes and non-current producing controls we determined that Desulfobulbus- and Geobacter-related populations were probably most important for current production in potting soil and rice field soil SMFCs, respectively. However, {delta}-proteobacterial Anaeromyxobacter spp., unclassified {delta}-proteobacteria and Anaerolineae were also part of the anode biofilm in rice field soil SMFCs and these populations might also play a role in current production. Moreover, distinct clusters of Geobacter and Anaeromyxobacter populations were stimulated by rice root exudates. Regarding Archaea, uncultured Euryarchaea were abundant on anodes of potting soil SMFCs indicating a potential role in current production. In both, rice field soil and potting soil SMFCs, a decrease of Methanosaeta, an acetotrophic methanogen, was detected on current producing anodes. In the second part we focused

Synthesis of nitrogen-doped and amino acid-functionalized graphene quantum dots from glycine, and their application to the fluorometric determination of ferric ion

International Nuclear Information System (INIS)

Li, Linbo; Li, Lin; Wang, Chao; Liu, Kangyu; Zhu, Ruohua; Qiang, Hong; Lin, Yuqing

2015-01-01

We report on a single-step thermolysis strategy to prepare highly luminescent nitrogen-doped and amino acid-functionalized graphene quantum dots (NA-GQDs) by using glycine as both carbon and nitrogen source. The NA-GQDs display an excitation wavelength-dependent fluorescence with maximum excitation and emission wavelengths of 380 and 450 nm, respectively, and a quantum yield of ∼16 %. Fluorescence is quenched by Fe(III) and Hg(II), and the effect was used to develop a method for the determination of Fe(III). Quenching by Fe(III) is attributed to its higher thermodynamic affinity (compared to other transition-metal ions) for the ligands on the GQDs in which nitrogen atoms mainly act as the chelating atoms. A linear relationship was observed between fluorescence intensity and the concentration of Fe(III) over the 0.5 μM to 0.5 mM range. The detection limit is 0.1 μM. (author)

Rapid arsenic(V)-reduction by fire in schwertmannite-rich soil enhances arsenic mobilisation

DEFF Research Database (Denmark)

Johnston, Scott G.; Bennett, William W.; Burton, Edward D.

2018-01-01

(III) formation (∼90%) within 5–10 min at 400–600 °C, followed by partial re-oxidation to As(V) thereafter. In contrast, heating As(V)-schwertmannite in the absence of soil-organic matter did not cause reduction of As(V) or Fe(III), nor form maghemite; thus highlighting the critical role of organic matter......Arsenic in acid sulfate soil (ASS) landscapes commonly associates with schwertmannite, a poorly crystalline Fe(III) mineral. Fires in ASS landscapes can thermally transform Fe(III) minerals to more crystalline phases, such as maghemite (γFe2O3). Although thermal genesis of maghemite requires...... and hematite at temperatures above 300–400 °C, with some transitory formation of magnetite, and electrons are readily transferred to both Fe(III) and As(V). As(V) reduction to As(III) is influenced by a combination of temperature, heating duration and carbon content and is significantly (P

Influence of iron redox transformations on plutonium sorption to sediments

Energy Technology Data Exchange (ETDEWEB)

Hixon, A.E.; Powell, B.A. [Environmental Engineering and Earth Sciences, Clemson Univ., Clemson, SC (United States); Hu, Y.J.; Nitsche, H. [Dept. of Chemistry, Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab., Berkeley, CA (United States); Kaplan, D.I. [Savannah River National Lab., Aiken, SC (United States); Kukkadapu, R.K.; Qafoku, O. [Pacific Northwest National Lab., Richland, WA (United States)

2010-07-01

Plutonium subsurface mobility is primarily controlled by its oxidation state, which in turn is loosely coupled to the oxidation state of iron in the system. Experiments were conducted to examine the effect of sediment iron mineral composition and oxidation state on plutonium sorption and reduction. A pH 6.3 vadose zone sediment containing iron oxides and iron-containing phyllosilicates was treated with various complexants (ammonium oxalate) and reductants (hydroxylamine hydrochloride and dithionite-citrate-bicarbonate (DCB)) to selectively leach and/or reduce iron oxide and phyllosilicate/clay Fe(III). {sup 57}Fe-Moessbauer spectroscopy was used to identify initial iron mineral composition of the sediment and monitor dissolution and reduction of iron oxides and reduction of phyllosilicate Fe(III). {sup 57}Fe-Moessbauer spectroscopy showed that the Fe-mineral composition of the untreated sediment is: 25-30% hematite, 60-65% small-particle/Al-goethite, and < 10% Fe(III) in phyllosilicate; there was no detectable Fe(II). Upon reduction with a strong chemical reductant (dithionite-citrate-bicarbonate buffer), much of the hematite and goethite was removed. Partial reduction of phyllosilicate Fe(III) was evident in the sediments subjected to DCB treatment. Sorption of Pu(V) was monitored over one week for the untreated and each of five treated sediment fractions. Plutonium oxidation state speciation in the aqueous and solid phases was monitored using solvent extraction, coprecipitation, and XANES. The rate of sorption appears to correlate with the fraction of Fe(II) in the sediment (untreated or treated). Pu(V) was the only oxidation state measured in the aqueous phase, irrespective of treatment, whereas Pu(IV) and much smaller amounts of Pu(V) and Pu(VI) were measured in the solid phase. Surface-mediated reduction of Pu(V) to Pu(IV) occurred in treated and untreated sediment samples; Pu(V) remained on untreated sediment surface for two days before reducing to Pu

Synthesis and structure of a ferric complex of 2,6-di(1H-pyrazol-3-yl)pyridine and its excellent performance in the redox-controlled living ring-opening polymerization of ε-caprolactone.

Science.gov (United States)

Fang, Yang-Yang; Gong, Wei-Jie; Shang, Xiu-Juan; Li, Hong-Xi; Gao, Jun; Lang, Jian-Ping

2014-06-14

The reaction of FeCl3 with a pincer ligand, 2,6-di(1H-pyrazol-3-yl)pyridine (bppyH2), produced a mononuclear Fe(III) complex [Fe(bppyH2)Cl3] (1), which could be reduced to the corresponding Fe(II) dichloride complex [Fe(bppyH2)Cl2] (2) by suitable reducing agents such as Cp2Co or Fe powder. 1 and 2 exhibited a reversible transformation from each other with appropriate redox reagents. 1 could be utilized as a pre-catalyst to initiate the ring-opening polymerization of ε-caprolactone in the presence of alcohol but did not work. The 1/alcohol system displayed characteristics of a well-controlled polymerization with the resulting poly(ε-caprolactone) having low molecular weight distributions, a linear tendency of molecular weight evolution with conversion, and polymer growth observed for the sequential additions of ε-caprolactone monomer to the polymerization reaction. The polymerization was completely turned off by the in situ reduction of the catalytic Fe center via Cp2Co and then turned back upon the addition of [Cp2Fe]PF6. The rate of polymerization was modified by switching in situ between the Fe(III) and Fe(II) species.

Rapid and simple colorimetric method for the quantification of AI-2 produced from Salmonella Typhimurium.

Science.gov (United States)

Wattanavanitchakorn, Siriluck; Prakitchaiwattana, Cheunjit; Thamyongkit, Patchanita

2014-04-01

The aim of this study was to evaluate the feasibility of Fe(III) ion reduction for the simple and rapid quantification of autoinducer-2 (AI-2) produced from bacteria using Salmonella Typhimurium as a model. Since the molecular structure of AI-2 is somewhat similar to ascorbic acid it was expected that AI-2 would also act as a reducing agent and reduce Fe(III) ions in the presence of 1,10-phenanthroline to form the colored [(o-phen)3 Fe(II)]SO4 ferroin complex that could be quantified colorimetrically. In support of this, colony rinses and cell free supernatants from cultures of all tested AI-2 producing strains, but not the AI-2 negative Sinorhizobium meliloti, formed a colored complex with a λmax of 510nm. The OD510 values of these culture supernatants or colony rinses were in broad agreement with the % activity observed in the same samples using the standard Vibrio harveyi bioluminescence assay for AI-2 detection, and with previously reported results. This methodology could potentially be developed as an alternative method for the simple and rapid quantification of AI-2 levels produced in bacterial cultures. Copyright © 2014 Elsevier B.V. All rights reserved.

Differentially expressed genes in iron-induced prion protein conversion

International Nuclear Information System (INIS)

Kim, Minsun; Kim, Eun-hee; Choi, Bo-Ran; Woo, Hee-Jong

2016-01-01

The conversion of the cellular prion protein (PrP C ) to the protease-resistant isoform is the key event in chronic neurodegenerative diseases, including transmissible spongiform encephalopathies (TSEs). Increased iron in prion-related disease has been observed due to the prion protein-ferritin complex. Additionally, the accumulation and conversion of recombinant PrP (rPrP) is specifically derived from Fe(III) but not Fe(II). Fe(III)-mediated PK-resistant PrP (PrP res ) conversion occurs within a complex cellular environment rather than via direct contact between rPrP and Fe(III). In this study, differentially expressed genes correlated with prion degeneration by Fe(III) were identified using Affymetrix microarrays. Following Fe(III) treatment, 97 genes were differentially expressed, including 85 upregulated genes and 12 downregulated genes (≥1.5-fold change in expression). However, Fe(II) treatment produced moderate alterations in gene expression without inducing dramatic alterations in gene expression profiles. Moreover, functional grouping of identified genes indicated that the differentially regulated genes were highly associated with cell growth, cell maintenance, and intra- and extracellular transport. These findings showed that Fe(III) may influence the expression of genes involved in PrP folding by redox mechanisms. The identification of genes with altered expression patterns in neural cells may provide insights into PrP conversion mechanisms during the development and progression of prion-related diseases. - Highlights: • Differential genes correlated with prion degeneration by Fe(III) were identified. • Genes were identified in cell proliferation and intra- and extracellular transport. • In PrP degeneration, redox related genes were suggested. • Cbr2, Rsad2, Slc40a1, Amph and Mvd were expressed significantly.

Influence of uranyl speciation and iron oxides on uranium biogeochemical redox reactions

Energy Technology Data Exchange (ETDEWEB)

Stewart, B.D.; Amos, R.T.; Nico, P.S.; Fendorf, S.

2010-03-15

Uranium is a pollutant of concern to both human and ecosystem health. Uranium's redox state often dictates its partitioning between the aqueous- and solid-phases, and thus controls its dissolved concentration and, coupled with groundwater flow, its migration within the environment. In anaerobic environments, the more oxidized and mobile form of uranium (UO{sub 2}{sup 2+} and associated species) may be reduced, directly or indirectly, by microorganisms to U(IV) with subsequent precipitation of UO{sub 2}. However, various factors within soils and sediments may limit biological reduction of U(VI), inclusive of alterations in U(VI) speciation and competitive electron acceptors. Here we elucidate the impact of U(VI) speciation on the extent and rate of reduction with specific emphasis on speciation changes induced by dissolved Ca, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite and hematite) varying in free energies of formation on U reduction. The amount of uranium removed from solution during 100 h of incubation with S. putrefaciens was 77% with no Ca or ferrihydrite present but only 24% (with ferrihydrite) and 14% (no ferrihydrite) were removed for systems with 0.8 mM Ca. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Dissimilatory reduction of Fe(III) and U(VI) can proceed through different enzyme pathways, even within a single organism, thus providing a potential second means by which Fe(III) bearing minerals may impact U(VI) reduction. We quantify rate coefficients for simultaneous dissimilatory reduction of Fe(III) and U(VI) in systems varying in Ca concentration (0 to 0.8 mM), and using a mathematical construct implemented with the reactive transport code MIN3P, we reveal the predominant influence of uranyl speciation, specifically the formation of uranyl

Formation, reactivity and aging of amorphous ferric oxides in the presence of model and membrane bioreactor derived organics.

Science.gov (United States)

Bligh, Mark W; Maheshwari, Pradeep; David Waite, T

2017-11-01

Iron salts are routinely dosed in wastewater treatment as a means of achieving effluent phosphorous concentration goals. The iron oxides that result from addition of iron salts partake in various reactions, including reductive dissolution and phosphate adsorption. The reactivity of these oxides is controlled by the conditions of formation and the processes, such as aggregation, that lead to a reduction in accessible surface sites following formation. The presence of organic compounds is expected to significantly impact these processes in a number of ways. In this study, amorphous ferric oxide (AFO) reactivity and aging was investigated following the addition of ferric iron (Fe(III)) to three solution systems: two synthetic buffered systems, either containing no organic or containing alginate, and a supernatant system containing soluble microbial products (SMPs) sourced from a membrane bioreactor (MBR). Reactivity of the Fe(III) phases in these systems at various times (1-60 min) following Fe(III) addition was quantified by determining the rate constants for ascorbate-mediated reductive dissolution over short (5 min) and long (60 min) dissolution periods and for a range (0.5-10 mM) of ascorbate concentrations. AFO particle size was monitored using dynamic light scattering during the aging and dissolution periods. In the presence of alginate, AFO particles appeared to be stabilized against aggregation. However, aging in the alginate system was remarkably similar to the inorganic system where aging is associated with aggregation. An aging mechanism involving restructuring within the alginate-AFO assemblage was proposed. In the presence of SMPs, a greater diversity of Fe(III) phases was evident with both a small labile pool of organically complexed Fe(III) and a polydisperse population of stabilized AFO particles present. The prevalence of low molecular weight organic molecules facilitated stabilization of the Fe(III) oxyhydroxides formed but subsequent aging

Ammonium Oxidation Under Iron Reducing Conditions: Environmental Factors Characterization and Process Optimization

Science.gov (United States)

Huang, Shan; Ruiz, Melany; Jaffe, Peter

2015-04-01

Ammonium (NH4+) oxidation coupled to iron (Fe) reduction in the absence of oxygen and nitrate/nitrite (NO3-/NO2-) has been reported by several investigators and is referred to as Feammox. Feammox is a biological reaction, where Fe(III) is the electron acceptor, which is reduced to Fe(II), and NH4+ is the electron donor, which is oxidized to NO2-. An Acidimicrobiaceae bacterium named A6, a previously unreported species in the Acidimicrobiaceae family, has been identified as being responsible for the Feammox process(1, 2) Feammox process was noted in riparian wetland soils in New Jersey(1,3), in tropical rainforest soils in Puerto Rico (4) and in paddy soils in China (5). In addition to these published locations, Feammox process was also found in samples collected from a series of local wetland-, upland-, as well as storm-water detention pond-sediments in New Jersey, river sediments from South Carolina, and forested soils near an acid mine drainage (Dabaoshan, Guangdong province) in China. Using primers acm342f - 439r (2), Acidimicrobiaceae bacterium A6 was detected in samples where Feammox was observed, after strictly anaerobic incubations. According to a canonical correspondence analysis with environmental characteristics and soil microbial communities, the species-environment relationship indicated that pH and Fe oxides content were the primary factors controlling Feammox process. Anaerobic incubations of Feammox enrichment cultures adjusted to different pH, revealed that the optimal pH for Feammox is 4 ~ 5, and the reaction does not proceed when pH > 7. No correlation was found between the distributions of Feammox bacteria and other NH4+ oxidation bacteria. Pure Acidimicrobiaceae bacterium A6 strain was isolated in an autotrophic medium, from an active Feammox membrane reactor (A6 was enriched to 65.8% of the total bacteria). A 13C labeled CO2 amendment was conducted, and the 13C in cells of A6 increased from 1.80% to 10.3% after 14 days incubation. In a separate

Iron in the aquifer system of Suffolk County, New York, 1990–98

Science.gov (United States)

Brown, Craig J.; Walter, Donald A.; Colabufo, Steven

1999-01-01

High concentrations of dissolved iron in ground water contribute to the biofouling of public-supply wells, and the treatment and remediation of biofouling are costly. Water companies on Long Island, N.Y., spend several million dollars annually to recondition, redevelop, and replace supply wells and distribution lines; treat dissolved iron with sequestering agents or by filtration; and respond to iron-related complaints by customers. This report summarizes the results of studies done by the U.S. Geological Survey, in cooperation with the Suffolk County Water Authority, to characterize the geochemistry and microbiology of iron in the aquifer system of Suffolk County. This information should be helpful for the siting and operation of supply wells.Concentrations of dissolved iron in Long Island's ground water, and the frequency of iron biofouling of wells, are highest in ground-water-discharge zones, particularly near the south shore. Ground water along a deep north-south flowpath of the Magothy aquifer in southwestern Suffolk County becomes anaerobic (oxygen deficient) and Fe(III) reducing at a distance of 8 to 10 kilometers south of the ground-water divide, and this change coincides with the downgradient increase in dissolved iron concentrations. The distribution of organic carbon, and the distribution and local variations in reactivity of Fe(III), in Magothy aquifer sediments have resulted in localized differences in redox microenvironments. For example, Fe(III)-reducing zones are associated with anaerobic conditions, where relatively large amounts of Fe(III) oxyhydroxide grain coatings are present, whereas sulfate-reducing zones are associated with lignite-rich lenses of silt and clay and appear to have developed in response to the depletion of available Fe(III) oxyhydroxides. The sulfate-reducing zones are characterized by relatively low concentrations of dissolved iron (resulting from iron-disulfide precipitation) and may be large enough to warrant water

Preservation of organic matter in nontronite against iron redox cycling.

Science.gov (United States)

Zeng, Q.

2015-12-01

It is generally believed that clay minerals can protect organic matter from degradation in redox active environments, but both biotic and abiotic factors can influence the redox process and thus potentially change the clay-organic associations. However, the specific mechanisms involved in this process remain poorly understood. In this study, a model organic compound, 12-Aminolauric acid (ALA) was selected to intercalate into the structural interlayer of nontronite (an iron-rich smectite, NAu-2) to form an ALA-intercalated NAu-2 composite (ALA-NAu-2). Shawanella putrefaciens CN32 and sodium dithionite were used to reduce structural Fe(III) to Fe(II) in NAu-2 and ALA-NAu-2. The bioreduced ALA-NAu-2 was subsequently re-oxidized by air. The rates and extents of bioreduction and air re-oxidation were determined with wet chemistry methods. ALA release from ALA-NAu-2 via redox process was monitored. Mineralogical changes after iron redox cycle were investigated with X-ray diffraction, infrared spectroscopy, and scanning and transmission electron microscopy. At the beginning stage of bioreduction, S. putrefaciens CN32 reduced Fe(III) from the edges of nontronite and preferentially reduced and dissolved small and poorly crystalline particles, and released ALA, resulting a positive correlation between ALA release and iron reduction extent (80%). Because bacteria are the principal agent for mediating redox process in natural environments, our results demonstrated that the structural interlayer of smectite can serve as a potential shelter to protect organic matter from oxidation.

Influence of Carbon Sources and Electron Shuttles on Ferric Iron Reduction by Cellulomonas sp. Strain ES6

Energy Technology Data Exchange (ETDEWEB)

Erin K. Field; Robin Gerlach; Sridhar Viamajala; Laura K. Jennings; Alfred B. Cunningham; Brent M. Peyton; William A. Apel

2011-09-01

The reduction of hexavalent chromium, Cr(VI), to trivalent chromium, Cr(III), can be an important aspect of remediation processes at Department of Energy (DOE) and other contaminated sites. Cellulomonas species are found at several Cr(VI) contaminated and uncontaminated locations at the DOE site in Hanford, Washington. Members of this genus have demonstrated the ability to effectively reduce Cr(VI) to Cr(III) fermentatively and therefore play a potential role in hexavalent chromium remediation at this site. Batch studies were conducted with Cellulomonas sp. strain ES6 to assess the influence of various carbon sources, iron minerals, and electron shuttling compounds on Cr(VI) reduction. These chemical species are likely to be present in these terrestrial environments during in situ bioremediation. Results indicated that there were a number of interactions between these compounds that influenced Cr(VI) reduction rates. The type of carbon source as well as the type of electron shuttle present influenced Cr(VI) reduction rates. When an electron shuttle, such as anthraquinone-2,6-disulfonate (AQDS), was present in the system, reduction rates increased significantly. Biologically reduced AQDS (AHDS) reduced Cr(VI) almost instantaneously. The presence of iron minerals and their concentrations did not significantly influence Cr(VI) reduction rates. However, strain ES6 or AQDS could directly reduce surface-associated Fe(III) to Fe(II) which was capable of reducing Cr(VI) at a near instantaneous rate. These results suggest the rate limiting step in these systems is the transfer of electrons from strain ES6 to the intermediate or terminal electron acceptor whether that is Cr(VI), Fe(III), or AQDS.

Biogeochemical modeling of CO2 and CH4 production in anoxic Arctic soil microcosms

Science.gov (United States)

Tang, Guoping; Zheng, Jianqiu; Xu, Xiaofeng; Yang, Ziming; Graham, David E.; Gu, Baohua; Painter, Scott L.; Thornton, Peter E.

2016-09-01

Soil organic carbon turnover to CO2 and CH4 is sensitive to soil redox potential and pH conditions. However, land surface models do not consider redox and pH in the aqueous phase explicitly, thereby limiting their use for making predictions in anoxic environments. Using recent data from incubations of Arctic soils, we extend the Community Land Model with coupled carbon and nitrogen (CLM-CN) decomposition cascade to include simple organic substrate turnover, fermentation, Fe(III) reduction, and methanogenesis reactions, and assess the efficacy of various temperature and pH response functions. Incorporating the Windermere Humic Aqueous Model (WHAM) enables us to approximately describe the observed pH evolution without additional parameterization. Although Fe(III) reduction is normally assumed to compete with methanogenesis, the model predicts that Fe(III) reduction raises the pH from acidic to neutral, thereby reducing environmental stress to methanogens and accelerating methane production when substrates are not limiting. The equilibrium speciation predicts a substantial increase in CO2 solubility as pH increases, and taking into account CO2 adsorption to surface sites of metal oxides further decreases the predicted headspace gas-phase fraction at low pH. Without adequate representation of these speciation reactions, as well as the impacts of pH, temperature, and pressure, the CO2 production from closed microcosms can be substantially underestimated based on headspace CO2 measurements only. Our results demonstrate the efficacy of geochemical models for simulating soil biogeochemistry and provide predictive understanding and mechanistic representations that can be incorporated into land surface models to improve climate predictions.

Photo-induced transformations of mercury(II) species in the presence of algae, Chlorella vulgaris

Energy Technology Data Exchange (ETDEWEB)

Deng Lin, E-mail: dlwhu@163.com [Department of Municipal Engineering, Southeast University, Nanjing 210096 (China); Fu Dafang [Department of Municipal Engineering, Southeast University, Nanjing 210096 (China); Deng Nansheng [School of Resources and Environmental Science, Wuhan University, Wuhan 430072 (China)

2009-05-30

The effects of algae (i.e., Chlorella vulgaris), Fe(III), humic substances, and pH on the photoreduction of Hg(II) under the irradiation of metal halide lamps ({lambda} {>=} 365 nm, 250 W) were investigated in this paper. The photoreduction rate of Hg(II) was found to increase with the increasing concentration of algae, Fe(III), and humic substances. The cooperation action of Fe(III) and humic substances accelerated the photoreduction of Hg(II). When the initial concentration of Hg(II) was in the range of 0.0-200.0 {mu}g L{sup -1} with initial algae concentrations 7.0 x 10{sup 9} cells L{sup -1} at pH 7.0, the initial photoreduction rate of Hg(II) could be expressed by the equation: -dC{sub Hg(II)}/dt = 0.65 x [C{sub Hg(II)}]{sup 0.39} with a correlation coefficient of R = 0.9912. The study on the photochemical process in terms of total mercury mass balance revealed that more than 40.86% of Hg(II) from the algal suspension was reduced to volatile metallic mercury. This paper discussed the photoreduction mechanism of Hg(II) in the presence of algae. This research will provide information for predicting the photoreduction of Hg(II) in the real environment. It will be helpful for understanding the photochemical transformation of Hg(II) and the formation of DGM in natural water in the presence of algae complexes. It will also be helpful for providing new methods to deal with heavy metal pollution.

Photo-induced transformations of mercury(II) species in the presence of algae, Chlorella vulgaris

International Nuclear Information System (INIS)

Deng Lin; Fu Dafang; Deng Nansheng

2009-01-01

The effects of algae (i.e., Chlorella vulgaris), Fe(III), humic substances, and pH on the photoreduction of Hg(II) under the irradiation of metal halide lamps (λ ≥ 365 nm, 250 W) were investigated in this paper. The photoreduction rate of Hg(II) was found to increase with the increasing concentration of algae, Fe(III), and humic substances. The cooperation action of Fe(III) and humic substances accelerated the photoreduction of Hg(II). When the initial concentration of Hg(II) was in the range of 0.0-200.0 μg L -1 with initial algae concentrations 7.0 x 10 9 cells L -1 at pH 7.0, the initial photoreduction rate of Hg(II) could be expressed by the equation: -dC Hg(II) /dt = 0.65 x [C Hg(II) ] 0.39 with a correlation coefficient of R = 0.9912. The study on the photochemical process in terms of total mercury mass balance revealed that more than 40.86% of Hg(II) from the algal suspension was reduced to volatile metallic mercury. This paper discussed the photoreduction mechanism of Hg(II) in the presence of algae. This research will provide information for predicting the photoreduction of Hg(II) in the real environment. It will be helpful for understanding the photochemical transformation of Hg(II) and the formation of DGM in natural water in the presence of algae complexes. It will also be helpful for providing new methods to deal with heavy metal pollution.

Redox speciation of particulate iron and manganese during river/ocean mixing

International Nuclear Information System (INIS)

Zaw, M.; Szymczak, R.; Payne, T.

2000-01-01

Full text: A synchrotron radiation experiment was performed at the Australian National Beamline Facility (Photon Factory, Tsukuba, Japan) to investigate changes in the physico-chemical nature of particles during estuarine mixing. X-ray absorption near edge structure spectra (XANES) analysis was used to determine solid-state redox speciation of iron and manganese throughout the river/ocean salinity transects. Particles (>0.4μm) collected using clean techniques were stored under nitrogen during TROPICS Project expeditions to the Fly and Sepik Rivers, PNG. Results indicated that initially, particulate manganese was mostly present as Mn(IV) and Mn(III) compounds with some surface-adsorbed Mn(II). Similarly, iron was present as particulate Fe(III) and Fe(II/III) compounds with some adsorbed Fe(II). During river-ocean mixing, the proportions of both Mn(II) and Fe(III) significantly increased. These observations maybe due to increasing photochemical activity in the river plume, surface-sorption of reduced species related to the estuarine residence time of particles, or enhanced scavenging of ocean-sourced elements. Copyright (2000) American Chemical Society

A novel method of simultaneous NH4+ and NO3- removal using Fe cycling as a catalyst: Feammox coupled with NAFO.

Science.gov (United States)

Li, Xiang; Yuan, Yan; Huang, Yong; Liu, Heng-Wei; Bi, Zhen; Yuan, Yi; Yang, Peng-Bin

2018-08-01

The feasibility of using Feammox coupled with nitrate-dependent Fe(II) oxidizing (NAFO) to cause the simultaneous conversion of NH 4 + and NO 3 - was explored by inoculation with Feammox sludge and the use Fe cycling as catalyst. After 61days operation, the simultaneous conversion of NO 3 - and NH 4 + occurred with the presence of interconversion between Fe(III) and Fe(II). The conversion ratio of NH 4 + to NO 3 - stabilized at 0.9-1. The results of isotopic tracing and microbial diversity analysis indicated that NH 4 + was first oxidized to NO 2 - by Fe(III), then NO 3 - was reduced to NO 2 - and N 2 by the Fe(II) produced in Feammox process, and finally, the NO 2 - produced in NAFO process underwent an Anammox process with the remaining NH 4 + to yield N 2 . The results showed the simultaneous continuous conversion process of NO 3 - and NH 4 + with limited Fe as a catalyst was a coupled process of Feammox, Anammox, and NAFO under the anaerobic conditions. Copyright © 2018 Elsevier B.V. All rights reserved.

The effect of water content on the magnetic and structural properties of goethite

International Nuclear Information System (INIS)

Betancur, J.D.; Barrero, C.A.; Greneche, J.M.; Goya, G.F.

2004-01-01

We have studied the effect of water content on the magnetic and structural properties of goethite. For that purpose, four samples were prepared using two different hydrothermal methods, one of them is derived on the Fe(II) precursors and the other one from Fe(III) precursors. The samples were characterized by X-ray diffraction (XRD), TGA, BET, FTIR, Moessbauer spectrometry at RT, 77 and 4.2 K and ZFC and FC curves. The results suggest that the goethites from the Fe(II) precursors are less crystalline, have higher water contents and do not show magnetic ordered structure at RT in comparison to the goethites from the Fe(III) precursors. The goethites from the last systems exhibit good crystallinity, low water content and magnetic ordering at room temperature. Our results suggest that both structural and adsorbed water contents reduce the magnetic hyperfine field at 4.2 K. A linear correlation with regression coefficient of 0.91 between the saturation hyperfine field and both the structural hydroxyl content and the surface area could be derived

Role of iron species in the photo-transformation of phenol in artificial and natural seawater

International Nuclear Information System (INIS)

Calza, Paola; Massolino, Cristina; Pelizzetti, Ezio; Minero, Claudio

2012-01-01

The role played by iron oxides (goethite and akaganeite) and iron(II)/(III) species as photo-sensitizers toward the transformation of organic matter was examined in saline water using phenol as a model molecule. The study was carried out in NaCl 0.7 M solution at pH 8, artificial (ASW) and natural (NSW) seawater, in a device simulating solar light spectrum and intensity. Under illumination phenol decomposition occurs in all the investigated cases. Conversely, dark experiments show that no reaction takes place, implying that phenol transformation is a light- activated process. Following the addition of Fe(II) ions to aerated solutions, Fe(II) is easily oxidized to Fe(III) and hydrogen peroxide is formed. Regardless of the addition of Fe(II) or Fe(III) ions, photo-activated degradation is mediated by Fe(III) species. Several (and different) hydroxylated and halogenated intermediates were identified. In ASW, akaganeite promotes the formation of ortho and para chloro derivatives (2- and 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol), while goethite induces the formation of 3-chlorophenol and bromophenols. Conversely, Fe(II) or Fe(III) addition causes the formation of 3- and 4-chlorophenol and 2,3- or 3,4-dichlorophenol. 4-Bromophenol was only identified when irradiating Fe(II) spiked solutions. Natural seawater sampled in the Gulf of Trieste, Italy, has been spiked with phenol and irradiated. Phenol photo-induced transformation in NSW mediated by natural photosensitizers occurs and leads to the formation of numerous halophenols, condensed products and nitrophenols. When NSW is spiked with phenol and iron oxides, Fe(II) or Fe(III), halophenols production is enhanced. A close analogy exists between Fe(III), Fe(II)/goethite in ASW and NSW products. Different halophenols production in the natural seawater samples depends on Fe(II)/goethite (above all for 3-chlorophenol, 2,3-dichlorophenol and 4-bromophenol formation) and on Fe(III) colloidal species (3

Microbial dissimilatory iron(III) reduction: Studies on the mechanism and on processes of environmental relevance

OpenAIRE

Jahn, Michael

2005-01-01

Many microbes are able to respire aerobically oxygen or anaerobically other electron acceptors for example sulphate, nitrate, manganese(IV) or Fe(III). As iron minerals are widespread in nature, dissimilatory iron(III) reduction by different microorganisms is a very important process of anaerobic respiration. The general goal of this work was to improve the knowledge of processes, in which iron-reducing microbes are said to play an important role. For this purpose, in one part the focus wa...

Removal of Cobalt Ion by Adsorbing Colloidal Flotation

Energy Technology Data Exchange (ETDEWEB)

Jung, In Ha; Lee, Jung Won [Korea Atomic Energy Research Institute, Taejon (Korea)

1998-09-30

Simulated waste liquid containing 50 ppm cobalt ion was treated by adsorbing colloidal flotation using Fe(III) or Al(III) as flocculant and a sodium lauryl sulfate as a collector. Parameters such as pH, surfactant concentration, Fe(III) or Al(III) concentration, gas flow rate, etc., were considered. The flotation with Fe(III) showed 99.8% removal efficiency of cobalt on the conditions of initial cobalt ion concentration 50 ppm, pH 9.5, gas flow rate 70 ml/min, and flotation time 30 min. When the waste solution was treated with 35% H{sub 2}O{sub 2} prior to adsorbing colloidal flotation, the optimal pH for removing cobalt shifted to weak alkaline range and flotation could be applied in wider range of pH as compared to non-use of H{sub 2}O{sub 2}. Additional use of 20 ppm Al(III) after precipitation of 50 ppm Co(II) with 50 ppm Fe(III) made the optimal pH range for preferable flotation wider. Foreign ions such as, NO{sub 3}{sup -}, SO{sub 4}{sup 2-}, Na{sup +}, Ca{sup 2+} were adopted and their effects were observed, Of which sulfate ion was found to be detrimental to removal of cobalt ion by flotation. Coprecipitation of Co ion with Fe(III) and Al(III) resulted in better removal efficiency of cobalt ion in the presence of sulfate ion. (author). 14 refs., 13 figs.

Abiotic Deposition of Fe Complexes onto Leptothrix Sheaths

Science.gov (United States)

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

2016-01-01

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

Abiotic Deposition of Fe Complexes onto Leptothrix Sheaths

Directory of Open Access Journals (Sweden)

Tatsuki Kunoh

2016-06-01

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

The First Example of a Nitrile Hydratase Model Complex that Reversibly Binds Nitriles

Science.gov (United States)

Shearer, Jason; Jackson, Henry L.; Schweitzer, Dirk; Rittenberg, Durrell K.; Leavy, Tanya M.; Kaminsky, Werner; Scarrow, Robert C.; Kovacs, Julie A.

2015-01-01

Nitrile hydratase (NHase) is an iron-containing metalloenzyme that converts nitriles to amides. The mechanism by which this biochemical reaction occurs is unknown. One mechanism that has been proposed involves nucleophilic attack of an Fe-bound nitrile by water (or hydroxide). Reported herein is a five-coordinate model compound ([FeIII(S2Me2N3(Et,Pr))]+) containing Fe(III) in an environment resembling that of NHase, which reversibly binds a variety of nitriles, alcohols, amines, and thiocyanate. XAS shows that five-coordinate [FeIII(S2Me2N3(Et,Pr))]+ reacts with both methanol and acetonitrile to afford a six-coordinate solvent-bound complex. Competitive binding studies demonstrate that MeCN preferentially binds over ROH, suggesting that nitriles would be capable of displacing the H2O coordinated to the iron site of NHase. Thermodynamic parameters were determined for acetonitrile (ΔH = −6.2(±0.2) kcal/mol, ΔS = −29.4(±0.8) eu), benzonitrile (−4.2(±0.6) kcal/mol, ΔS = −18(±3) eu), and pyridine (ΔH = −8(±1) kcal/mol, ΔS = −41(±6) eu) binding to [FeIII(S2Me2N3(Et,Pr))]+ using variable-temperature electronic absorption spectroscopy. Ligand exchange kinetics were examined for acetonitrile, iso-propylnitrile, benzonitrile, and 4-tert-butylpyridine using 13C NMR line-broadening analysis, at a variety of temperatures. Activation parameters for ligand exchange were determined to be ΔH‡ = 7.1(±0.8) kcal/mol, ΔS‡ = −10(±1) eu (acetonitrile), ΔH‡ = 5.4(±0.6) kcal/mol, ΔS‡ = −17(±2) eu (iso-propionitrile), ΔH‡ = 4.9(±0.8) kcal/mol, ΔS‡ = −20(±3) eu (benzonitrile), and ΔH‡ = 4.7(±1.4) kcal/mol ΔS‡ = −18(±2) eu (4-tert-butylpyridine). The thermodynamic parameters for pyridine binding to a related complex, [FeIII(S2Me2N3(Pr,Pr))]+ (ΔH = −5.9(±0.8) kcal/mol, ΔS = −24(±3) eu), are also reported, as well as kinetic parameters for 4-tert-butylpyridine exchange (ΔH‡ = 3.1(±0.8) kcal/mol, ΔS‡)−25(±3) eu

Turkeyen Campus, P.O. Box 10 1110, Georgetown, Guyana (S ...

African Journals Online (AJOL)

a

K values) for Fe(III) and Cr(III) complexes, respectively, at 35 oC and ionic strength 0.1 M. KEY WORDS: Paper ... A study on the feasibility of controlling the level of iron(III) and chromium(III) metal ions by ... 10-3 M. Metal spots were detected on the paper using potassium ferrocyanide solution (BDH, Poole,. UK) for Fe(III) and ...

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

Science.gov (United States)

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

2002-11-01

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

EPR, UV-Visible, and Near-Infrared Spectroscopic Characterization of Dolomite

Directory of Open Access Journals (Sweden)

S. Lakshmi Reddy

2008-01-01

Full Text Available Dolomite mineral samples having white and light green colors of Indian origin have been characterized by EPR, optical, and NIR spectroscopy. The optical spectrum exhibits a number of electronic bands due to presence of Fe(III ions in the mineral. From EPR studies, the parameters of g for Fe(III and g,A, and D for Mn(II are evaluated and the data confirm that the ions are in distorted octahedron. Optical absorption studies reveal that Fe(III is in distorted octahedron. The bands in NIR spectra are due to the overtones and combinations of water molecules. Thus EPR and optical absorption spectral studies have proven useful for the study of the solid state chemistry of dolomite.

Layered rare-earth hydroxide (LRH, R = Tb, Y) composites with fluorescein: delamination, tunable luminescence and application in chemosensoring for detecting Fe(iii) ions.

Science.gov (United States)

Su, Feifei; Guo, Rong; Yu, Zihuan; Li, Jian; Liang, Zupei; Shi, Keren; Ma, Shulan; Sun, Genban; Li, Huifeng

2018-04-17

We demonstrate a novel example of tunable luminescence and the application of the delaminated FLN/OS-LRH composites (LRHs are layered rare-earth hydroxides, R = Tb, Y; FLN is the fluorescein named 2-(6-hydroxy-3-oxo-(3H)-xanthen-9-yl)benzoic acid; OS is the anionic surfactant 1-octane sulfonic acid sodium) in detecting Fe(iii) ions. The FLNxOS1-x species (x = 0.02, 0.05, 0.10, and 0.20) are intercalated into the LTbyY1-yH layers (y = 1, 0.9, 0.7, 0.5, 0.3, 0.1 and 0) by ion exchange reactions to yield the composites FLNxOS1-x-LTbyY1-yH. In the solid state, the LYH composites display green emission (564 nm) arising from the organic FLN, while in LTbH composites, the luminescence of the Tb3+ in the layers (545 nm) and the FLN in the interlayers is co-quenched. In the delaminated state in formamide (FM), FLNxOS1-x-LTbH composites display green to yellowish-green luminescence (540-574 nm) following the increasing FLN/OS ratio; while the FLN0.02OS0.98-LTbyY1-yH composites show green emission at ∼540 nm. The fluorescence lifetimes of the composites (4.22-4.63 ns) are comparable to the free FLN-Na, and the quantum yields (31.62-78.70%) of the composites especially that (78.70%) of the FLN0.02OS0.98-LYH are much higher than that (28.40%) of free FLN-Na. The recognition ability of the FLN0.02OS0.98-LYH composite for metal cations is researched. The delaminated FLN0.02OS0.98-LYH colloidal suspension exhibits high selectivity for Fe3+ over other ions (Mg2+, Al3+, Ni2+, Co2+, Cu2+, Zn2+, Mn2+, Pb2+, and Cd2+) with fluorescence quenching, which can work as a kind of turn-off fluorescence sensor for the detection of Fe3+. The detection limit of Fe3+ is determined to be 2.58 × 10-8 M and the quenching constant (Ksv) is 1.70 × 103 M-1. This is the first work on LRH materials working as a chemosensor for recognising metal cations. It provides a new approach for the design of LRH materials to be applied in fluorescence chemosensing.

Selective solid-phase extraction using oxidized activated carbon modified with triethylenetetramine for preconcentration of metal ions

Science.gov (United States)

Zhang, Li; Chang, Xijun; Li, Zhenhua; He, Qun

2010-02-01

A new selective solid-phase extractant using activated carbon as matrix which was purified, oxidized and modified by triethylenetetramine (AC-TETA) was prepared and characterized by FT-IR spectroscopy. At pH 4, quantitative extraction of trace Cr(III), Fe(III) and Pb(II) was obtained and determined by inductively coupled plasma optical emission spectrometry (ICP-OES). Complete elution of the adsorbed metal ions from the sorbent surface was carried out using 0.5 mol L -1 HCl. The maximum static adsorption capacity of sorbent for Cr(III), Fe(III) and Pb(II) was 34.6, 36.5 and 51.9 mg g -1, respectively. The time of quantitative adsorption was less than 2 min. The detection limits of the method was found to be 0.71, 0.35 and 0.45 ng mL -1 for Cr(III), Fe(III) and Pb(II), and the relative standard deviation (RSD) was 3.7%, 2.2% and 2.5%, respectively. Moreover, the method was free from interference with common coexiting ions. The method was also successfully applied to the preconcentration of trace Cr(III), Fe(III) and Pb(II) in synthetic samples and a real sample with satisfactory results.

Enhanced⁹⁹Tc retention in glass waste form using Tc(IV)-incorporated Fe minerals

OpenAIRE

Um, W; Luksic, SA; Wang, G; Saslow, S; Kim, DS; Schweiger, MJ; Soderquist, CZ; Bowden, ME; Lukens, WW; Kruger, AA

2017-01-01

© 2017 Elsevier B.V. Technetium ( 99 Tc) immobilization by doping into iron oxide mineral phases may alleviate the problems with Tc volatility during vitrification of nuclear waste. Because reduced Tc, Tc(IV), substitutes for Fe(III) in the crystal structure by a process of Tc reduction from Tc(VII) to Tc(IV) followed by co-precipitation of Fe oxide minerals, two Tc-incorporated Fe minerals (Tc-goethite and Tc-magnetite/maghemite) were prepared and tested for Tc retention in glass melt sample...

1-(2-Formamidoethyl)-3-phenylurea functionalized activated carbon for selective solid-phase extraction and preconcentration of metal ions

Energy Technology Data Exchange (ETDEWEB)

Tu Zhifeng; He Qun [Department of Chemistry, Lanzhou University, Lanzhou 730000 (China); Chang, Xijun, E-mail: tuzhf07@lzu.cn [Department of Chemistry, Lanzhou University, Lanzhou 730000 (China); Hu Zheng; Gao Ru; Zhang Lina; Li Zhenhua [Department of Chemistry, Lanzhou University, Lanzhou 730000 (China)

2009-09-07

A novel method that utilizes 1-(2-formamidoethyl)-3-phenylurea-modified activated carbon (AC-1-(2-formamidoethyl)-3-phenylurea) as a solid-phase extractant has been developed for simultaneous preconcentration of trace Cr(III), Cu(II), Fe(III) and Pb(II) prior to the measurement by inductively coupled plasma atomic emission spectrometry (ICP-AES). Experimental conditions for effective adsorption of trace levels of Cr(III), Cu(II), Fe(III) and Pb(II) were optimized using batch and column procedures in detail. The optimum pH value for the separation of metal ions simultaneously on the new sorbent was 4. And the adsorbed metal ions could be completely eluted by using 2.0 mL 2.0 mol L{sup -1} HCl solution. Common coexisting ions did not interfere with the separation and determination of target metal ions. The maximum static adsorption capacity of the sorbent at optimum conditions was found to be 39.8, 39.9, 77.8 and 17.3 mg g{sup -1} for Cr(III), Cu(II), Fe(III) and Pb(II), respectively. The detection limits of the method were found to be 0.15, 0.41, 0.27 and 0.36 ng mL{sup -1} for Cr(III), Cu(II), Fe(III) and Pb(II), respectively. The relative standard deviation (RSD) of the method was lower than 4.0% (n = 8). The method was successfully applied for the preconcentration of trace Cr(III), Cu(II), Fe(III) and Pb(II) in natural and certified samples with satisfactory results.

1-(2-Formamidoethyl)-3-phenylurea functionalized activated carbon for selective solid-phase extraction and preconcentration of metal ions.

Science.gov (United States)

Tu, Zhifeng; He, Qun; Chang, Xijun; Hu, Zheng; Gao, Ru; Zhang, Lina; Li, Zhenhua

2009-09-07

A novel method that utilizes 1-(2-formamidoethyl)-3-phenylurea-modified activated carbon (AC-1-(2-formamidoethyl)-3-phenylurea) as a solid-phase extractant has been developed for simultaneous preconcentration of trace Cr(III), Cu(II), Fe(III) and Pb(II) prior to the measurement by inductively coupled plasma atomic emission spectrometry (ICP-AES). Experimental conditions for effective adsorption of trace levels of Cr(III), Cu(II), Fe(III) and Pb(II) were optimized using batch and column procedures in detail. The optimum pH value for the separation of metal ions simultaneously on the new sorbent was 4. And the adsorbed metal ions could be completely eluted by using 2.0 mL 2.0 mol L(-1) HCl solution. Common coexisting ions did not interfere with the separation and determination of target metal ions. The maximum static adsorption capacity of the sorbent at optimum conditions was found to be 39.8, 39.9, 77.8 and 17.3 mg g(-1) for Cr(III), Cu(II), Fe(III) and Pb(II), respectively. The detection limits of the method were found to be 0.15, 0.41, 0.27 and 0.36 ng mL(-1) for Cr(III), Cu(II), Fe(III) and Pb(II), respectively. The relative standard deviation (RSD) of the method was lower than 4.0% (n=8). The method was successfully applied for the preconcentration of trace Cr(III), Cu(II), Fe(III) and Pb(II) in natural and certified samples with satisfactory results.

1-(2-Formamidoethyl)-3-phenylurea functionalized activated carbon for selective solid-phase extraction and preconcentration of metal ions

International Nuclear Information System (INIS)

Tu Zhifeng; He Qun; Chang, Xijun; Hu Zheng; Gao Ru; Zhang Lina; Li Zhenhua

2009-01-01

A novel method that utilizes 1-(2-formamidoethyl)-3-phenylurea-modified activated carbon (AC-1-(2-formamidoethyl)-3-phenylurea) as a solid-phase extractant has been developed for simultaneous preconcentration of trace Cr(III), Cu(II), Fe(III) and Pb(II) prior to the measurement by inductively coupled plasma atomic emission spectrometry (ICP-AES). Experimental conditions for effective adsorption of trace levels of Cr(III), Cu(II), Fe(III) and Pb(II) were optimized using batch and column procedures in detail. The optimum pH value for the separation of metal ions simultaneously on the new sorbent was 4. And the adsorbed metal ions could be completely eluted by using 2.0 mL 2.0 mol L -1 HCl solution. Common coexisting ions did not interfere with the separation and determination of target metal ions. The maximum static adsorption capacity of the sorbent at optimum conditions was found to be 39.8, 39.9, 77.8 and 17.3 mg g -1 for Cr(III), Cu(II), Fe(III) and Pb(II), respectively. The detection limits of the method were found to be 0.15, 0.41, 0.27 and 0.36 ng mL -1 for Cr(III), Cu(II), Fe(III) and Pb(II), respectively. The relative standard deviation (RSD) of the method was lower than 4.0% (n = 8). The method was successfully applied for the preconcentration of trace Cr(III), Cu(II), Fe(III) and Pb(II) in natural and certified samples with satisfactory results.

Isolation of phyllosilicate-iron redox cycling microorganisms from an illite-smectite rich hydromorphic soil.

Science.gov (United States)

Shelobolina, Evgenya; Konishi, Hiromi; Xu, Huifang; Benzine, Jason; Xiong, Mai Yia; Wu, Tao; Blöthe, Marco; Roden, Eric

2012-01-01

The biogeochemistry of phyllosilicate-Fe redox cycling was studied in a Phalaris arundinacea (reed canary grass) dominated redoximorphic soil from Shovelers Sink, a small glacial depression near Madison, WI. The clay size fraction of Shovelers Sink soil accounts for 16% of the dry weight of the soil, yet contributes 74% of total Fe. The dominant mineral in the clay size fraction is mixed layer illite-smectite, and in contrast to many other soils and sediments, Fe(III) oxides are present in low abundance. We examined the Fe biogeochemistry of Shovelers Sink soils, estimated the abundance of Fe redox cycling microorganisms, and isolated in pure culture representative phyllosilicate-Fe oxidizing and reducing organisms. The abundance of phyllosilicate-Fe reducing and oxidizing organisms was low compared to culturable aerobic heterotrophs. Both direct isolation and dilution-to-extinction approaches using structural Fe(II) in Bancroft biotite as a Fe(II) source, and O(2) as the electron acceptor, resulted in recovery of common rhizosphere organisms including Bradyrhizobium spp. and strains of Cupriavidus necator and Ralstonia solanacearum. In addition to oxidizing biotite and soluble Fe(II) with O(2), each of these isolates was able to oxidize Fe(II) in reduced NAu-2 smectite with [Formula: see text] as the electron acceptor. Oxidized NAu-2 smectite or amorphous Fe(III) oxide served as electron acceptors for enrichment and isolation of Fe(III)-reducing microorganisms, resulting in recovery of a strain related to Geobacter toluenoxydans. The ability of the recovered microorganisms to cycle phyllosilicate-Fe was verified in an experiment with native Shovelers Sink clay. This study confirms that Fe in the native Shovelers Sink clay is readily available for microbial redox transformation and can be cycled by the Fe(III)-reducing and Fe(II)-oxidizing microorganisms recovered from the soil.

Isolation of Phyllosilicate–Iron Redox Cycling Microorganisms from an Illite–Smectite Rich Hydromorphic Soil

Science.gov (United States)

Shelobolina, Evgenya; Konishi, Hiromi; Xu, Huifang; Benzine, Jason; Xiong, Mai Yia; Wu, Tao; Blöthe, Marco; Roden, Eric

2012-01-01

The biogeochemistry of phyllosilicate–Fe redox cycling was studied in a Phalaris arundinacea (reed canary grass) dominated redoximorphic soil from Shovelers Sink, a small glacial depression near Madison, WI. The clay size fraction of Shovelers Sink soil accounts for 16% of the dry weight of the soil, yet contributes 74% of total Fe. The dominant mineral in the clay size fraction is mixed layer illite–smectite, and in contrast to many other soils and sediments, Fe(III) oxides are present in low abundance. We examined the Fe biogeochemistry of Shovelers Sink soils, estimated the abundance of Fe redox cycling microorganisms, and isolated in pure culture representative phyllosilicate–Fe oxidizing and reducing organisms. The abundance of phyllosilicate–Fe reducing and oxidizing organisms was low compared to culturable aerobic heterotrophs. Both direct isolation and dilution-to-extinction approaches using structural Fe(II) in Bancroft biotite as a Fe(II) source, and O2 as the electron acceptor, resulted in recovery of common rhizosphere organisms including Bradyrhizobium spp. and strains of Cupriavidus necator and Ralstonia solanacearum. In addition to oxidizing biotite and soluble Fe(II) with O2, each of these isolates was able to oxidize Fe(II) in reduced NAu-2 smectite with NO3- as the electron acceptor. Oxidized NAu-2 smectite or amorphous Fe(III) oxide served as electron acceptors for enrichment and isolation of Fe(III)-reducing microorganisms, resulting in recovery of a strain related to Geobacter toluenoxydans. The ability of the recovered microorganisms to cycle phyllosilicate–Fe was verified in an experiment with native Shovelers Sink clay. This study confirms that Fe in the native Shovelers Sink clay is readily available for microbial redox transformation and can be cycled by the Fe(III)-reducing and Fe(II)-oxidizing microorganisms recovered from the soil. PMID:22493596

An isoelectronic NO dioxygenase reaction using a nonheme iron(III)-peroxo complex and nitrosonium ion.

Science.gov (United States)

Yokoyama, Atsutoshi; Han, Jung Eun; Karlin, Kenneth D; Nam, Wonwoo

2014-02-18

Reaction of a nonheme iron(III)-peroxo complex, [Fe(III)(14-TMC)(O2)](+), with NO(+), a transformation which is essentially isoelectronic with that for nitric oxide dioxygenases [Fe(III)(O2˙(-)) + NO], affords an iron(IV)-oxo complex, [Fe(IV)(14-TMC)(O)](2+), and nitrogen dioxide (NO2), followed by conversion to an iron(III)-nitrato complex, [Fe(III)(14-TMC)(NO3)(F)](+).

Quantitative Environmental Cell - Transmission Electron Microscopy: Studies of Microbial Cr(VI) and Fe(III) Reduction

National Research Council Canada - National Science Library

Daulton, Tyron

2002-01-01

.... Measurements by EELS demonstrated that cell boundaries became saturated with low concentrations of Cr and the precipitates encrusting bacterial cells contained a reduced form of Cr in oxidation state +3 or lower...

Iron Isotope Fractionation during Fe(II) Oxidation Mediated by the Oxygen-Producing Marine Cyanobacterium Synechococcus PCC 7002

Energy Technology Data Exchange (ETDEWEB)

Swanner, E. D.; Bayer, T.; Wu, W.; Hao, L.; Obst, M.; Sundman, A.; Byrne, J. M.; Michel, F. M.; Kleinhanns, I. C.; Kappler, A.; Schoenberg, R.

2017-04-11

In this study, we couple iron isotope analysis to microscopic and mineralogical investigation of iron speciation during circumneutral Fe(II) oxidation and Fe(III) precipitation with photosynthetically produced oxygen. In the presence of the cyanobacterium Synechococcus PCC 7002, aqueous Fe(II) (Fe(II)_aq) is oxidized and precipitated as amorphous Fe(III) oxyhydroxide minerals (iron precipitates, Fe_ppt), with distinct isotopic fractionation (ε⁵⁶Fe) values determined from fitting the δ⁵⁶Fe(II)_aq (1.79‰ and 2.15‰) and the δ⁵⁶Fe_ppt (2.44‰ and 2.98‰) data trends from two replicate experiments. Additional Fe(II) and Fe(III) phases were detected using microscopy and chemical extractions and likely represent Fe(II) and Fe(III) sorbed to minerals and cells. The iron desorbed with sodium acetate (FeNaAc) yielded heavier δ⁵⁶Fe compositions than Fe(II)_aq. Modeling of the fractionation during Fe(III) sorption to cells and Fe(II) sorption to Feppt, combined with equilibration of sorbed iron and with Fe(II)_aq using published fractionation factors, is consistent with our resulting δ⁵⁶FeNaAc. The δ⁵⁶Fe_ppt data trend is inconsistent with complete equilibrium exchange with Fe(II)aq. Because of this and our detection of microbially excreted organics (e.g., exopolysaccharides) coating Feppt in our microscopic analysis, we suggest that electron and atom exchange is partially suppressed in this system by biologically produced organics. These results indicate that cyanobacteria influence the fate and composition of iron in sunlit environments via their role in Fe(II) oxidation through O₂ production, the capacity of their cell surfaces to sorb iron, and the interaction of secreted organics with Fe(III) minerals.

Investigating the effect of ascorbate on the Fe(II)-catalyzed transformation of the poorly crystalline iron mineral ferrihydrite.

Science.gov (United States)

Xiao, Wei; Jones, Adele M; Collins, Richard N; Waite, T David

2018-05-09

The inorganic core of the iron storage protein, ferritin, is recognized as being analogous to the poorly crystalline iron mineral, ferrihydrite (Fh). Fh is also abundant in soils where it is central to the redox cycling of particular soil contaminants and trace elements. In geochemical circles, it is recognized that Fh can undergo Fe(II)-catalyzed transformation to form more crystalline iron minerals, vastly altering the reactivity of the iron oxide and, in some cases, the redox poise of the system. Of relevance to both geochemical and biological systems, we investigate here if the naturally occurring reducing agent, ascorbate, can effect such an Fe(II)-catalyzed transformation of Fh at 25 °C and circumneutral pH. The transformation of ferrihydrite to possible secondary Fe(III) mineralization products was quantified using Fourier transform infrared (FTIR) spectroscopy, with supporting data obtained using X-ray absorbance spectroscopy (XAS) and X-ray diffraction (XRD). Whilst the amount of Fe(II) formed in the presence of ascorbate has resulted in Fh transformation in previous studies, no transformation of Fh to more crystalline Fe(III) (oxyhydr)oxides was observed in this study. Further experiments indicated this was due to the ability of ascorbate to inhibit the formation of goethite, lepidocrocite and magnetite. The manner in which ascorbate associated with Fh was investigated using FTIR and total organic carbon (TOC) analysis. The majority of ascorbate was found to adsorb to the Fh surface under anoxic conditions but, under oxic conditions, ascorbate was initially adsorbed then became incorporated within the Fe(III) (oxyhydr)oxide structure (i.e., co-precipitated) over time. Copyright © 2018 Elsevier B.V. All rights reserved.

Arsenite and ferrous iron oxidation linked to chemolithotrophic denitrification for the immobilization of arsenic in anoxic environments

Science.gov (United States)

Sun, W.; Sierra-Alvarez, R.; Milner, L.; Oremland, R.; Field, J.A.

2009-01-01

The objective of this study was to explore a bioremediation strategy based on injecting NO3- to support the anoxic oxidation of ferrous iron (Fe(II)) and arsenite (As(III)) in the subsurface as a means to immobilize As in the form of arsenate (As(V)) adsorbed onto biogenic ferric (Fe(III)) (hydr)oxides. Continuous flows and filled columns were used to simulate a natural anaerobic groundwater and sediment system with co-occurring As(III) and Fe(II) in the presence (column SF1) or absence (column SF2) of nitrate, respectively. During operation for 250 days, the average influent arsenic concentration of 567 ??g L-1 was reduced to 10.6 (??9.6) ??g L-1 in the effluent of column SF1. The cumulative removal of Fe(II) and As(III) in SF1 was 6.5 to 10-fold higher than that in SF2. Extraction and measurement of the mass of iron and arsenic immobilized on the sand packing of the columns were close to the iron and arsenic removed from the aqueous phase during column operation. The dominant speciation of the immobilized iron and arsenic was Fe(III) and As(V) in SF1, compared with Fe(II) and As(III) in SF2. The speciation was confirmed by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results indicate that microbial oxidation of As(III) and Fe(II) linked to denitrification resulted in the enhanced immobilization of aqueous arsenic in anaerobic environments by forming Fe(III) (hydr)oxide coated sands with adsorbed As(V). ?? 2009 American Chemical Society.

Study of uranium oxidation states in geological material.

Science.gov (United States)

Pidchenko, I; Salminen-Paatero, S; Rothe, J; Suksi, J

2013-10-01

A wet chemical method to determine uranium (U) oxidation states in geological material has been developed and tested. The problem faced in oxidation state determinations with wet chemical methods is that U redox state may change when extracted from the sample material, thereby leading to erroneous results. In order to quantify and monitor U redox behavior during the acidic extraction in the procedure, an analysis of added isotopic redox tracers, (236)U(VI) and (232)U(IV), and of variations in natural uranium isotope ratio ((234)U/(238)U) of indigenous U(IV) and U(VI) fractions was performed. Two sample materials with varying redox activity, U bearing rock and U-rich clayey lignite sediment, were used for the tests. The Fe(II)/Fe(III) redox-pair of the mineral phases was postulated as a potentially disturbing redox agent. The impact of Fe(III) on U was studied by reducing Fe(III) with ascorbic acid, which was added to the extraction solution. We observed that ascorbic acid protected most of the U from oxidation. The measured (234)U/(238)U ratio in U(IV) and U(VI) fractions in the sediment samples provided a unique tool to quantify U oxidation caused by Fe(III). Annealing (sample heating) to temperatures above 500 °C was supposed to heal ionizing radiation induced defects in the material that can disturb U redox state during extraction. Good agreement between two independent methods was obtained for DL-1a material: an average 38% of U(IV) determined by redox tracer corrected wet chemistry and 45% for XANES. Copyright © 2013 Elsevier Ltd. All rights reserved.

Synthesis of Highly Reactive Subnano-sized Zero-valent Iron using Smectite Clay Templates

Science.gov (United States)

Gu, Cheng; Jia, Hanzhang; Li, Hui; Teppen, Brian J.; Boyd, Stephen A.

2010-01-01

A novel method was developed for synthesizing subnano-sized zero-valent iron (ZVI) using smectite clay layers as templates. Exchangeable Fe(III) cations compensating the structural negative charges of smectites were reduced with NaBH4, resulting in the formation of ZVI. The unique structure of smectite clay, in which isolated exchangeable Fe(III) cations reside near the sites of structural negative charges, inhibited the agglomeration of ZVI resulting in the formation of discrete regions of subnanoscale ZVI particles in the smectite interlayer regions. X-ray diffraction revealed an interlayer spacing of ~ 5 Å. The non-structural iron content of this clay yields a calculated ratio of two atoms of ZVI per three cation exchange sites, in full agreement with the XRD results since the diameter of elemental Fe is 2.5 Å. The clay-templated ZVI showed superior reactivity and efficiency compared to other previously reported forms of ZVI as indicated by the reduction of nitrobenzene; structural Fe within the aluminosilicate layers was nonreactive. At a 1:3 molar ratio of nitrobenzene:non-structural Fe, a reaction efficiency of 83% was achieved, and over 80% of the nitrobenzene was reduced within one minute. These results confirm that non-structural Fe from Fe(III)-smectite was reduced predominantly to ZVI which was responsible for the reduction of nitrobenzene to aniline. This new form of subnano-scale ZVI may find utility in the development of remediation technologies for persistent environmental contaminants, e.g. as components of constructed reactive domains such as reactive caps for contaminated sediments. PMID:20446730

Synthesis of highly reactive subnano-sized zero-valent iron using smectite clay templates.

Science.gov (United States)

Gu, Cheng; Jia, Hanzhong; Li, Hui; Teppen, Brian J; Boyd, Stephen A

2010-06-01

A novel method was developed for synthesizing subnano-sized zero-valent iron (ZVI) using smectite clay layers as templates. Exchangeable Fe(III) cations compensating the structural negative charges of smectites were reduced with NaBH(4), resulting in the formation of ZVI. The unique structure of smectite clay, in which isolated exchangeable Fe(III) cations reside near the sites of structural negative charges, inhibited the agglomeration of ZVI resulting in the formation of subnanoscale ZVI particles in the smectite interlayer regions. X-ray diffraction revealed an interlayer spacing of approximately 5 A. The non-structural iron content of this clay yields a calculated ratio of two atoms of ZVI per three cation exchange sites, in full agreement with the X-ray diffraction (XRD) results since the diameter of elemental Fe is 2.5 A. The clay-templated ZVI showed superior reactivity and efficiency compared to other previously reported forms of ZVI as indicated by the reduction of nitrobenzene; structural Fe within the aluminosilicate layers was nonreactive. At a 1:3 molar ratio of nitrobenzene/non-structural Fe, a reaction efficiency of 83% was achieved, and over 80% of the nitrobenzene was reduced within one minute. These results confirm that non-structural Fe from Fe(III)-smectite was reduced predominantly to ZVI which was responsible for the reduction of nitrobenzene to aniline. This new form of subnanoscale ZVI may find utility in the development of remediation technologies for persistent environmental contaminants, for example, as components of constructed reactive domains such as reactive caps for contaminated sediments.

Reduction of Ferrrihydrite and Akaganeite by Shewanella alga (PAH93)

Science.gov (United States)

Jung, M.; Kim, Y.; Lee, Y.; Kwon, K.; Roh, Y.

2009-12-01

Shewanella species are capable of oxidizing diverse organic acids coupled to reducing Fe(III) (oxy)hydroxides to crystalline Fe(II)-containing phases such as magnetite, siderite, and vivianite. The objective of this study was to examine reduction of ferrihydrite and akaganeite as the electron acceptors using various organic acids as the electron donors by Shewanella alga (PAH93) isolated from Yeosu, South Korea. Microbial reduction of akaganeite (40 mM) and ferrihydrite (40 mM) was examined using acetate (10 mM), glucose (10 mM), and lactate (10 mM) as electron donors at room temperature. Ferrozine method was used to analyze both water soluble and HCl soluble Fe(II) concentrations during the microbial Fe(III) reduction. XRD and TEM-EDX analyses were used to characterize biominerals formed by PAH93. PAH93 was completely reduced ferrihydrite to Fe(II), which transformed as siderite (FeCO3). PAH93 was oxidized acetate, glucose, and lactate coupled to reducing akaganeite to magnetite or green rust. Microbial reduction of ferrihydrite resulted in higher soluble Fe(II) concentration (446 - 498 mg/L) than the reduction of akaganeite (255 - 284 mg/L) within 6 days of incubation. For 21 days of incubation, souble Fe(II) concentration during akaganeite reduction (945 - 1316 mg/L) was higher than ferrihydrite reduction (120 - 738 mg/L). It may be attributed to the differences of crystallinity of the iron minerals used for microbial iron reduction. This study indicates types of the electron acceptors, ferrihydrite and akaganeite, affect Fe(II) reduction rate and types of the biotransformed minerals.

An isoelectronic NO dioxygenase reaction using a nonheme iron(III)-peroxo complex and nitrosonium ion†

Science.gov (United States)

Yokoyama, Atsutoshi; Han, Jung Eun; Karlin, Kenneth D.; Nam, Wonwoo

2014-01-01

Reaction of a nonheme iron(III)-peroxo complex, [FeIII(14-TMC)(O2)]+, with NO+, a transformation which is essentially isoelectronic with that for nitric oxide dioxygenases [Fe(III)(O2•−) + NO], affords an iron(IV)-oxo complex, [FeIV(14-TMC)(O)]2+, and nitrogen dioxide (NO2), followed by conversion to an iron(III)-nitrato complex, [FeIII(14-TMC)(NO3)(F)]+. PMID:24394960

An isoelectronic NO dioxygenase reaction using a nonheme iron(III)-peroxo complex and nitrosonium ion†

OpenAIRE

Yokoyama, Atsutoshi; Han, Jung Eun; Karlin, Kenneth D.; Nam, Wonwoo

2014-01-01

Reaction of a nonheme iron(III)-peroxo complex, [FeIII(14-TMC)(O2)]+, with NO+, a transformation which is essentially isoelectronic with that for nitric oxide dioxygenases [Fe(III)(O2•−) + NO], affords an iron(IV)-oxo complex, [FeIV(14-TMC)(O)]2+, and nitrogen dioxide (NO2), followed by conversion to an iron(III)-nitrato complex, [FeIII(14-TMC)(NO3)(F)]+.

Iron Isotope Variations in Reduced Groundwater and in Drinking Water Supplies: A Case Study of Hanoi, Vietnam

Science.gov (United States)

Teutsch, N.; Berg, M.; von Gunten, U.; Halliday, A.

2004-12-01

In reduced groundwater iron is involved in biotic and abiotic transformation processes, both of which could lead to iron isotope fractionation. The reduced groundwater aquifers in the area of the Vietnamese capital of Hanoi are the main drinking water sources for the city. These groundwaters contain arsenic, which imposes a serious health threat to millions of people. Dissolved arsenic is related to the reducing conditions prevalent in the groundwater, and iron and arsenic contents are correlated in the sediments. We are employing iron isotope composition as a tool to better understand the processes leading to the transformation of iron in the groundwater and its role in various biogeochemical processes in reduced environments. Drinking water is supplied to the city of Hanoi from several water treatment plants (WTP) which pump the raw groundwater from a lower aquifer, while the rural surroundings pump untreated groundwater from an upper aquifer by private tubewells. Surface water from the Red River delta is the main source of recharge to these two aquifers. Due to high content of particulate natural organic matter (NOM) in the sediment leading to extensive microbial activity, the groundwaters are anoxic and rich in dissolved iron(II). The iron(II) removal in the WTPs is carried by a multi-step treatment including aeration, settling, filtration, and chlorination. We have collected natural groundwater samples for isotopic analysis from two aquifers at several locations, a groundwater depth profile and its corresponding sediment phases from the upper aquifer and the underlying aquitard, raw and treated water from several WTPs, as well as the corresponding iron(III) precipitates. The iron concentrations of groundwaters analysed in this study range from 3 to 28 mg/L and δ 57Fe (57/54 deviation from IRMM 014) values vary between -1.2 and +1.5 ‰ . The sediment depth profile has a δ 57Fe around +0.3 ‰ , which implies that the high values obtained in the groundwater

Responses of microbial community functional structures to pilot-scale uranium in situ bioremediation

Energy Technology Data Exchange (ETDEWEB)

Xu, M.; Wu, W.-M.; Wu, L.; He, Z.; Van Nostrand, J.D.; Deng, Y.; Luo, J.; Carley, J.; Ginder-Vogel, M.; Gentry, T.J.; Gu, B.; Watson, D.; Jardine, P.M.; Marsh, T.L.; Tiedje, J.M.; Hazen, T.C.; Criddle, C.S.; Zhou, J.

2010-02-15

A pilot-scale field test system with an inner loop nested within an outer loop was constructed for in situ U(VI) bioremediation at a US Department of Energy site, Oak Ridge, TN. The outer loop was used for hydrological protection of the inner loop where ethanol was injected for biostimulation of microorganisms for U(VI) reduction/immobilization. After 2 years of biostimulation with ethanol, U(VI) levels were reduced to below drinking water standard (<30 {micro}gl{sup -1}) in the inner loop monitoring wells. To elucidate the microbial community structure and functions under in situ uranium bioremediation conditions, we used a comprehensive functional gene array (GeoChip) to examine the microbial functional gene composition of the sediment samples collected from both inner and outer loop wells. Our study results showed that distinct microbial communities were established in the inner loop wells. Also, higher microbial functional gene number, diversity and abundance were observed in the inner loop wells than the outer loop wells. In addition, metal-reducing bacteria, such as Desulfovibrio, Geobacter, Anaeromyxobacter and Shewanella, and other bacteria, for example, Rhodopseudomonas and Pseudomonas, are highly abundant in the inner loop wells. Finally, the richness and abundance of microbial functional genes were highly correlated with the mean travel time of groundwater from the inner loop injection well, pH and sulfate concentration in groundwater. These results suggest that the indigenous microbial communities can be successfully stimulated for U bioremediation in the groundwater ecosystem, and their structure and performance can be manipulated or optimized by adjusting geochemical and hydrological conditions.

ARSENIC ADSORPTION AND REDUCTION IN IRON-RICH SOILS NEARBY LANDFILLS IN NORTHWEST FLORIDA

Directory of Open Access Journals (Sweden)

Hongqin Xue

2016-01-01

Full Text Available In Florida, soils are mainly composed of Myakka, an acid soil characterized by a subsurface accumulation of humus and Al(III and Fe(III oxides. Downgradient of the landfills in Northwest Florida, elevated levels of iron and arsenic observations had been made in the groundwater from monitoring wells, which was attributed to the geomicrobial iron and arsenic reduction. There is thus an immediate research need for a better understanding of the reduction reactions that are responsible for the mobilization of iron and arsenic in the subsurface soil nearby landfills. Owing to the high Fe(III oxide content, As(V adsorption reactions with Fe(III oxide surfaces are particularly important, which may control As(V reduction. This research focused on the investigation of the biogeochemical processes of the subsurface soil nearby landfills of Northwest Florida. Arsenic and iron reduction was studied in batch reactors and quantified based on Monod-type microbial kinetic growth simulations. As(V adsorption in iron-rich Northwest Floridian soils was further investigated to explain the reduction observations. It was demonstrated in this research that solubilization of arsenic in the subsurface soil nearby landfills in Northwest Florida would likely occur under conditions favoring Fe(III dissimilatory reduction.

Selective recognition by novel calix system: ICT based chemosensor for metal ions

Energy Technology Data Exchange (ETDEWEB)

Bhatt, Keyur D.; Makwana, Bharat A.; Vyas, Disha J.; Mishra, Divya R.; Jain, Vinod K., E-mail: drvkjain@hotmail.com

2014-02-15

A new calix[4]pyrrole derivative bearing four dansyl groups through hydroxyl groups has been synthesized and duly characterized by FT-IR, NMR and ESI-MS. Tetra dansylated calix[4]pyrrole (TDCP) shows selective behavior for U(VI), Th(IV) and Fe(III) ions among all other metal ions, e.g. Li(I), Na(I), K(I), Ca(II), Ni(II), Cd(II), Cu(II), Zn(II), Pb(II), Hg(II) and Ag(I), in the absorption spectra as well as in the emission spectra. The absorption spectra show a bathochromic shift while the emission spectra along with red-shift exhibit quenching for U(VI), Th(IV) and Fe(III) ions. The binding constants, stoichiometry and quantum yields have been determined. The mechanism of quenching by Stern–Vohmer equation has also been discussed. -- highlights: • A new selective turn-off fluorescent sensor i.e. tetra dansylated calix[4]pyrrole (TDCP) was synthesized and characterized. • The sensor shows selective behavior for U(VI), Th(IV) and Fe(III) ions among various other metal ions. • The absorption spectra show a bathochromic shift while the emission spectra along with red-shift exhibit quenching for U(VI), Th(IV) and Fe(III) ions. • The sensor binds metal ions in 1:1 stoichiometry with good binding constant.

Nanoparticulate iron(III) oxo-hydroxide delivers safe iron that is well absorbed and utilised in humans

Science.gov (United States)

Pereira, Dora I.A.; Bruggraber, Sylvaine F.A.; Faria, Nuno; Poots, Lynsey K.; Tagmount, Mani A.; Aslam, Mohamad F.; Frazer, David M.; Vulpe, Chris D.; Anderson, Gregory J.; Powell, Jonathan J.

2014-01-01

Iron deficiency is the most common nutritional disorder worldwide with substantial impact on health and economy. Current treatments predominantly rely on soluble iron which adversely affects the gastrointestinal tract. We have developed organic acid-modified Fe(III) oxo-hydroxide nanomaterials, here termed nano Fe(III), as alternative safe iron delivery agents. Nano Fe(III) absorption in humans correlated with serum iron increase (P solubility. The most promising preparation (iron hydroxide adipate tartrate: IHAT) showed ~80% relative bioavailability to Fe(II) sulfate in humans and, in a rodent model, IHAT was equivalent to Fe(II) sulfate at repleting haemoglobin. Furthermore, IHAT did not accumulate in the intestinal mucosa and, unlike Fe(II) sulfate, promoted a beneficial microbiota. In cellular models, IHAT was 14-fold less toxic than Fe(II) sulfate/ascorbate. Nano Fe(III) manifests minimal acute intestinal toxicity in cellular and murine models and shows efficacy at treating iron deficiency anaemia. From the Clinical Editor This paper reports the development of novel nano-Fe(III) formulations, with the goal of achieving a magnitude less intestinal toxicity and excellent bioavailability in the treatment of iron deficiency anemia. Out of the tested preparations, iron hydroxide adipate tartrate met the above criteria, and may become an important tool in addressing this common condition. PMID:24983890

Selective recognition by novel calix system: ICT based chemosensor for metal ions

International Nuclear Information System (INIS)

Bhatt, Keyur D.; Makwana, Bharat A.; Vyas, Disha J.; Mishra, Divya R.; Jain, Vinod K.

2014-01-01

A new calix[4]pyrrole derivative bearing four dansyl groups through hydroxyl groups has been synthesized and duly characterized by FT-IR, NMR and ESI-MS. Tetra dansylated calix[4]pyrrole (TDCP) shows selective behavior for U(VI), Th(IV) and Fe(III) ions among all other metal ions, e.g. Li(I), Na(I), K(I), Ca(II), Ni(II), Cd(II), Cu(II), Zn(II), Pb(II), Hg(II) and Ag(I), in the absorption spectra as well as in the emission spectra. The absorption spectra show a bathochromic shift while the emission spectra along with red-shift exhibit quenching for U(VI), Th(IV) and Fe(III) ions. The binding constants, stoichiometry and quantum yields have been determined. The mechanism of quenching by Stern–Vohmer equation has also been discussed. -- highlights: • A new selective turn-off fluorescent sensor i.e. tetra dansylated calix[4]pyrrole (TDCP) was synthesized and characterized. • The sensor shows selective behavior for U(VI), Th(IV) and Fe(III) ions among various other metal ions. • The absorption spectra show a bathochromic shift while the emission spectra along with red-shift exhibit quenching for U(VI), Th(IV) and Fe(III) ions. • The sensor binds metal ions in 1:1 stoichiometry with good binding constant

Effects of molecular composition of natural organic matter on ferric iron complexation at circumneutral pH.

Science.gov (United States)

Fujii, Manabu; Imaoka, Akira; Yoshimura, Chihiro; Waite, T D

2014-04-15

Thermodynamic and kinetic parameters for ferric iron (Fe[III]) complexation by well-characterized humic substances (HS) from various origins were determined by a competitive ligand method with 5-sulfosalicylic acid at circumneutral pH (6.0-8.0) and an ionic strength of ∼0.06 M. The measured Fe binding properties including conditional stability constants and complexation capacities ranged over more than 2 orders of magnitude, depending on the origin and the particular operationally defined fraction of HS examined. Statistical comparison of the complexation parameters to a range of chemical properties of the HS indicated a strong positive correlation between Fe(III) complexation capacity and aromatic carbon content in the HS at all pHs examined. In contrast, the complexation capacity was determined to be up to a few orders of magnitude smaller than the concentration of carboxylic and phenolic groups present. Therefore, specific functional groups including those resident in the proximity of aromatic structures within the HS are likely preferable for Fe(III) coordination under the conditions examined. Overall, our results suggest that the concentration of dissolved Fe(III) complexes in natural waters is substantially influenced by variation in HS characteristics in addition to other well-known factors such as HS concentration and nature and concentration of competing cations present.

Preparation of iron molybdate catalysts for methanol to formaldehyde oxidation based on ammonium molybdoferrate(II precursor

Directory of Open Access Journals (Sweden)

N.V. Nikolenko

2018-03-01

Full Text Available It was demonstrated that iron molybdate catalysts for methanol oxidation can be prepared using Fe(II as a precursor instead of Fe(III. This would allow for reduction of acidity of preparation solutions as well as elimination of Fe(III oxide impurities which are detrimental for the process selectivity. The system containing Fe(II and Mo(VI species in aqueous solution was investigated using UV–Vis spectroscopy. It was demonstrated that three types of chemical reactions occur in the Fe(II–Mo(VI system: (i formation of complexes between Fe(II and molybdate(VI ions, (ii inner sphere oxidation of coordinated Fe(II by Mo(VI and (iii decomposition of the Fe–Mo complexes to form scarcely soluble Fe(III molybdate, Mo(VI hydrous trioxide and molybdenum blue. Solid molybdoferrate(II prepared by interaction of Fe(II and Mo(VI in solution was characterized by EDXA, TGA, DTA and XRD and a scheme of its thermal evolution proposed. The iron molybdate catalyst prepared from Fe(II precursor was tested in methanol-to-formaldehyde oxidation in a continuous flow fixed-bed reactor to show similar activity and selectivity to the conventional catalyst prepared with the use of Fe(III.

Assessing the Role of Iron Sulfides in the Long Term Sequestration of Uranium by Sulfate-Reducing Bacteria

Energy Technology Data Exchange (ETDEWEB)

Hayes, Kim F. [Univ. of Michigan, Ann Arbor, MI (United States); Bi, Yuqiang [Univ. of Michigan, Ann Arbor, MI (United States); Carpenter, Julian [Univ. of Michigan, Ann Arbor, MI (United States); Hyng, Sung Pil [Univ. of Michigan, Ann Arbor, MI (United States); Rittmann, Bruce E. [Arizona State Univ., Tempe, AZ (United States); Zhou, Chen [Arizona State Univ., Tempe, AZ (United States); Vannela, Raveender [Arizona State Univ., Tempe, AZ (United States); Davis, James A. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

2013-12-31

This overarching aim of this project was to identify the role of biogenic and synthetic iron-sulfide minerals in the long-term sequestration of reduced U(IV) formed under sulfate-reducing conditions when subjected to re-oxidizing conditions. The work reported herein was achieved through the collaborative research effort conducted at Arizona State University (ASU) and the University of Michigan (UM). Research at ASU, focused on the biogenesis aspects, examined the biogeochemical bases for iron-sulfide production by Desulfovibrio vulgaris, a Gram-negative bacterium that is one of the most-studied strains of sulfate-reducing bacteria. A series of experimental studies were performed to investigate comprehensively important metabolic and environmental factors that affect the rates of sulfate reduction and iron-sulfide precipitation, the mineralogical characteristics of the iron sulfides, and how uranium is reduced or co-reduced by D. vulagaris. FeS production studies revealed that controlling the pH affected the growth of D. vulgaris and strongly influenced the formation and growth of FeS solids. In particular, lower pH produced larger-sized mackinawite (Fe_1+xS). Greater accumulation of free sulfide, from more sulfate reduction by D. vulgaris, also led to larger-sized mackinawite and stimulated mackinawite transformation to greigite (Fe₃S₄) when the free sulfide concentration was 29.3 mM. On the other hand, using solid Fe(III) (hydr)oxides as the iron source led to less productivity of FeS due to their slow and incomplete dissolution and scavenging of sulfide. Furthermore, sufficient free Fe²⁺, particularly during Fe(III) (hydr)oxide reductions, led to the additional formation of vivianite [Fe₃(PO₄)₂•8(H₂O)]. The U(VI) reduction studies revealed that D. vulgaris reduced U(VI) fastest when accumulating sulfide from concomitant sulfate reduction, since direct enzymatic and sulfide

XPS and FTIR spectroscopic study on microwave treated high phosphorus iron ore

International Nuclear Information System (INIS)

Omran, Mamdouh; Fabritius, Timo; Elmahdy, Ahmed M.; Abdel-Khalek, Nagui A.; El-Aref, Mortada; Elmanawi, Abd El-Hamid

2015-01-01

Highlights: • The effect of microwave radiation on structure and chemical state of high phosphorus iron ore was studied. • FTIR analyses showed that after microwave radiation the functional chemical groups of phosphorus bearing minerals (fluorapatite) dissociated. • High resolution XPS analyses of Fe 2p peaks showed that after microwave radiation a portion of Fe(+III) was reduced to Fe(+II). • Microwave radiation had a positive effect on the magnetic properties of iron oxide, through formation of ferromagnetic phases. - Abstract: A growing interest in microwave heating has emerged recently. Several potential microwave applications regarding minerals’ processing have been investigated. This paper investigates the effect of microwave radiation on Egyptian high phosphorus iron ore. Three different iron ore samples have varying Fe 2 O 3 and P 2 O 5 contents and mineralogical textures were studied. A comparative study has been carried out between untreated and microwave treated iron ore. XRD and FTIR analyses showed that after microwave radiation the crystallinity of iron bearing minerals (hematite) increased, while the functional chemical groups of phosphorus bearing minerals (fluorapatite) and other gangues dissociated. High resolution XPS analyses of Fe 2p peaks showed that after microwave radiation a portion of Fe(+III) was reduced to Fe(+II). This means that after microwave radiation iron oxide (hematite, Fe 3+ ) transformed into more magnetic phase. The results indicated that microwave radiation had a positive effect on the magnetic properties of iron oxide, through formation of ferromagnetic phases

Iron chemistry of Hawaiian rainforest soil solution: Biogeochemical implications of multiple Fe redox cycles

Science.gov (United States)

Thompson, A.; Chorover, J.; Chadwick, O.

2003-12-01

Iron (Fe)-oxides are important sorbents for nutrients, pollutants and natural organic matter (NOM). When flucutations in soil oxygen status exist, Fe can cycle through reduced and oxidized forms and thus greatly affect the aqueous conc. of nutrients and metals. We are examining the influence of oscillating oxic/anoxic conditions on Fe-oxide formation and biogeochemical processes (microbial community composition, and carbon, nutrient and trace metal availability). Our work makes use of a natural rainfall gradient ranging from 2.2 to 4.2 m mean annual precipitation (MAP) on the island of Maui, Hawaii, USA. All sites developed on a 400ky basaltic lava flow and comprise soils under similar vegetation. Solid phase Fe concentration and oxidation state vary systematically across this rainfall gradient with a sharp decrease in pedogenic Fe between 2.8 m and 3.5 m MAP that corresponds with an Eh of 330 mV (1-yr ave.). Fe isotopic composition and Fe-oxide associated rare earth elements (REE) also suggest a shift from ligand-promoted to redutive Fe dissolution with increasing rainfall. To examine the effects of multiple Fe oxidation/reduction cycles, we constructed a set of redox-stat reactors that maintain Eh values within a set range by small Eh-triggered additions of oxygen. Triplicate soil slurry reactors are subjected to redox (Eh) oscillations such that Fe is repeatedly cycled from oxidized to reduced forms. During our current experiment, we measure pH and Eh dynamics and monitor the distribution of Fe(II) and Fe(III), major ion and anion concentrations, a range of trace metals including the REE, and total organic carbon (TOC) in three Stokes-effective particle size fractions (DNA fingerprinting is used to track changes in the microbial community. Prior to implementing the rigorous sampling procedure above, we completed two preliminary reactor experiments focusing only on Fe distribution between aqueous, HCl, and oxalate extractions. These experiments illustrated (1) a

Prevention of Acid Mine Drainage Through Complexation of Ferric Iron by Soluble Microbial Growth Products

Science.gov (United States)

Pandey, S.; Yacob, T. W.; Silverstein, J.; Rajaram, H.; Minchow, K.; Basta, J.

2011-12-01

Acid mine drainage (AMD) is a widespread environmental problem with deleterious impacts on water quality in streams and watersheds. AMD is generated largely by the oxidation of metal sulfides (i.e. pyrite) by ferric iron. This abiotic reaction is catalyzed by conversion of ferrous to ferric iron by iron and sulfur oxidizing microorganisms. Biostimulation is currently being investigated as an attempt to inhibit the oxidation of pyrite and growth of iron oxidizing bacteria through addition of organic carbon. This may stimulate growth of indigenous communities of acidophilic heterotrophic bacteria to compete for oxygen. The goal of this research is to investigate a secondary mechanism associated with carbon addition: complexation of free Fe(III) by soluble microbial growth products (SMPs) produced by microorganisms growing in waste rock. Exploratory research at the laboratory scale examined the effect of soluble microbial products (SMPs) on the kinetics of oxidation of pure pyrite during shaker flask experiments. The results confirmed a decrease in the rate of pyrite oxidation that was dependent upon the concentration of SMPs in solution. We are using these data to verify results from a pyrite oxidation model that accounts for SMPs. This reactor model involves differential-algebraic equations incorporating total component mass balances and mass action laws for equilibrium reactions. Species concentrations determined in each time step are applied to abiotic pyrite oxidation rate expressions from the literature to determine the evolution of total component concentrations. The model was embedded in a parameter estimation algorithm to determine the reactive surface area of pyrite in an abiotic control experiment, yielding an optimized value of 0.0037 m2. The optimized model exhibited similar behavior to the experiment for this case; the root mean squared of residuals for Fe(III) was calculated to be 7.58 x 10-4 M, which is several orders of magnitude less than the actual

Radiotracer Imaging of Sediment Columns

Science.gov (United States)

Moses, W. W.; O'Neil, J. P.; Boutchko, R.; Nico, P. S.; Druhan, J. L.; Vandehey, N. T.

2010-12-01

Nuclear medical PET and SPECT cameras routinely image radioactivity concentration of gamma ray emitting isotopes (PET - 511 keV; SPECT - 75-300 keV). We have used nuclear medical imaging technology to study contaminant transport in sediment columns. Specifically, we use Tc-99m (T1/2 = 6 h, Eγ = 140 keV) and a SPECT camera to image the bacteria mediated reduction of pertechnetate, [Tc(VII)O4]- + Fe(II) → Tc(IV)O2 + Fe(III). A 45 mL bolus of Tc-99m (32 mCi) labeled sodium pertechnetate was infused into a column (35cm x 10cm Ø) containing uranium-contaminated subsurface sediment from the Rifle, CO site. A flow rate of 1.25 ml/min of artificial groundwater was maintained in the column. Using a GE Millennium VG camera, we imaged the column for 12 hours, acquiring 44 frames. As the microbes in the sediment were inactive, we expected most of the iron to be Fe(III). The images were consistent with this hypothesis, and the Tc-99m pertechnetate acted like a conservative tracer. Virtually no binding of the Tc-99m was observed, and while the bolus of activity propagated fairly uniformly through the column, some inhomogeneity attributed to sediment packing was observed. We expect that after augmentation by acetate, the bacteria will metabolically reduce Fe(III) to Fe(II), leading to significant Tc-99m binding. Imaging sediment columns using nuclear medicine techniques has many attractive features. Trace quantities of the radiolabeled compounds are used (micro- to nano- molar) and the half-lives of many of these tracers are short (Image of Tc-99m distribution in a column containing Rifle sediment at four times.

The microbial ferrous wheel in a neutral pH groundwater seep

Directory of Open Access Journals (Sweden)

Eric eRoden

2012-05-01

Full Text Available Evidence for microbial Fe redox cycling was documented in a circumneutral pH groundwater seep near Bloomington, Indiana. Geochemical and microbiological analyses were conducted at two sites, a semi-consolidated microbial mat and a floating puffball structure. In situ voltammetric microelectrode measurements revealed steep opposing gradients of O2 and Fe(II at both sites, similar to other groundwater seep and sedimentary environments known to support microbial Fe redox cycling. The puffball structure showed an abrupt increase in dissolved Fe(II just at its surface (~ 5 cm depth, suggesting an internal Fe(II source coupled to active Fe(III reduction. MPN enumerations detected microaerophilic Fe(II-oxidizing bacteria (FeOB and dissimilatory Fe(III-reducing bacteria (FeRB at densities of 102-105 cells mL-1 in samples from both sites. In vitro Fe(III reduction experiments revealed the potential for immediate reduction (no lag period of native Fe(III oxides. Conventional full-length 16S rRNA gene clone libraries were compared withhigh throughput barcode sequencing of the V1, V4 or V6 variable regions of 16S rRNA genes in order to evaluate the extent to which new sequencing approaches could provide enhanced insight into the composition of Fe redox cycling microbial community structure. The composition of the clone libraries suggested a lithotroph-dominated microbial community centered around taxa related to known FeOB (e.g. Gallionella, Sideroxydans, Aquabacterium. Sequences related to recognized FeRB (e.g. Rhodoferax, Aeromonas, Geobacter, Desulfovibrio were also well represented. Overall, sequences related to known FeOB and FeRB accounted for 88 and 59% of total clone sequences in the mat and puffball libraries, respectively. Taxa identified in the barcode libraries showed partial overlap with the clone libraries, but were not always consistent across different variable regions and sequencing platforms. However, the barcode libraries provided

Structure elucidation and chemical synthesis of stigmolone, a novel type of prokaryotic pheromone.

Science.gov (United States)

Hull, W E; Berkessel, A; Plaga, W

1998-09-15

Approximately 2 micromol of a novel prokaryotic pheromone, involved in starvation-induced aggregation and formation of fruiting bodies by the myxobacterium Stigmatella aurantiaca, were isolated by a large-scale elution procedure. The pheromone was purified by HPLC, and high-resolution MS, IR, 1H-NMR, and 13C-NMR were used to identify the active substance as the hydroxy ketone 2,5, 8-trimethyl-8-hydroxy-nonan-4-one, which has been named stigmolone. The analysis was complicated by a solvent-dependent equilibrium between stigmolone and the cyclic enol-ether 3,4-dihydro-2,2, 5-trimethyl-6-(2-methylpropyl)-2H-pyran formed by intramolecular nucleophilic attack of the 8-OH group at the ketone C4 followed by loss of H2O. Both compounds were synthesized chemically, and their structures were confirmed by NMR analysis. Natural and synthetic stigmolone have the same biological activity at ca. 1 nM concentration.

New Sesquiterpene Oxidations with CYP260A1 and CYP264B1 from Sorangium cellulosum So ce56.

Science.gov (United States)

Schifrin, Alexander; Litzenburger, Martin; Ringle, Michael; Ly, Thuy T B; Bernhardt, Rita

2015-12-01

Sesquiterpenes are natural products derived from the common precursor farnesyl pyrophosphate (FPP) but are highly diverse in structure and function. Cytochrome P450 enzymes (P450s) exhibit the unique ability to introduce molecular oxygen into non-activated C-H bonds. In plant biosynthetic pathways, P450s commonly derivatize sesquiterpene hydrocarbons. However, the potential of bacterial P450s for terpene derivatization is still underinvestigated. This work compares the substrate specificities and regioselectivities of the sesquiterpene hydroxylases CYP260A1 and CYP264B1 from myxobacterium Sorangium cellulosum So ce56. Four tested substrate classes (eremophilanes, humulanes, caryophyllanes, and cedranes) were converted by both P450s. The achievable variety of oxidations is demonstrated on the model substrates (+)-nootkatone and zerumbone. Increasing the number of functionally investigated P450s, this study represents a step towards the selective derivatization of sesquiterpenes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Potential for Methanosarcina to contribute to uranium reduction during acetate-promoted groundwater bioremediation

DEFF Research Database (Denmark)

Holmes, Dawn E; Orellana, Roberto; Giloteaux, Ludovic

2017-01-01

Previous studies of in situ bioremediation of uranium-contaminated groundwater with acetate injections have focused on the role of Geobacter species in U(VI) reduction because of a lack of other abundant known U(VI)-reducing microorganisms. Monitoring the levels of methyl CoM reductase subunit...... an important role in the long-term bioremediation of uranium-contaminated aquifers after depletion of Fe(III) oxides limits the growth of Geobacter species. The results also suggest that Methanosarcina have the potential to influence uranium geochemistry in a diversity of anaerobic sedimentary environments....

Echo detected EPR as a tool for detecting radiation-induced defect signals in pottery

International Nuclear Information System (INIS)

Zoleo, Alfonso; Bortolussi, Claudia; Brustolon, Marina

2011-01-01

Archaeological fragments of pottery have been investigated by using CW-EPR and Echo Detected EPR (EDEPR). EDEPR allows to remove the CW-EPR dominant Fe(III) background spectrum, hiding much weaker signals potentially useful for dating purpose. EDEPR spectra attributed to a methyl radical and to feldspar defects have been recorded at room and low temperature for an Iron Age cooking ware (700 B.C.). A study on the dependence of EDEPR intensity over absorbed dose on a series of γ-irradiated brick samples (estimated age of 562 ± 140 B.C.) has confirmed the potential efficacy of the proposed method for spotting defect signals out of the strong iron background. - Highlights: → Fe(III) CW-EPR signals cover CW-EPR-detectable defects in ceramics. → Echo detected EPR gets rid of Fe(III) signals, disclosing defect signals. → Echo detected EPR detects defect signals even at relatively low doses.

In situ immobilization on the silica gel surface and adsorption capacity of polymer-based azobenzene on toxic metal ions

Science.gov (United States)

Savchenko, Irina; Yanovska, Elina; Sternik, Dariusz; Kychkyruk, Olga; Ol'khovik, Lidiya; Polonska, Yana

2018-03-01

In situ immobilization of poly[(4-methacryloyloxy-(4'-carboxy)azobenzene] on silica gel surface has been performed by radical polymerization of monomer. The fact of polymer immobilization is confirmed by IR spectroscopy. TG and DSC-MS analysis showed that the mass of the immobilized polymer was 10.61%. The SEM-microphotograph-synthesized composite analysis showed that the immobilized polymer on the silica gel surface is placed in the form of fibers. It has been found that the synthesized composite exhibits the sorption ability in terms of microquantities of Cu(II), Cd(II), Pb(II), Mn(II) and Fe(III) ions in a neutral aqueous medium. The quantitative sorption of microquantities of Pb(II) and Fe(III) ions has been recorded. It has been found that immobilization of the silica gel surface leads to an increase in its sorption capacitance for Fe(III), Cu(II) and Pb(II) ions by half.

Chemically-modified activated carbon with ethylenediamine for selective solid-phase extraction and preconcentration of metal ions.

Science.gov (United States)

Li, Zhenhua; Chang, Xijun; Zou, Xiaojun; Zhu, Xiangbing; Nie, Rong; Hu, Zheng; Li, Ruijun

2009-01-26

A new method that utilizes ethylenediamine-modified activated carbon (AC-EDA) as a solid-phase extractant has been developed for simultaneous preconcentration of trace Cr(III), Fe(III), Hg(II) and Pb(II) prior to the measurement by inductively coupled plasma optical emission spectrometry (ICP-OES). The new sorbent was prepared by oxidative surface modification. Experimental conditions for effective adsorption of trace levels of Cr(III), Fe(III), Hg(II) and Pb(II) were optimized with respect to different experimental parameters using batch and column procedures in detail. The optimum pH value for the separation of metal ions simultaneously on the new sorbent was 4.0. Complete elution of absorbed metal ions from the sorbent surface was carried out using 3.0 mL of 2% (%w/w) thiourea and 0.5 mol L(-1) HCl solution. Common coexisting ions did not interfere with the separation and determination of target metal ions. The maximum static adsorption capacity of the sorbent at optimum conditions was found to be 39.4, 28.9, 60.5 and 49.9 mg g(-1) for Cr(III), Fe(III), Hg(II) and Pb(II), respectively. The time for 94% adsorption of target metal ions was less than 2 min. The detection limits of the method was found to be 0.28, 0.22, 0.09 and 0.17 ng mL(-1) for Cr(III), Fe(III), Hg(II) and Pb(II), respectively. The precision (R.S.D.) of the method was lower 4.0% (n=8). The prepared sorbent as solid-phase extractant was successfully applied for the preconcentration of trace Cr(III), Fe(III), Hg(II) and Pb(II) in natural and certified samples with satisfactory results.

Arsenic removal with iron(II) and iron(III) in waters with high silicate and phosphate concentrations.

Science.gov (United States)

Roberts, Linda C; Hug, Stephan J; Ruettimann, Thomas; Billah, Morsaline; Khan, Abdul Wahab; Rahman, Mohammad Tariqur

2004-01-01

Arsenic removal by passive treatment, in which naturally present Fe(II) is oxidized by aeration and the forming iron(III) (hydr)oxides precipitate with adsorbed arsenic, is the simplest conceivable water treatment option. However, competing anions and low iron concentrations often require additional iron. Application of Fe(II) instead of the usually applied Fe(III) is shown to be advantageous, as oxidation of Fe(II) by dissolved oxygen causes partial oxidation of As(III) and iron(III) (hydr)oxides formed from Fe(II) have higher sorption capacities. In simulated groundwater (8.2 mM HCO3(-), 2.5 mM Ca2+, 1.6 mM Mg2+, 30 mg/L Si, 3 mg/L P, 500 ppb As(III), or As(V), pH 7.0 +/- 0.1), addition of Fe(II) clearly leads to better As removal than Fe(III). Multiple additions of Fe(II) further improved the removal of As(II). A competitive coprecipitation model that considers As(III) oxidation explains the observed results and allows the estimation of arsenic removal under different conditions. Lowering 500 microg/L As(III) to below 50 microg/L As(tot) in filtered water required > 80 mg/L Fe(III), 50-55 mg/L Fe(II) in one single addition, and 20-25 mg/L in multiple additions. With As(V), 10-12 mg/L Fe(II) and 15-18 mg/L Fe(III) was required. In the absence of Si and P, removal efficiencies for Fe(II) and Fe(III) were similar: 30-40 mg/L was required for As(II), and 2.0-2.5 mg/L was required for As(V). In a field study with 22 tubewells in Bangladesh, passive treatment efficiently removed phosphate, but iron contents were generally too low for efficient arsenic removal.

Metabolic response of Geobacter sulfurreducens towards electron donor/acceptor variation

Directory of Open Access Journals (Sweden)

Lovley Derek R

2010-11-01

Full Text Available Abstract Background Geobacter sulfurreducens is capable of coupling the complete oxidation of organic compounds to iron reduction. The metabolic response of G. sulfurreducens towards variations in electron donors (acetate, hydrogen and acceptors (Fe(III, fumarate was investigated via 13C-based metabolic flux analysis. We examined the 13C-labeling patterns of proteinogenic amino acids obtained from G. sulfurreducens cultured with 13C-acetate. Results Using 13C-based metabolic flux analysis, we observed that donor and acceptor variations gave rise to differences in gluconeogenetic initiation, tricarboxylic acid cycle activity, and amino acid biosynthesis pathways. Culturing G. sulfurreducens cells with Fe(III as the electron acceptor and acetate as the electron donor resulted in pyruvate as the primary carbon source for gluconeogenesis. When fumarate was provided as the electron acceptor and acetate as the electron donor, the flux analysis suggested that fumarate served as both an electron acceptor and, in conjunction with acetate, a carbon source. Growth on fumarate and acetate resulted in the initiation of gluconeogenesis by phosphoenolpyruvate carboxykinase and a slightly elevated flux through the oxidative tricarboxylic acid cycle as compared to growth with Fe(III as the electron acceptor. In addition, the direction of net flux between acetyl-CoA and pyruvate was reversed during growth on fumarate relative to Fe(III, while growth in the presence of Fe(III and acetate which provided hydrogen as an electron donor, resulted in decreased flux through the tricarboxylic acid cycle. Conclusions We gained detailed insight into the metabolism of G. sulfurreducens cells under various electron donor/acceptor conditions using 13C-based metabolic flux analysis. Our results can be used for the development of G. sulfurreducens as a chassis for a variety of applications including bioremediation and renewable biofuel production.

Fe electron transfer and atom exchange in goethite: influence of Al-substitution and anion sorption.

Science.gov (United States)

Latta, Drew E; Bachman, Jonathan E; Scherer, Michelle M

2012-10-02

The reaction of Fe(II) with Fe(III) oxides and hydroxides is complex and includes sorption of Fe(II) to the oxide, electron transfer between sorbed Fe(II) and structural Fe(III), reductive dissolution coupled to Fe atom exchange, and, in some cases mineral phase transformation. Much of the work investigating electron transfer and atom exchange between aqueous Fe(II) and Fe(III) oxides has been done under relatively simple aqueous conditions in organic buffers to control pH and background electrolytes to control ionic strength. Here, we investigate whether electron transfer is influenced by cation substitution of Al(III) in goethite and the presence of anions such as phosphate, carbonate, silicate, and natural organic matter. Results from (57)Fe Mössbauer spectroscopy indicate that both Al-substitution (up to 9%) and the presence of common anions (PO(4)(3-), CO(3)(2-), SiO(4)(4-), and humic acid) does not inhibit electron transfer between aqueous Fe(II) and Fe(III) in goethite under the conditions we studied. In contrast, sorption of a long-chain phospholipid completely shuts down electron transfer. Using an enriched isotope tracer method, we found that Al-substitution in goethite (10%), does, however, significantly decrease the extent of atom exchange between Fe(II) and goethite (from 43 to 12%) over a month's time. Phosphate, somewhat surprisingly, appears to have little effect on the rate and extent of atom exchange between aqueous Fe(II) and goethite. Our results show that electron transfer between aqueous Fe(II) and solid Fe(III) in goethite can occur under wide range of geochemical conditions, but that the extent of redox-driven Fe atom exchange may be dependent on the presence of substituting cations such as Al.

Development of a surfactant liquid membrane extraction process for the cleansing of industrial aqueous effluents containing metallic cation traces

International Nuclear Information System (INIS)

Rapaumbya Akaye, Guy-Roland

1994-01-01

The purpose of this work was to develop a process of surfactant liquid membrane extraction to purify industrial waste solution containing Cu(II), Fe(III), and Zn(II) (about 0,1 g/L). The extractant is the ammonium salt of Cyanex 306 and Aliquat 336. The first part of this work deals with the study of the liquid-liquid extraction of the metals. The efficiency of the extractant has been shown for the extraction of each metal alone and for Cu(II) and Zn(II) in the case of a mixture of the three metals. During this study we have observed that Fe(III) is reduced to Fe(II) (which is not extracted by the salt of Cyanex 301) in presence of Cu(II) and the quaternary ammonium salt (Aliquat 336). The optimisation of the experimental conditions for the discontinuous surfactant liquid membrane process led us to choose the following composition of the emulsion: 1,5 % of Cyanex 301 salt, 2,5 % of ECA 4360, dodecan. The internal phase is an aqueous solution containing 3,5 mol/L of NaOH and 0,5 mol/L tri-ethanolamin The residual concentration of Cu(II) and Zn(II) in the external phase is very low. In the case of iron, only 60 % are extracted because of the reduction phenomenon (10 % in liquid-liquid extraction). The realisation of the continuous process in pulsed column, after optimisation of hydrodynamics conditions, leads to similar results. In stationary conditions, we obtain a raffinate containing less than 0,5 mg/L of Cu(II) and Zn(II) and 36 mg/L of iron. The internal phase contains about 2 g/L of Cu(II) an Zn(II). We tried and minimize the reduction of Fe(III) in surfactant liquid membrane process. Less than 16 % of iron cannot be reduced. This leads to a purification of only 84 % In the basis of these results, processes of purification have been proposed for effluents of various composition. They enable to purify the effluent and besides to concentrate the pollutants about twenty times. (author) [fr

Preservation of water samples for arsenic(III/V) determinations: An evaluation of the literature and new analytical results

Science.gov (United States)

McCleskey, R. Blaine; Nordstrom, D. Kirk; Maest, A.S.

2004-01-01

Published literature on preservation procedures for stabilizing aqueous inorganic As(III/V) redox species contains discrepancies. This study critically evaluates published reports on As redox preservation and explains discrepancies in the literature. Synthetic laboratory preservation experiments and time stability experiments were conducted for natural water samples from several field sites. Any field collection procedure that filters out microorganisms, adds a reagent that prevents dissolved Fe and Mn oxidation and precipitation, and isolates the sample from solar radiation will preserve the As(III/V) ratio. Reagents that prevent Fe and Mn oxidation and precipitation include HCl, H 2SO4, and EDTA, although extremely high concentrations of EDTA are necessary for some water samples high in Fe. Photo-catalyzed Fe(III) reduction causes As(III) oxidation; however, storing the sample in the dark prevents photochemical reactions. Furthermore, the presence of Fe(II) or SO 4 inhibits the oxidation of As(III) by Fe(III) because of complexation reactions and competing reactions with free radicals. Consequently, fast abiotic As(III) oxidation reactions observed in the laboratory are not observed in natural water samples for one or more of the following reasons: (1) the As redox species have already stabilized, (2) most natural waters contain very low dissolved Fe(III) concentrations, (3) the As(III) oxidation caused by Fe(III) photoreduction is inhibited by Fe(II) or SO4.

Nonanuclear Spin-Crossover Complex Containing Iron(II) and Iron(III) Based on a 2,6-Bis(pyrazol-1-yl)pyridine Ligand Functionalized with a Carboxylate Group.

Science.gov (United States)

Abhervé, Alexandre; Recio-Carretero, María José; López-Jordà, Maurici; Clemente-Juan, Juan Modesto; Canet-Ferrer, Josep; Cantarero, Andrés; Clemente-León, Miguel; Coronado, Eugenio

2016-09-19

The synthesis and magnetostructural characterization of [Fe(III)3(μ3-O)(H2O)3[Fe(II)(bppCOOH)(bppCOO)]6](ClO4)13·(CH3)2CO)6·(solvate) (2) are reported. This compound is obtained as a secondary product during synthesis of the mononuclear complex [Fe(II)(bppCOOH)2](ClO4)2 (1). The single-crystal X-ray diffraction structure of 2 shows that it contains the nonanuclear cluster of the formula [Fe(III)3(μ3-O)(H2O)3[Fe(II)(bppCOOH)(bppCOO)]6](13+), which is formed by a central Fe(III)3O core coordinated to six partially deprotonated [Fe(II)(bppCOOH)(bppCOO)](+) complexes. Raman spectroscopy studies on single crystals of 1 and 2 have been performed to elucidate the spin and oxidation states of iron in 2. These studies and magnetic characterization indicate that most of the iron(II) complexes of 2 remain in the low-spin (LS) state and present a gradual and incomplete spin crossover above 300 K. On the other hand, the Fe(III) trimer shows the expected antiferromagnetic behavior. From the structural point of view, 2 represents the first example in which bppCOO(-) acts as a bridging ligand, thus forming a polynuclear magnetic complex.

Preservation of water samples for arsenic(III/V) determinations: an evaluation of the literature and new analytical results

International Nuclear Information System (INIS)

McCleskey, R.Blaine; Nordstrom, D.Kirk; Maest, Ann S.

2004-01-01

Published literature on preservation procedures for stabilizing aqueous inorganic As(III/V) redox species contains discrepancies. This study critically evaluates published reports on As redox preservation and explains discrepancies in the literature. Synthetic laboratory preservation experiments and time stability experiments were conducted for natural water samples from several field sites. Any field collection procedure that filters out microorganisms, adds a reagent that prevents dissolved Fe and Mn oxidation and precipitation, and isolates the sample from solar radiation will preserve the As(III/V) ratio. Reagents that prevent Fe and Mn oxidation and precipitation include HCl, H 2 SO 4 , and EDTA, although extremely high concentrations of EDTA are necessary for some water samples high in Fe. Photo-catalyzed Fe(III) reduction causes As(III) oxidation; however, storing the sample in the dark prevents photochemical reactions. Furthermore, the presence of Fe(II) or SO 4 inhibits the oxidation of As(III) by Fe(III) because of complexation reactions and competing reactions with free radicals. Consequently, fast abiotic As(III) oxidation reactions observed in the laboratory are not observed in natural water samples for one or more of the following reasons: (1) the As redox species have already stabilized, (2) most natural waters contain very low dissolved Fe(III) concentrations, (3) the As(III) oxidation caused by Fe(III) photoreduction is inhibited by Fe(II) or SO 4

Effect of Aqueous Media on the Recovery of Scandium by Selective Precipitation

Directory of Open Access Journals (Sweden)

Bengi Yagmurlu

2018-05-01

Full Text Available This research presents a novel precipitation method for scandium (Sc concentrate refining from bauxite residue leachates and the effect of aqueous media on this triple-stage successive precipitation process. The precipitation pattern and the precipitation behavior of the constituent elements was investigated using different precipitation agents in three major mineral acid media, namely, H2SO4, HNO3, and HCl in a comparative manner. Experimental investigations showed behavioral similarities between HNO3 and HCl media, while H2SO4 media was different from them because of the nature of the formed complexes. NH4OH was found to be the best precipitation agent in every leaching media to remove Fe(III with low Sc co-precipitation. To limit Sc loss from the system, Fe(III removal was divided into two steps, leading to more than 90% of Fe(III removal at the end of the process. Phosphate concentrates were produced in the final step of the precipitation process with dibasic phosphates which have a strong affinity towards Sc. Concentrates containing more than 50% of ScPO4 were produced in each case from the solutions after Fe(III removal, as described. A flow diagram of the selective precipitation process is proposed for these three mineral acid media with their characteristic parameters.

Variation of iron redox kinetics and its relation with molecular composition of standard humic substances at circumneutral pH

OpenAIRE

Lee, Ying Ping; Fujii, Manabu; Kikuchi, Tetsuro; Terao, Koumei; Yoshimura, Chihiro

2017-01-01

Oxidation and reduction kinetics of iron (Fe) and proportion of steady-state Fe(II) concentration relative to total dissolved Fe (steady-state Fe(II) fraction) were investigated in the presence of various types of standard humic substances (HS) with particular emphasis on the photochemical and thermal reduction of Fe(III) and oxidation of Fe(II) by dissolved oxygen (O2) and hydrogen peroxide (H2O2) at circumneutral pH (pH 7-8). Rates of Fe(III) reduction were spectrophotometrically determined...

Contrasting distributions of groundwater arsenic and uranium in the western Hetao basin, Inner Mongolia: Implication for origins and fate controls

International Nuclear Information System (INIS)

Guo, Huaming; Jia, Yongfeng; Wanty, Richard B.; Jiang, Yuxiao; Zhao, Weiguang; Xiu, Wei; Shen, Jiaxing; Li, Yuan; Cao, Yongsheng; Wu, Yang; Zhang, Di; Wei, Chao; Zhang, Yilong; Cao, Wengeng

2016-01-01

Although As concentrations have been investigated in shallow groundwater from the Hetao basin, China, less is known about U and As distributions in deep groundwater, which would help to better understand their origins and fate controls. Two hundred and ninety-nine groundwater samples, 122 sediment samples, and 14 rock samples were taken from the northwest portion of the Hetao basin, and analyzed for geochemical parameters. Results showed contrasting distributions of groundwater U and As, with high U and low As concentrations in the alluvial fans along the basin margins, and low U and high As concentrations downgradient in the flat plain. The probable sources of both As and U in groundwater were ultimately traced to the bedrocks in the local mountains (the Langshan Mountains). Chemical weathering of U-bearing rocks (schist, phyllite, and carbonate veins) released and mobilized U as UO_2(CO_3)_2"2"− and UO_2(CO_3)_3"4"− species in the alluvial fans under oxic conditions and suboxic conditions where reductions of Mn and NO_3"− were favorable (OSO), resulting in high groundwater U concentrations. Conversely, the recent weathering of As-bearing rocks (schist, phyllite, and sulfides) led to the formation of As-bearing Fe(III) (hydr)oxides in sediments, resulting in low groundwater As concentrations. Arsenic mobilization and U immobilization occurred in suboxic conditions where reduction of Fe(III) oxides was favorable and reducing conditions (SOR). Reduction of As-bearing Fe(III) (hydr)oxides, which were formed during palaeo-weathering and transported and deposited as Quaternary aquifer sediments, was believed to release As into groundwater. Reduction of U(VI) to U(IV) would lead to the formation of uraninite, and therefore remove U from groundwater. We conclude that the contrasting distributions of groundwater As and U present a challenge to ensuring safe drinking water in analogous areas, especially with high background values of U and As. - Highlights: �

Contrasting distributions of groundwater arsenic and uranium in the western Hetao basin, Inner Mongolia: Implication for origins and fate controls

Energy Technology Data Exchange (ETDEWEB)

Guo, Huaming, E-mail: hmguo@cugb.edu.cn [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Beijing 100083 (China); School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing 100083 (China); Jia, Yongfeng [School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing 100083 (China); Wanty, Richard B. [U.S. Geological Survey, MS 964d Denver Federal Center, Denver, CO 80225 (United States); Jiang, Yuxiao; Zhao, Weiguang [School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing 100083 (China); Xiu, Wei [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Beijing 100083 (China); School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing 100083 (China); Shen, Jiaxing [School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing 100083 (China); Li, Yuan [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Beijing 100083 (China); School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing 100083 (China); Cao, Yongsheng [School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing 100083 (China); Wu, Yang [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Beijing 100083 (China); Zhang, Di [School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing 100083 (China); Wei, Chao [School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing 100083 (China); The National Institute of Metrology, Beijing 100013 (China); Zhang, Yilong; Cao, Wengeng [Institute of Hydrogeology and Environmental Geology, China Academy of Geological Sciences, Shijiazhuang, Hebei, 050061 (China); and others

2016-01-15

Although As concentrations have been investigated in shallow groundwater from the Hetao basin, China, less is known about U and As distributions in deep groundwater, which would help to better understand their origins and fate controls. Two hundred and ninety-nine groundwater samples, 122 sediment samples, and 14 rock samples were taken from the northwest portion of the Hetao basin, and analyzed for geochemical parameters. Results showed contrasting distributions of groundwater U and As, with high U and low As concentrations in the alluvial fans along the basin margins, and low U and high As concentrations downgradient in the flat plain. The probable sources of both As and U in groundwater were ultimately traced to the bedrocks in the local mountains (the Langshan Mountains). Chemical weathering of U-bearing rocks (schist, phyllite, and carbonate veins) released and mobilized U as UO{sub 2}(CO{sub 3}){sub 2}{sup 2−} and UO{sub 2}(CO{sub 3}){sub 3}{sup 4−} species in the alluvial fans under oxic conditions and suboxic conditions where reductions of Mn and NO{sub 3}{sup −} were favorable (OSO), resulting in high groundwater U concentrations. Conversely, the recent weathering of As-bearing rocks (schist, phyllite, and sulfides) led to the formation of As-bearing Fe(III) (hydr)oxides in sediments, resulting in low groundwater As concentrations. Arsenic mobilization and U immobilization occurred in suboxic conditions where reduction of Fe(III) oxides was favorable and reducing conditions (SOR). Reduction of As-bearing Fe(III) (hydr)oxides, which were formed during palaeo-weathering and transported and deposited as Quaternary aquifer sediments, was believed to release As into groundwater. Reduction of U(VI) to U(IV) would lead to the formation of uraninite, and therefore remove U from groundwater. We conclude that the contrasting distributions of groundwater As and U present a challenge to ensuring safe drinking water in analogous areas, especially with high

Corrosion of steel in carbonated media: The oxidation processes of chukanovite (Fe2(OH)2CO3)

International Nuclear Information System (INIS)

Azoulay, I.; Rémazeilles, C.; Refait, Ph.

2014-01-01

Highlights: • Oxidation of chukanovite does not lead to carbonated green rust. • Both lepidocrocite and goethite can result from the oxidation of chukanovite. • Violent oxidation of chukanovite by hydrogen peroxide leads to a Fe(III) oxycarbonate. • Chukanovite crystal structure withstands a partial oxidation of Fe(II) to Fe(III). - Abstract: The oxidation of aqueous suspensions of chukanovite (Fe 2 (OH) 2 CO 3 ) obtained by mixing NaOH, FeCl 2 and Na 2 CO 3 solutions was studied. The reaction was monitored by recording the pH and the redox potential of a platinum electrode immersed in the suspension. The precipitate was analyzed at various oxidation stages by infrared spectroscopy. The end products were also characterized by X-ray diffraction. The oxidation by air of the suspensions leads to lepidocrocite and goethite without formation of an intermediate green rust compound. Violent oxidation of chukanovite by hydrogen peroxide leads to a Fe(III) oxycarbonate with a crystal structure closely related to that of chukanovite

Determination of lead, iron and nickel in water and vegetable samples after preconcentration with aspergillus niger loaded on silica gel

Energy Technology Data Exchange (ETDEWEB)

Baytak, Sitki [Harran University, Arts and Science Faculty, Department of Chemistry, Sanliurfa (Turkey); Kocyigit, Abdurrahim [Harran University, Faculty of Medicine, Department of Biochemistry, Sanliurfa (Turkey); Rehber Tuerker, Ali [Gazi University, Arts and Science Faculty, Department of Chemistry, Ankara (Turkey)

2007-12-15

A method for the determination of Fe(III), Pb(II), and Ni(II) by flame atomic absorption spectrometry (FAAS) after preconcentrating on a column containing Aspergillus niger loaded on silica gel 60 (Biosorbent) is described. The effect of experimental parameters such as pH, flow rate of sample solution, and volume of sample solution were investigated on the recovery of the analytes. The effect of interfering ions on the recovery of the analytes has also been investigated. Recoveries of Fe(III), Pb(II), and Ni(II) were (98 {+-} 2), (98 {+-} 3), (99 {+-} 2)% at the 95% confidence level, respectively. For the analytes, 50-fold preconcentration was obtained. The analytical detection limits for Fe(III), Pb(II), and Ni(II) were 1.7, 5.2, and 1.6 ng/mL, respectively. The proposed method was applied to the determination of trace metals in various water and vegetable samples. The analytes have been determined with relative error lower than 7%. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

An anaerobic field injection experiment in a landfill leachate plume, Grindsted, Denmark: 2. Deduction of anaerobic (methanogenic, sulfate-, and Fe (III)-reducing) redox conditions

Science.gov (United States)

Albrechtsen, Hans-JøRgen; Bjerg, Poul L.; Ludvigsen, Liselotte; Rügge, Kirsten; Christensen, Thomas H.

1999-04-01

Redox conditions may be environmental factors which affect the fate of the xenobiotic organic compounds. Therefore the redox conditions were characterized in an anaerobic, leachate-contaminated aquifer 15-60 m downgradient from the Grindsted Landfill, Denmark, where an field injection experiment was carried out. Furthermore, the stability of the redox conditions spatially and over time were investigated, and different approaches to deduce the redox conditions were evaluated. The redox conditions were evaluated in a set of 20 sediment and groundwater samples taken from locations adjacent to the sediment samples. Samples were investigated with respect to groundwater chemistry, including hydrogen and volatile fatty acids (VFAs) and sediment geochemistry, and bioassays were performed. The groundwater chemistry, including redox sensitive species for a large number of samples, varied over time during the experimental period of 924 days owing to variations in the leachate from the landfill. However, no indication of change in the redox environment resulting from the field injection experiment or natural variation was observed in the individual sampling points. The methane, Fe(II), hydrogen, and VFA groundwater chemistry parameters strongly indicated a Fe(III)-reducing environment. This was further supported by the bioassays, although methane production and sulfate-reduction were also observed in a few samples close to the landfill. On the basis of the calculated carbon conversion, Fe(III) was the dominant electron acceptor in the region of the aquifer, which was investigated. Because of the complexity of a landfill leachate plume, several redox processes may occur simultaneously, and an array of methods must be applied for redox characterization in such multicomponent systems.

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

Science.gov (United States)

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

2017-03-01

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

Studies on effect of Microbial Iron Chelators on Candida Albican

International Nuclear Information System (INIS)

Rehmani, Fouzia S.; Milicent, S.; Zaheer-Uddin

2005-01-01

Iron is an essential for the life of all microbe cells. It generally exists in the oxidized form Fe(III). Even under anaerobic reducing condition the metal appear to be taken up as Fe(III). Thus free-living microorganisms require specific and effective ferric ion transport system to cope with low availability of the metal. In iron deficient environment they produce a low molecular weight specific chelators called siderphores or microbial iron chelators. Siderphores compete for limited supplied of iron. These compounds came out of the cell but can not re-enter without iron due to high affinity of these siderphores often have more than one catechol/hydroxamate functions and are multidentate (usually hexadentate ligands). The aim of the present research is to check the effect of iron chelators, namely gallic acid and salisyl hydroxamate on the growth of Candida albican in vitro. C. albican is the opportunistic paltogen present as the normal flora inside human body. In vivo the growth of C. albican is distributed by the use of antibiotics and immuno suppressers. In cases of iron over-dosage in human being, the patients are treated with certain a-iron chelators. Hence an attempt is made to notice the effect that might be inhibition or enhancement of the organism in vitro. (author)

Selection of Clostridium spp. in biological sand filters neutralizing synthetic acid mine drainage.

Science.gov (United States)

Ramond, Jean-Baptiste; Welz, Pamela J; Le Roes-Hill, Marilize; Tuffin, Marla I; Burton, Stephanie G; Cowan, Don A

2014-03-01

In this study, three biological sand filter (BSF) were contaminated with a synthetic iron- [1500 mg L⁻¹ Fe(II), 500 mg L⁻¹ Fe(III)] and sulphate-rich (6000 mg L⁻¹ SO₄²⁻) acid mine drainage (AMD) (pH = 2), for 24 days, to assess the remediation capacity and the evolution of autochthonous bacterial communities (monitored by T-RFLP and 16S rRNA gene clone libraries). To stimulate BSF bioremediation involving sulphate-reducing bacteria, a readily degradable carbon source (glucose, 8000 mg L⁻¹) was incorporated into the influent AMD. Complete neutralization and average removal efficiencies of 81.5 (±5.6)%, 95.8 (±1.2)% and 32.8 (±14.0)% for Fe(II), Fe(III) and sulphate were observed, respectively. Our results suggest that microbial iron reduction and sulphate reduction associated with iron precipitation were the main processes contributing to AMD neutralization. The effect of AMD on BSF sediment bacterial communities was highly reproducible. There was a decrease in diversity, and notably a single dominant operational taxonomic unit (OTU), closely related to Clostridium beijerinckii, which represented up to 65% of the total community at the end of the study period. © 2013 Federation of European Microbiological Societies. Published by John Wiley & Sons Ltd. All rights reserved.

Enhancement of Bacterial Transport in Aerobic and Anaerobic Environments: Assessing the Effect of Metal Oxide Chemical Heterogeneities

International Nuclear Information System (INIS)

T.C. Onstott

2005-01-01

The goal of our research was to understand the fundamental processes that control microbial transport in physically and chemically heterogeneous aquifers and from this enhanced understanding determine the requirements for successful, field-scale delivery of microorganisms to metal contaminated subsurface sites. Our specific research goals were to determine; (1) the circumstances under which the preferential adsorption of bacteria to Fe, Mn, and Al oxyhydroxides influences field-scale bacterial transport, (2) the extent to which the adhesion properties of bacterial cells affect field-scale bacterial transport, (3) whether microbial Fe(III) reduction can enhance field-scale transport of Fe reducing bacteria (IRB) and other microorganisms and (4) the effect of field-scale physical and chemical heterogeneity on all three processes. Some of the spin-offs from this basic research that can improve biostimulation and bioaugmentation remediation efforts at contaminated DOE sites have included; (1) new bacterial tracking tools for viable bacteria; (2) an integrated protocol which combines subsurface characterization, laboratory-scale experimentation, and scale-up techniques to accurately predict field-scale bacterial transport; and (3) innovative and inexpensive field equipment and methods that can be employed to enhance Fe(III) reduction and microbial transport and to target microbial deposition under both aerobic and anaerobic conditions

XPS and FTIR spectroscopic study on microwave treated high phosphorus iron ore

Energy Technology Data Exchange (ETDEWEB)

Omran, Mamdouh, E-mail: mamdouh.omran@oulu.fi [Process Metallurgy Research Group, Faculty of Technology, University of Oulu (Finland); Mineral Processing and Agglomeration Lab, Central Metallurgical Research and Development Institute, Cairo (Egypt); Fabritius, Timo [Process Metallurgy Research Group, Faculty of Technology, University of Oulu (Finland); Elmahdy, Ahmed M.; Abdel-Khalek, Nagui A. [Mineral Processing and Agglomeration Lab, Central Metallurgical Research and Development Institute, Cairo (Egypt); El-Aref, Mortada; Elmanawi, Abd El-Hamid [Geology Department, Faculty of Science, Cairo University, Giza 12613 (Egypt)

2015-08-01

Highlights: • The effect of microwave radiation on structure and chemical state of high phosphorus iron ore was studied. • FTIR analyses showed that after microwave radiation the functional chemical groups of phosphorus bearing minerals (fluorapatite) dissociated. • High resolution XPS analyses of Fe 2p peaks showed that after microwave radiation a portion of Fe(+III) was reduced to Fe(+II). • Microwave radiation had a positive effect on the magnetic properties of iron oxide, through formation of ferromagnetic phases. - Abstract: A growing interest in microwave heating has emerged recently. Several potential microwave applications regarding minerals’ processing have been investigated. This paper investigates the effect of microwave radiation on Egyptian high phosphorus iron ore. Three different iron ore samples have varying Fe{sub 2}O{sub 3} and P{sub 2}O{sub 5} contents and mineralogical textures were studied. A comparative study has been carried out between untreated and microwave treated iron ore. XRD and FTIR analyses showed that after microwave radiation the crystallinity of iron bearing minerals (hematite) increased, while the functional chemical groups of phosphorus bearing minerals (fluorapatite) and other gangues dissociated. High resolution XPS analyses of Fe 2p peaks showed that after microwave radiation a portion of Fe(+III) was reduced to Fe(+II). This means that after microwave radiation iron oxide (hematite, Fe{sup 3+}) transformed into more magnetic phase. The results indicated that microwave radiation had a positive effect on the magnetic properties of iron oxide, through formation of ferromagnetic phases.

Seasonal changes in Fe species and soluble Fe concentration in the atmosphere in the Northwest Pacific region based on the analysis of aerosols collected in Tsukuba, Japan

Directory of Open Access Journals (Sweden)

Y. Takahashi

2013-08-01

Full Text Available Atmospheric iron (Fe can be a significant source of nutrition for phytoplankton inhabiting remote oceans, which in turn has a large influence on the Earth's climate. The bioavailability of Fe in aerosols depends mainly on the fraction of soluble Fe (= [FeSol]/[FeTotal], where [FeSol] and [FeTotal] are the atmospheric concentrations of soluble and total Fe, respectively. However, the numerous factors affecting the soluble Fe fraction have not been fully understood. In this study, the Fe species, chemical composition, and soluble Fe concentrations in aerosols collected in Tsukuba, Japan were investigated over a year (nine samples from December 2002 to October 2003 to identify the factors affecting the amount of soluble Fe supplied into the ocean. The soluble Fe concentration in aerosols is correlated with those of sulfate and oxalate originated from anthropogenic sources, suggesting that soluble Fe is mainly derived from anthropogenic sources. Moreover, the soluble Fe concentration is also correlated with the enrichment factors of vanadium and nickel emitted by fossil fuel combustion. These results suggest that the degree of Fe dissolution is influenced by the magnitude of anthropogenic activity, such as fossil fuel combustion. X-ray absorption fine structure (XAFS spectroscopy was performed in order to identify the Fe species in aerosols. Fitting of XAFS spectra coupled with micro X-ray fluorescence analysis (μ-XRF showed the main Fe species in aerosols in Tsukuba to be illite, ferrihydrite, hornblende, and Fe(III sulfate. Moreover, the soluble Fe fraction in each sample measured by leaching experiments is closely correlated with the Fe(III sulfate fraction determined by the XAFS spectrum fitting, suggesting that Fe(III sulfate is the main soluble Fe in the ocean. Another possible factor that can control the amount of soluble Fe supplied into the ocean is the total Fe(III concentration in the atmosphere, which was high in spring due to the high

Solid-solution partitioning and thionation of diphenylarsinic acid in a flooded soil under the impact of sulfate and iron reduction

Energy Technology Data Exchange (ETDEWEB)

Zhu, Meng [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Tu, Chen [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); Hu, Xuefeng; Zhang, Haibo [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Zhang, Lijuan [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); Wei, Jing [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); Li, Yuan [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Luo, Yongming, E-mail: ymluo@yic.ac.cn [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Christie, Peter [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China)

2016-11-01

Diphenylarsinic acid (DPAA) is a major organic arsenic (As) compound derived from abandoned chemical weapons. The solid-solution partitioning and transformation of DPAA in flooded soils are poorly understood but are of great concern. The identification of the mechanisms responsible for the mobilization and transformation of DPAA may help to develop effective remediation strategies. Here, soil and Fe mineral incubation experiments were carried out to elucidate the partitioning and transformation of DPAA in anoxic (without addition of sulfate or sodium lactate) and sulfide (with the addition of sulfate and sodium lactate) soil and to examine the impact of sulfate and Fe(III) reduction on these processes. Results show that DPAA was more effectively mobilized and thionated in sulfide soil than in anoxic soil. At the initial incubation stages (0–4 weeks), 6.7–74.5% of the total DPAA in sulfide soil was mobilized likely by sorption competition with sodium lactate. At later incubation stage (4–8 weeks), DPAA was almost completely released into the solution likely due to the near-complete Fe(III) reduction. Scanning transmission X-ray microscopy (STXM) results provide further direct evidence of elevated DPAA release coupled with Fe(III) reduction in sulfide environments. The total DPAA fraction decreased significantly to 24.5% after two weeks and reached 3.4% after eight weeks in sulfide soil, whereas no obvious elimination of DPAA occurred in anoxic soil at the initial two weeks and the total DPAA fraction decreased to 10.9% after eight weeks. This can be explained in part by the enhanced mobilization of DPAA and sulfate reduction in sulfide soil compared with anoxic soil. These results suggest that under flooded soil conditions, Fe(III) and sulfate reduction significantly promote DPAA mobilization and thionation, respectively, and we suggest that it is essential to consider both sulfate and Fe(III) reduction to further our understanding of the environmental fate of

Dynamics of arsenic adsorption in the targeted arsenic-safe aquifers in Matlab, south-eastern Bangladesh: Insight from experimental studies

International Nuclear Information System (INIS)

Robinson, Clare; Broemssen, Mattias von; Bhattacharya, Prosun; Haeller, Sara; Biven, Annelie; Hossain, Mohammed; Jacks, Gunnar; Ahmed, Kazi Matin; Hasan, M. Aziz; Thunvik, Roger

2011-01-01

Research highlights: → Adsorption behaviour of shallow oxidized sediments from Matlab Region in SE Bangladesh is investigated. → Oxidized sediments have a high capacity to adsorb arsenic. → Adsorption capacity will be reduced by high concentration of reactive organic C. → Monitoring of groundwater quality over 5 year period shows relatively stable water chemistry. - Abstract: Targeting shallow low-As aquifers based on sediment colour may be a viable solution for supplying As-safe drinking water to rural communities in some regions of Bangladesh and West Bengal in India. The sustainability of this solution with regard to the long-term risk of As-safe oxidized aquifers becoming enriched with As needs to be assessed. This study focuses on the adsorption behaviour of shallow oxidized sediments from Matlab Region, Bangladesh, and their capacity to attenuate As if cross-contamination of the oxidized aquifers occurs. Water quality analyses of samples collected from 20 tube-wells in the region indicate that while there may be some seasonal variability, the groundwater chemistry in the reduced and oxidized aquifers was relatively stable from 2004 to 2009. Although sediment extractions indicate a relatively low amount of As in the oxidized sediments, below 2.5 mg kg -1 , batch isotherm experiments show that the sediments have a high capacity to adsorb As. Simulations using a surface complexation model that considers adsorption to amorphous Fe(III) oxide minerals only, under-predict the experimental isotherms. This suggests that a large proportion of the adsorption sites in the oxidized sediments may be associated with crystalline Fe(III) oxides, Mn(IV) and Al(III) oxides, and clay minerals. Replicate breakthrough column experiments conducted with lactose added to the influent solution demonstrate that the high adsorption capacity of the oxidized sediments may be reduced if water drawn down into the oxidized aquifers contains high levels of electron donors such as

Non-enzymatic U(VI) interactions with biogenic mackinawite

Science.gov (United States)

Veeramani, H.; Qafoku, N. P.; Kukkadapu, R. K.; Murayama, M.; Hochella, M. F.

2011-12-01

Reductive immobilization of hexavalent uranium [U(VI)] by stimulation of dissimilatory metal and/or sulfate reducing bacteria (DMRB or DSRB) has been extensively researched as a remediation strategy for subsurface U(VI) contamination. These bacteria derive energy by reducing oxidized metals as terminal electron acceptors, often utilizing organic substrates as electron donors. Thus, when evaluating the potential for in-situ uranium remediation in heterogeneous subsurface media, it is important to understand how the presence of alternative electron acceptors such as Fe(III) and sulfate affect U(VI) remediation and the long term behavior and reactivity of reduced uranium. Iron, an abundant subsurface element, represents a substantial sink for electrons from DMRB, and the reduction of Fe(III) leads to the formation of dissolved Fe(II) or to reactive biogenic Fe(II)- and mixed Fe(II)/Fe(III)- mineral phases. Consequently, abiotic U(VI) reduction by reactive forms of biogenic Fe(II) minerals could be a potentially important process for uranium immobilization. In our study, the DMRB Shewanella putrefaciens CN32 was used to synthesize a biogenic Fe(II)-bearing sulfide mineral: mackinawite, that has been characterized by XRD, SEM, HRTEM and Mössbauer spectroscopy. Batch experiments involving treated biogenic mackinawite and uranium (50:1 molar ratio) were carried out at room temperature under strict anoxic conditions. Following complete removal of uranium from solution, the biogenic mackinawite was analyzed by a suite of analytical techniques including XAS, HRTEM and Mössbauer spectroscopy to determine the speciation of uranium and investigate concomitant Fe(II)-phase transformation. Determining the speciation of uranium is critical to success of a remediation strategy. The present work elucidates non-enzymatic/abiotic molecular scale redox interactions between biogenic mackinawite and uranium.

Antioxidant properties of various solvent extracts from purple basil

Science.gov (United States)

Yeşiloğlu, Yeşim; Şit, Latifşah

2012-09-01

Water, ethanol and acetone extracts from leaves and flowers of purple basil, one of the most popular spices consumed in the Thrace region of Turkey, were tested in vitro for their ability to inhibit peroxidation of lipids, to scavenge DPPH, hydrogen peroxide, superoxide anion, to reduce Fe(III) to Fe(II) and to chelate Fe(II) ions. The results showed that purple basil contained naturally occurring antioxidant components and possessed antioxidant activity which may be attributed to its lipid peroxidation inhibitory, radical scavenging and metal chelating activities. It was concluded that purple basil might be a potential source of antioxidants.

Some aspects of the electrochemical behaviour of mild steel in carbonate/bicarbonate solutions

International Nuclear Information System (INIS)

Rangel, C.M.; Leitao, R.A.; Fonseca, I.T.

1986-01-01

The electrochemical behaviour of mild steel in aqueous solutions of sodium carbonate/sodium bicarbonate (600 ppm) has been investigated using potentiodynamic polarization. In the pre-passive region three well-defined peaks are observed associated to reduction peaks corresponding to Fe(II) and Fe(III) species. A transpassive anodic peak is also observed being attributed to Fe(VI) species showing, in sweep reversal experiments, an associated reduction peak and an increase in the peak associated to the reduction of Fe(III) species. The characterization of the transpassive peak will be subject of further publication. (author)

Influence of microbial acitivity on the stability of activated sludge flocs

DEFF Research Database (Denmark)

Wilén, Britt-Marie; Nielsen, Jeppe Lund; Keiding, Kristian

2000-01-01

. These results strongly suggested that microorganisms using oxygen and/or nitrate as electron acceptors were important for maintaining the floc strength. The increase in turbidity under deflocculation was well correlated with the number of bacteria and concentration of protein, humic substances and carbohydrates...... sludge. Furthermore, the importance of Fe(III) for the floc strength was illustrated by removal of Fe(III) from the sludge matrix by adding sulphide, which resulted in strong deflocculation. Thus, the deflocculation observed could be either directly due to lack of aerobic microbial activity or indirectly...

Pathways of coupled arsenic and iron cycling in high arsenic groundwater of the Hetao basin, Inner Mongolia, China: an iron isotope approach

Science.gov (United States)

Guo, Huaming; Liu, Chen; Lu, Hai; Wanty, Richard B.; Wang, Jun; Zhou, Yinzhu

2013-01-01

High As groundwater is widely distributed all over the world, which has posed a significant health impact on millions of people. Iron isotopes have recently been used to characterize Fe cycling in aqueous environments, but there is no information on Fe isotope characteristics in the groundwater. Since groundwater As behavior is closely associated with Fe cycling in the aquifers, Fe isotope signatures may help to characterize geochemical processes controlling As concentrations of shallow groundwaters. This study provides the first observation of Fe isotope fractionation in high As groundwater and evaluation of Fe cycling and As behaviors in shallow aquifers in terms of Fe isotope signatures. Thirty groundwater samples were taken for chemical and isotopic analysis in the Hetao basin, Inner Mongolia. Thirty-two sediments were sampled as well from shallow aquifers for Fe isotope analysis. Results showed that groundwater was normally enriched in isotopically light Fe with δ56Fe values between −3.40‰ and 0.58‰ and median of −1.14‰, while heavier δ56Fe values were observed in the sediments (between −1.10‰ and 0.75‰, median +0.36‰). In reducing conditions, groundwaters generally had higher δ56Fe values, in comparison with oxic conditions. High As groundwaters, generally occurring in reducing conditions, had high δ56Fe values, while low As groundwaters normally had low δ56Fe values. Although sediment δ56Fe values were generally independent of lithological conditions, a large variation in sediment δ56Fe values was observed in the oxidation–reduction transition zone. Three pathways were identified for Fe cycling in shallow groundwater, including dissimilatory reduction of Fe(III) oxides, re-adsorption of Fe(II), and precipitation of pyrite and siderite. Dissimilatory reduction of Fe(III) oxides resulted in light δ56Fe values (around −1.0‰) and high As concentration (>50 μg/L) in groundwater in anoxic conditions. Re-adsorption of isotopically

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

Energy Technology Data Exchange (ETDEWEB)

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

2012-06-30

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

Analytical application of aminohydroxamic acids

International Nuclear Information System (INIS)

Fadl Elmoula, Abd ELfatah Abdella

2000-11-01

Anthranilic hydroxamic acid was prepared by coupling of methylanthranilate (prepared by esterification of anthranilic acid with methyl alcohol using the fisher-speir method) with freshly prepared hydroxylamine. The lignad was characterized by the usual reaction of hydroxamic acid with acidic V(V) and Fe(III) solutions that gives blood-red colour in amyl alcohol and deep-violet colour in aqueous solution, respectively. The absorbance of Fe(III)-hydroxamic acids complexes increases with increase of pH. In this study, the effect of pH on the absorbance of Fe(III)-anthranilic hydroxamic acid was in accordance with this trend. The maximum absorbance was obtained at pH 5.0 at maximum wavelength of 482 nm. For Cu(II)-anthranilic hydroxamic acid complex, the use of acidic basic pH lead to precipitation of Cu(II)-ligand complex. But when using buffer pH (acetic acid/sodium acetate) a clear green colour of Cu(II)-ligand complex was obtained. The maximum wavelength of 390 nm. V(V)-anthranilic hydroxamic acid complex was extracted in acidic medium in amyl alcohol at pH 2.0 because in aqueous solution V(V)-anthranilic hydroxamic acid complex has not clear colour. It was observed the the maximum extraction in acidic medium decrease sharply with the increasing of pH value. The maximum wavelength for maximum absorbance was recorded at 472 nm. V(V) interfered with determination of Fe(III)) above concentration of 2 ppm, whereas Cu(II) interferes slightly with the determination of Fe(III) ions even at a high concentration of the Cu(II) ions. Both Cu(II) and Ni(II) do not interfere with the determination of V(V) ions even at high concentrations, Fe(III) ion produced slight interference, while Mo(VI) ions have a pronounced interference. Both V(V) and Fe(III) ions interfered markedly with the determination of Cu(II) ions, and made impractical under conditions. However, the calibration curves for the three metal ions produced a practical linear dynamic range.(Author)

Magnetic properties of Fe-doped organic-inorganic nanohybrids

Science.gov (United States)

Silva, N. J. O.; Amaral, V. S.; Carlos, L. D.; de Zea Bermudez, V.

2003-05-01

We present a magnetic study of Fe-doped diureasils (siloxane-based networks to which poly(ethylene oxide)-based chains are grafted by urea cross linkages doped with Fe(II) or Fe(III) ions. Structural studies show that the Fe(II) ions interact mainly with the organic chain, whereas the incorporation of Fe(III) leads to the formation of iron-based nanoclusters, with radius increasing from 20 to 40 Å. Fe(II)-doped samples behave as simple paramagnets, with μeff=5.32μB. Fe(III)-doped hybrids present antiferromagnetic interactions, with TN increasing with Fe(III) concentration up to 13.6 K for 6% doping. Thermal irreversibility was observed below ˜40 K and is stronger for higher concentrations. The coercive fields (HC) are of the order of 1000 Oe at 5 K. Hysteresis cycles are shifted to negative fields, revealing the presence of exchange anisotropy interactions with exchange fields (HE) of the order of 100 Oe. Both fields decrease rapidly with increasing temperature. We analyze this behavior in terms of the contribution of surface spin disorder to exchange anisotropy.

Study of the role of the ligands coordinated at the surface of pure Wuestite nanoparticles prepared following a room temperature organometallic method: Evidence of ferromagnetic - in shell- and antiferromagnetic - in core magnetic behaviors

Energy Technology Data Exchange (ETDEWEB)

Glaria, Arnaud [CNRS, LCC (Laboratoire de Chimie de Coordination), 205, route de Narbonne, F-31077 Toulouse (France); Universite de Toulouse, UPS, INPT, LCC, F-31077 Toulouse (France); Kahn, Myrtil L., E-mail: myrtil.kahn@lcc-toulouse.fr [CNRS, LCC (Laboratoire de Chimie de Coordination), 205, route de Narbonne, F-31077 Toulouse (France); Universite de Toulouse, UPS, INPT, LCC, F-31077 Toulouse (France); Chaudret, Bruno [CNRS, LCC (Laboratoire de Chimie de Coordination), 205, route de Narbonne, F-31077 Toulouse (France); Universite de Toulouse, UPS, INPT, LCC, F-31077 Toulouse (France); Lecante, Pierre; Casanove, Marie-Jose [CNRS, CEMES (Centre d' Elaboration des Materiaux et d' Etudes Structurales), 29 rue Jeanne Marvig, BP 4347, 31055 Toulouse Cedex (France); Barbara, Bernard, E-mail: bernard.barbara@grenoble.cnrs.fr [Institut Louis Neel, CNRS, 25 Av. des martyrs, BP 166, 38042 Grenoble Cedex 09 (France)

2011-09-15

Highlights: {yields} Pure Wuestite (Fe{sub 1-y}O) nanoparticles synthesized by organometallic chemistry. {yields} The influence of the surface ligands on the magnetic properties. {yields} Ferromagnetic core-antiferromagnetic shell magnetic nanoparticles. - Abstract: Wuestite particles (Fe{sub 1-y}O) are synthesized using controlled hydrolysis at room temperature of [Fe(N(SiMe{sub 3}){sub 2}){sub 2}] and stabilized by amine ligands. This method leads to 5 nm pure wuestite particles. This phase is clearly identified by transmission electron microscopy and wide angle X-ray scattering. Distortion in the crystallographic structure has been demonstrated. Particular attention is paid on the Fe(III) formation. Moreover, a combination of Moessbauer spectroscopy and SQuID measurements, revealed that the particles are composed of an antiferromagnetic core surrounded by a ferromagnetic shell. According to the Neel theory, the Fe(III) and Fe(II) ions present in the particles are ferromagnetically coupled and the proportion of Fe(III) ions varies from 3.9 to 7.1% as a function of the amine ligand.

Evaluation of selectivity and radiolysis behavior of some promising isonicotinamids and dipicolinamides as extractants

Energy Technology Data Exchange (ETDEWEB)

Mowafy, E.A. [Atomic Energy Authority, Cairo (Egypt). Hot Labs. Center

2007-07-01

A series of long chain isonicotinamides (pyridine-4-carboxamides) and dipicolinamides (pyridine-2,6-dicarboxamides) have been prepared with different substituting groups and the extracting ability for Fe(III), Am(III), Eu(III), Sr(II), Co(II) and Cs(I) from nitric acid solutions has been studied. Distribution ratios of Fe(III) as function of nitric acid concentration, extractants concentration and salting-out agent have been measured by using N,N'-dioctylisonicotinamide (DOINA) and N,N,N',N'-tetraoctyldipicolinamide (TODPA) which were chosen for further studies. Irradiation of DOINA and TOBPA by different gamma doses showed a different extraction behavior for Fe(III). The radiolytic degradation of the investigated amides has been estimated by quantitive IR spectroscopy. The results indicated that the radiolytic stability is influenced by the structure of the investigated amides. Symmetrical isonicotinamides or dipicolinamide seems to be less affected by radiation compared with unsymmetrical isonicotiniamides or dipicolinamides. The extraction of iron from aqueous solutions with the investigated extractants is fast. Separation of iron(III) based on kinetic basis was carried out. (orig.)

Crystal structure of octakis(4-methoxypyridinium bis(4-methoxypyridine-κNtetrakis(thiocyanato-κNferrate(III bis[(4-methoxypyridine-κNpentakis(thiocyanato-κNferrate(III] hexakis(thiocyanato-κNferrate(III with iron in three different octahedral coordination environments

Directory of Open Access Journals (Sweden)

Aleksej Jochim

2018-03-01

Full Text Available The crystal structure of the title salt, (C6H8NO8[Fe(NCS4(C6H7NO2][Fe(NCS5(C6H7NO]2[Fe(NCS6], comprises three negatively charged octahedral FeIII complexes with different coordination environments in which the FeIII atoms are coordinated by a different number of thiocyanate anions and 4-methoxypyridine ligands. Charge balance is achieved by 4-methoxypyridinium cations. The asymmetric unit consists of three FeIII cations, one of which is located on a centre of inversion, one on a twofold rotation axis and one in a general position, and ten thiocyanate anions, two 4-methoxypyridine ligands and 4-methoxypyridinium cations (one of which is disordered over two sets of sites. Beside to Coulombic interactions between organic cations and the ferrate(III anions, weak N—H...S hydrogen-bonding interactions involving the pyridinium N—H groups of the cations and the thiocyanate S atoms of the complex anions are mainly responsible for the cohesion of the crystal structure.

Propiedades prooxidantes del camu camu (Myrciaria dubia

Directory of Open Access Journals (Sweden)

Henry Guija

2005-12-01

Full Text Available Objetivo: Determinar el efecto del ion férrico sobre las propiedades prooxidantes del camu camu (Myrciaria dubia. Diseño: Estudio analítico, experimental, prospectivo y longitudinal. Materiales y Métodos: Se ha evaluado las propiedades prooxidantes del camu camu (Myrciaria dubia, fruto caracterizado por tener un elevado contenido de vitamina C, frente a Fe(III, etilendiamino tetraacético (EDTA, tiourea y manitol. Resultados: El camu camu en presencia de Fe-III en tampón fosfato a pH 7,4 incrementó notablemente la generación de radicales libres a través de una cinética de saturación, efecto que fue dependiente de la concentración del metal. La presencia de tiourea o manitol, compuestos de conocida acción antioxidante, inhibieron la formación de radicales libres, en cambio el EDTA lo incrementó. Conclusión: El camu camu incrementa la generación de radicales libres en presencia de Fe(III y EDTA.

Microbial community analysis in rice paddy soils irrigated by acid mine drainage contaminated water.

Science.gov (United States)

Sun, Min; Xiao, Tangfu; Ning, Zengping; Xiao, Enzong; Sun, Weimin

2015-03-01

Five rice paddy soils located in southwest China were selected for geochemical and microbial community analysis. These rice fields were irrigated with river water which was contaminated by Fe-S-rich acid mine drainage. Microbial communities were characterized by high-throughput sequencing, which showed 39 different phyla/groups in these samples. Among these phyla/groups, Proteobacteria was the most abundant phylum in all samples. Chloroflexi, Acidobacteria, Nitrospirae, and Bacteroidetes exhibited higher relative abundances than other phyla. A number of rare and candidate phyla were also detected. Moreover, canonical correspondence analysis suggested that pH, sulfate, and nitrate were significant factors that shaped the microbial community structure. In addition, a wide diversity of Fe- and S-related bacteria, such as GOUTA19, Shewanella, Geobacter, Desulfobacca, Thiobacillus, Desulfobacterium, and Anaeromyxobacter, might be responsible for biogeochemical Fe and S cycles in the tested rice paddy soils. Among the dominant genera, GOUTA19 and Shewanella were seldom detected in rice paddy soils.

Rapid arsenic(V)-reduction by fire in schwertmannite-rich soil enhances arsenic mobilisation

Science.gov (United States)

Johnston, Scott G.; Bennett, William W.; Burton, Edward D.; Hockmann, Kerstin; Dawson, Nigel; Karimian, Niloofar

2018-04-01

Arsenic in acid sulfate soil (ASS) landscapes commonly associates with schwertmannite, a poorly crystalline Fe(III) mineral. Fires in ASS landscapes can thermally transform Fe(III) minerals to more crystalline phases, such as maghemite (γFe2O3). Although thermal genesis of maghemite requires electron transfer via organic matter pyrolysis, the possibility of fire causing concurrent transfer of electrons to schwertmannite-bound As(V) remains unexplored. Here, we subject an organic-rich soil with variable carbon content (∼9-44% organic C) mixed (4:1) with As(V)-bearing schwertmannite (total As of 4.7-5.4 μmol g-1), to various temperatures (200-800 °C) and heating durations (5-120 min). We explore the consequences for As and Fe via X-ray absorption spectroscopy, X-ray diffraction, 57Fe Mössbauer spectroscopy and selective extracts. Heating transforms schwertmannite to mainly maghemite and hematite at temperatures above 300-400 °C, with some transitory formation of magnetite, and electrons are readily transferred to both Fe(III) and As(V). As(V) reduction to As(III) is influenced by a combination of temperature, heating duration and carbon content and is significantly (P moderate fires in ASS landscapes, even of short duration, may generate considerable labile As(III) species and cause a pulse of As(III)aq mobilisation following initial re-wetting. Further research is warranted to examine if analogous As(III) formation occurs during combustion of organic-rich soil containing common As-bearing Fe(III) minerals such as ferrihydrite and goethite.

Quality monitoring methods of initial and terminal manufacture of LiFePO4 based lithium ion batteries by capillary electrophoresis.

Science.gov (United States)

Xie, Xia; Yang, Yang; Zhou, Henghui; Li, Meixian; Zhu, Zhiwei

2018-03-01

Magnetic impurities of lithium ion battery degrade both the capacity and cycling rates, even jeopardize the safety of the battery. During the material manufacture of LiFePO 4 , two opposite and extreme cases (trace impurity Fe(II) with high content of Fe(III) background in FePO 4 of initial end and trace Fe(III) with high content of Fe(II) background in LiFePO 4 of terminal end) can result in the generation of magnetic impurities. Accurate determination of impurities and precise evaluation of raw material or product are necessary to ensure reliability, efficiency and economy in lithium ion battery manufacture. Herein, two kinds of rapid, simple, and sensitive capillary electrophoresis (CE) methods are proposed for quality monitoring of initial and terminal manufacture of LiFePO 4 based lithium ion batteries. The key to success includes the smart use of three common agents 1,10-phenanthroline (phen), EDTA and cetyltrimethyl ammonium bromide (CTAB) in sample solution or background electrolyte (BGE), as well as sample stacking technique of CE feature. Owing to the combination of field-enhanced sample injection (FESI) technique with high stacking efficiency, detection limits of 2.5nM for Fe(II) and 0.1μM for Fe(III) were obtained corresponding to high content of Fe(III) and Fe(II), respectively. The good recoveries and reliability demonstrate that the developed methods are accurate approaches for quality monitoring of LiFePO 4 manufacture. Copyright © 2017 Elsevier B.V. All rights reserved.

The reactivity of Fe(II) associated with goethite formed during short redox cycles toward Cr(VI) reduction under oxic conditions

Energy Technology Data Exchange (ETDEWEB)

Tomaszewski, Elizabeth J.; Lee, Seungyeol; Rudolph, Jared; Xu, Huifang; Ginder-Vogel, Matthew (UW)

2017-08-01

Chromium (Cr) is a toxic metal that causes a myriad of health problems and enters the environment as a result of anthropogenic activities and/or natural processes. The toxicity and solubility of chromium is linked to its oxidation state; Cr(III) is poorly soluble and relatively nontoxic, while Cr(VI) is soluble and a known carcinogen. Solid Fe(II) in iron-bearing minerals, such as pyrite, magnetite, and green rusts, reduce the oxidation state of chromium, reducing its toxicity and mobility. However, these minerals are not the only potential sources of solid-associated Fe(II) available for Cr(VI) reduction. For example, ferric (Fe(III)) (hydr)oxides, such as goethite or hematite, can have Fe(II) in the solid without phase transformation; however, the reactivity of Fe(II) within Fe(III) (hydr)oxides with contaminants, has not been previously investigated. Here, we cyclically react goethite with dissolved Fe(II) followed by dissolved O2, leading to the formation of reactive Fe(II) associated with goethite. In separate reactors, the reactivity of this Fe(II) is probed under oxic conditions, by exposure to chromate (CrO42 -) after either one, two, three or four redox cycles. Cr is not present during redox cycling; rather, it is introduced to a subset of the solid after each oxidation half-cycle. Analysis of X-ray absorption near edge structure (XANES) spectra reveals that the extent of Cr(VI) reduction to Cr(III) depends not only on solid Fe(II) content but also surface area and mean size of ordered crystalline domains, determined by BET surface area analysis and X-ray diffraction (XRD), respectively. Shell-by-shell fitting of the extended X-ray absorption fine structure (EXAFS) spectra demonstrates chromium forms both single and double corner sharing complexes on the surface of goethite, in addition to sorbed Cr(III) species. Finally, transmission electron microscope (TEM) imaging and X-ray energy-dispersive spectroscopy (EDS) illustrate that Cr preferentially

Selective Iron(III ion uptake using CuO-TiO2 nanostructure by inductively coupled plasma-optical emission spectrometry

Directory of Open Access Journals (Sweden)

Rahman Mohammed M

2012-12-01

Full Text Available Abstract Background CuO-TiO2 nanosheets (NSs, a kind of nanomaterials is one of the most attracting class of transition doped semiconductor materials due to its interesting and important optical, electrical, and structural properties and has many technical applications, such as in metal ions detection, photocatalysis, Chemi-sensors, bio-sensors, solar cells and so on. In this paper the synthesis of CuO-TiO2 nanosheets by the wet-chemically technique is reported. Methods CuO-TiO2 NSs were prepared by a wet-chemical process using reducing agents in alkaline medium and characterized by UV/vis., FT-IR spectroscopy, X-ray photoelectron spectroscopy (XPS, powder X-ray diffraction (XRD, and field-emission scanning electron microscopy (FE-SEM etc. Results The structural and optical evaluation of synthesized NSs were measured by XRD pattern, Fourier transform infrared (FT-IR and UV–vis spectroscopy, respectively which confirmed that the obtained NSs are well-crystalline CuO-TiO2 and possessing good optical properties. The morphological analysis of CuO-TiO2 NSs was executed by FE-SEM, which confirmed that the doped products were sheet-shaped and growth in large quantity. Here, the analytical efficiency of the NSs was applied for a selective adsorption of iron(III ion prior to detection by inductively coupled plasma-optical emission spectrometry (ICP-OES. The selectivity of NSs towards various metal ions, including Au(III, Cd(II, Co(II, Cr(III, Fe(III, Pd(II, and Zn(II was analyzed. Conclusions Based on the selectivity study, it was confirmed that the selectivity of doped NSs phase was the most towards Fe(III ion. The static adsorption capacity for Fe(III was calculated to be 110.06 mgg−1. Results from adsorption isotherm also verified that the adsorption process was mainly monolayer-adsorption onto a surface containing a finite number of CuO-TiO2 NSs adsorption sites.

Preconcentration of trace elements by using 1-(2-Pyridylazo-2-naphthol functionalized Amberlite XAD-1180 resin and their determination by FAAS

Directory of Open Access Journals (Sweden)

Tokalioglu Serife

2006-01-01

Full Text Available In this study, Amberlite XAD-1180 resin functionalized by 1-(2-pyridylazo-2-naphthol (PAN was synthesized and the resulting resin was used for preconcentration of Cr(III, Mn(II, Fe(III, Ni(II, Cu(II, Cd(II and Pb(II elements present at trace levels in different matrices. For this purpose, the copolymer was nitrated, reduced to the corresponding amine, converted to the diazonium salt with nitrite and reacted with PAN to produce the XAD-1180-PAN chelating resin. For the described method, the effect of some analytical parameters, such as pH, sample volume, resin amount, flow rates of uptake and stripping, volume and type of eluent, on the recovery of the trace elements was investigated. The metals retained on the XAD-1180-PAN resin were eluted by 2 mol L-1 HNO3. The influence of matrix ions, i.e., Na(I, K(I, Ca(II and Mg(II, on the recovery of trace elements was also examined by using the developed method when they occurred both individually and together. The repeatability of the method at the optimum conditions determined experimentally was investigated. The recovery values for all the elements, except for Cr(III, were found to be >92% and the relative standard deviation was <8.5%. The 3s/b detection limits for Cr(III, Mn(II, Fe(III, Ni(II, Cu(II, Cd(II and Pb(II were found to be 4.1, 0.13, 2.7, 1.2, 0.19, 0.06 and 0.13 µg L-1, respectively. The developed method was utilized for preconcentration and determination of Mn(II, Fe(III, Ni(II, Cu(II, Cd(II and Pb(II in tap water, rain water, and stream water, and of Ni(II, Cd(II and Pb(II in a certified reference material (RM 8704 Buffalo river sediment by flame atomic absorption spectrometry (FAAS.

Spectroscopic and functional characterization of iron-bound forms of Azotobacter vinelandii (Nif)IscA.

Science.gov (United States)

Mapolelo, Daphne T; Zhang, Bo; Naik, Sunil G; Huynh, Boi Hanh; Johnson, Michael K

2012-10-16

The ability of Azotobacter vinelandii(Nif)IscA to bind Fe has been investigated to assess the role of Fe-bound forms in NIF-specific Fe-S cluster biogenesis. (Nif)IscA is shown to bind one Fe(III) or one Fe(II) per homodimer and the spectroscopic and redox properties of both the Fe(III)- and Fe(II)-bound forms have been characterized using the UV-visible absorption, circular dichroism, and variable-temperature magnetic circular dichroism, electron paramagnetic resonance, Mössbauer and resonance Raman spectroscopies. The results reveal a rhombic intermediate-spin (S = 3/2) Fe(III) center (E/D = 0.33, D = 3.5 ± 1.5 cm(-1)) that is most likely 5-coordinate with two or three cysteinate ligands and a rhombic high spin (S = 2) Fe(II) center (E/D = 0.28, D = 7.6 cm(-1)) with properties similar to reduced rubredoxins or rubredoxin variants with three cysteinate and one or two oxygenic ligands. Iron-bound (Nif)IscA undergoes reversible redox cycling between the Fe(III)/Fe(II) forms with a midpoint potential of +36 ± 15 mV at pH 7.8 (versus NHE). l-Cysteine is effective in mediating release of free Fe(II) from both the Fe(II)- and Fe(III)-bound forms of (Nif)IscA. Fe(III)-bound (Nif)IscA was also shown to be a competent iron source for in vitro NifS-mediated [2Fe-2S] cluster assembly on the N-terminal domain of NifU, but the reaction occurs via cysteine-mediated release of free Fe(II) rather than direct iron transfer. The proposed roles of A-type proteins in storing Fe under aerobic growth conditions and serving as iron donors for cluster assembly on U-type scaffold proteins or maturation of biological [4Fe-4S] centers are discussed in light of these results.

Contrasting distributions of groundwater arsenic and uranium in the western Hetao basin, Inner Mongolia: Implication for origins and fate controls

Science.gov (United States)

Guo, Huaming; Jia, Yongfeng; Wanty, Richard B.; Jiang, Yuxiao; Zhao, Weiguang; Xiu, Wei; Shen, Jiaxing; Li, Yuan; Cao, Yongsheng; Wu, Yang; Zhang, Di; Wei, Chao; Zhang, Yilong; Cao, Wengeng; Foster, Andrea L.

2016-01-01

Although As concentrations have been investigated in shallow groundwater from the Hetao basin, China, less is known about U and As distributions in deep groundwater, which would help to better understand their origins and fate controls. Two hundred and ninety-nine groundwater samples, 122 sediment samples, and 14 rock samples were taken from the northwest portion of the Hetao basin, and analyzed for geochemical parameters. Results showed contrasting distributions of groundwater U and As, with high U and low As concentrations in the alluvial fans along the basin margins, and low U and high As concentrations downgradient in the flat plain. The probable sources of both As and U in groundwater were ultimately traced to the bedrocks in the local mountains (the Langshan Mountains). Chemical weathering of U-bearing rocks (schist, phyllite, and carbonate veins) released and mobilized U as UO2(CO3)22 − and UO2(CO3)34 − species in the alluvial fans under oxic conditions and suboxic conditions where reductions of Mn and NO3− were favorable (OSO), resulting in high groundwater U concentrations. Conversely, the recent weathering of As-bearing rocks (schist, phyllite, and sulfides) led to the formation of As-bearing Fe(III) (hydr)oxides in sediments, resulting in low groundwater As concentrations. Arsenic mobilization and U immobilization occurred in suboxic conditions where reduction of Fe(III) oxides was favorable and reducing conditions (SOR). Reduction of As-bearing Fe(III) (hydr)oxides, which were formed during palaeo-weathering and transported and deposited as Quaternary aquifer sediments, was believed to release As into groundwater. Reduction of U(VI) to U(IV) would lead to the formation of uraninite, and therefore remove U from groundwater. We conclude that the contrasting distributions of groundwater As and U present a challenge to ensuring safe drinking water in analogous areas, especially with high background values of U and As.

Cytoprophet: a Cytoscape plug-in for protein and domain interaction networks inference.

Science.gov (United States)

Morcos, Faruck; Lamanna, Charles; Sikora, Marcin; Izaguirre, Jesús

2008-10-01

Cytoprophet is a software tool that allows prediction and visualization of protein and domain interaction networks. It is implemented as a plug-in of Cytoscape, an open source software framework for analysis and visualization of molecular networks. Cytoprophet implements three algorithms that predict new potential physical interactions using the domain composition of proteins and experimental assays. The algorithms for protein and domain interaction inference include maximum likelihood estimation (MLE) using expectation maximization (EM); the set cover approach maximum specificity set cover (MSSC) and the sum-product algorithm (SPA). After accepting an input set of proteins with Uniprot ID/Accession numbers and a selected prediction algorithm, Cytoprophet draws a network of potential interactions with probability scores and GO distances as edge attributes. A network of domain interactions between the domains of the initial protein list can also be generated. Cytoprophet was designed to take advantage of the visual capabilities of Cytoscape and be simple to use. An example of inference in a signaling network of myxobacterium Myxococcus xanthus is presented and available at Cytoprophet's website. http://cytoprophet.cse.nd.edu.

Determination of stability constants of iron(III and chromium(III-nitrilotriacetate-methyl cysteine mixed complexes by electrophoretic technique

Directory of Open Access Journals (Sweden)

Brij Bhushan Tewari

2004-06-01

Full Text Available The stability constants of Fe(III and Cr(III with methyl cysteine and nitrilotriacetate (NTA were determined by paper electrophoretic technique. Beside binary ternary complexes have also been studied, in which nitrilotriacetate and methyl cysteine acts as primary and secondary ligand, respectively. The stability constants of mixed ligand complexes metal (M-nitrilotriacetate-methyl cysteine have been found to be 5.72 plus or minus 0.09 and 5.54 plus or minus 0.11 (log K values for Fe(III and Cr(III complexes, respectively, at 35 oC and ionic strength 0.1 M.

Moessbauer effect and electron paramagnetic resonance studies on yeast aconitase

International Nuclear Information System (INIS)

Suzuki, Takashi; Maeda, Yutaka; Sakai, Hiroshi; Fujimoto, Shigeru; Morita, Yuhei.

1975-01-01

The Moessbauer effect and electron paramagnetic resonance (EPR) of yeast aconitase [EC 4.2.1.3] purified from the cells of Candida lipolytica (ATCC 20114) were measured. Moessbauer spectra suggested that yeast acontitase mostly contained two high-spin Fe(III) ions in an antiferromagnetically coupled binuclear complex that resembled oxidized 2 Fe ferredoxins, together with a small amount of high-spin Fe(II). EPR spectra recorded no signal at 77 0 K, but showed a slightly asymmetric signal centered at g=2.0 at 4.2 0 K, presumably due to the small amount of Fe(II) Fe(III) pairs. (auth.)

Solid-Phase Fe Speciation along the Vertical Redox Gradients in Floodplains using XAS and Mössbauer Spectroscopies

Energy Technology Data Exchange (ETDEWEB)

Chen, Chunmei [Department; Kukkadapu, Ravi K. [Environmental; Lazareva, Olesya [Department; Sparks, Donald L. [Department

2017-06-30

Properties of Fe minerals are poorly understood in natural soils and sediments with variable redox conditions. In this study, we combined 57Fe Mössbauer and Fe K-edge X-ray absorption spectroscopic techniques to assess solid-phase Fe speciation along the vertical redox gradients of floodplain profiles, which exhibited a succession of oxic, anoxic and suboxic-oxic zones with increasing depth along the vertical profiles. The anoxic conditions at the intermediate horizon (55-80 cm) of the eastern floodplain resulted in extensive depletion of Fe(III)-oxides including both ferrihydrite and goethite, concurrent with a corresponding reduction of phyllosilicates(PS)-Fe(III) to PS-Fe(II). In addition, the anoxic conditions increased the crystallinity of Fe(III)-oxides in this reduced zone, relative to the oxic zones. In the most reduced intermediate sediments at 80-120cm of the western floodplain, the anoxic conditions drove the complete reductive dissolution of Fe(III) oxides, as well as the greatest reduction (48-55%) in PS-Fe(III). In both oxic near-surface horizon and oxic-suboxic gravel aquifers beneath the soil horizons, Fe(III)-oxides were mainly present as ferrihydrite with a less amount of goethite, which preferentially occurred as nanogoethite or Al/Si-substituted goethite. Ferrihydrite with varying crystallinity or impurities such as organic matter, Al or Si, persisted under suboxic-oxic conditions in the floodplain. This study indicates that vertical redox gradients exert a major control on the quantity and speciation of Fe(III) oxides as well as the oxidation state of structural Fe in PS, which could significantly affect nutrient cycling and carbon (de)stabilization.

Link Between Capacity for Current Production and Syntrophic Growth in Geobacter species

Directory of Open Access Journals (Sweden)

Amelia-Elena eRotaru

2015-07-01

Full Text Available Electrodes are unnatural electron acceptors, and it is yet unknown how some Geobacter species evolved to use electrodes as terminal electron acceptors. Analysis of different Geobacter species revealed that they varied in their capacity for current production. G. metallireducens and G. hydrogenophilus generated high current densities (ca. 0.05 mA/cm2, comparable to G. sulfurreducens. G. bremensis, G. chapellei, G. humireducens, and G. uranireducens, produced much lower currents (ca. 0.05 mA/cm2 and G. bemidjiensis was previously found to not produce current. There was no correspondence between the effectiveness of current generation and Fe(III oxide reduction rates. Some high-current-density strains (G. metallireducens and G. hydrogenophilus reduced Fe(III-oxides as fast as some low-current-density strains (G. bremensis, G. humireducens, and G. uranireducens whereas other low-current-density strains (G. bemidjiensis and G. chapellei reduced Fe(III oxide as slowly as G. sulfurreducens, a high-current-density strain. However, there was a correspondence between the ability to produce higher currents and the ability to grow syntrophically. G. hydrogenophilius was found to grow in co-culture with Methanosarcina barkeri, which is capable of direct interspecies electron transfer (DIET, but not with Methanospirillium hungatei capable only of H2 or formate transfer. Conductive granular activated carbon (GAC stimulated metabolism of the G. hydrogenophilus - M. barkeri co-culture, consistent with electron exchange via DIET. These findings, coupled with the previous finding that G. metallireducens and G. sulfurreducens are also capable of DIET, suggest that evolution to optimize DIET has fortuitiously conferred the capability for high-density current production to some Geobacter species.

Microbial Community and Functional Gene Changes in Arctic Tundra Soils in a Microcosm Warming Experiment

Directory of Open Access Journals (Sweden)

Ziming Yang

2017-09-01

Full Text Available Microbial decomposition of soil organic carbon (SOC in thawing Arctic permafrost is important in determining greenhouse gas feedbacks of tundra ecosystems to climate. However, the changes in microbial community structure during SOC decomposition are poorly known. Here we examine these changes using frozen soils from Barrow, Alaska, USA, in anoxic microcosm incubation at −2 and 8°C for 122 days. The functional gene array GeoChip was used to determine microbial community structure and the functional genes associated with SOC degradation, methanogenesis, and Fe(III reduction. Results show that soil incubation after 122 days at 8°C significantly decreased functional gene abundance (P < 0.05 associated with SOC degradation, fermentation, methanogenesis, and iron cycling, particularly in organic-rich soil. These observations correspond well with decreases in labile SOC content (e.g., reducing sugar and ethanol, methane and CO2 production, and Fe(III reduction. In contrast, the community functional structure was largely unchanged in the −2°C incubation. Soil type (i.e., organic vs. mineral and the availability of labile SOC were among the most significant factors impacting microbial community structure. These results demonstrate the important roles of microbial community in SOC degradation and support previous findings that SOC in organic-rich Arctic tundra is highly vulnerable to microbial degradation under warming.

Oxidation of a Dimethoxyhydroquinone by Ferrihydrite and Goethite Nanoparticles: Iron Reduction versus Surface Catalysis.

Science.gov (United States)

Krumina, Lelde; Lyngsie, Gry; Tunlid, Anders; Persson, Per

2017-08-15

Hydroquinones are important mediators of electron transfer reactions in soils with a capability to reduce Fe(III) minerals and molecular oxygen, and thereby generating Fenton chemistry reagents. This study focused on 2,6-dimethoxy hydroquinone (2,6-DMHQ), an analogue to a common fungal metabolite, and its reaction with ferrihydrite and goethite under variable pH and oxygen concentrations. Combined wet-chemical and spectroscopic analyses showed that both minerals effectively oxidized 2,6-DMHQ in the presence of oxygen. Under anaerobic conditions the first-order oxidation rate constants decreased by one to several orders of magnitude depending on pH and mineral. Comparison between aerobic and anaerobic results showed that ferrihydrite promoted 2,6-DMHQ oxidation both via reductive dissolution and heterogeneous catalysis while goethite mainly caused catalytic oxidation. These results were in agreement with changes in the reduction potential (E H ) of the Fe(III) oxide/Fe(II) aq redox couple as a function of dissolved Fe(II) where E H of goethite was lower than ferrihydrite at any given Fe(II) concentration, which makes ferrihydrite more prone to reductive dissolution by the 2,6-DMBQ/2,6-DMHQ redox couple. This study showed that reactions between hydroquinones and iron oxides could produce favorable conditions for formation of reactive oxygen species, which are required for nonenzymatic Fenton-based decomposition of soil organic matter.

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

Binding of heavy metal ions in aggregates of microbial cells, EPS and biogenic iron minerals measured in-situ using metal- and glycoconjugates-specific fluorophores

Science.gov (United States)

Hao, Likai; Guo, Yuan; Byrne, James M.; Zeitvogel, Fabian; Schmid, Gregor; Ingino, Pablo; Li, Jianli; Neu, Thomas R.; Swanner, Elizabeth D.; Kappler, Andreas; Obst, Martin

2016-05-01

Aggregates consisting of bacterial cells, extracellular polymeric substances (EPS) and Fe(III) minerals formed by Fe(II)-oxidizing bacteria are common at bulk or microscale chemical interfaces where Fe cycling occurs. The high sorption capacity and binding capacity of cells, EPS, and minerals controls the mobility and fate of heavy metals. However, it remains unclear to which of these component(s) the metals will bind in complex aggregates. To clarify this question, the present study focuses on 3D mapping of heavy metals sorbed to cells, glycoconjugates that comprise the majority of EPS constituents, and Fe(III) mineral aggregates formed by the phototrophic Fe(II)-oxidizing bacteria Rhodobacter ferrooxidans SW2 using confocal laser scanning microscopy (CLSM) in combination with metal- and glycoconjugates-specific fluorophores. The present study evaluated the influence of glycoconjugates, microbial cell surfaces, and (biogenic) Fe(III) minerals, and the availability of ferrous and ferric iron on heavy metal sorption. Analyses in this study provide detailed knowledge on the spatial distribution of metal ions in the aggregates at the sub-μm scale, which is essential to understand the underlying mechanisms of microbe-mineral-metal interactions. The heavy metals (Au3+, Cd2+, Cr3+, CrO42-, Cu2+, Hg2+, Ni2+, Pd2+, tributyltin (TBT) and Zn2+) were found mainly sorbed to cell surfaces, present within the glycoconjugates matrix, and bound to the mineral surfaces, but not incorporated into the biogenic Fe(III) minerals. Statistical analysis revealed that all ten heavy metals tested showed relatively similar sorption behavior that was affected by the presence of sorbed ferrous and ferric iron. Results in this study showed that in addition to the mineral surfaces, both bacterial cell surfaces and the glycoconjugates provided most of sorption sites for heavy metals. Simultaneously, ferrous and ferric iron ions competed with the heavy metals for sorption sites on the organic

Cyanide binding to ferrous and ferric microperoxidase-11.

Science.gov (United States)

Ascenzi, Paolo; Sbardella, Diego; Santucci, Roberto; Coletta, Massimo

2016-07-01

Microperoxidase-11 (MP11) is an undecapeptide derived from horse heart cytochrome c (cytc). MP11 is characterized by a covalently linked solvent-exposed heme group, the heme-Fe atom being axially coordinated by a histidyl residue. Here, the reactions of ferrous and ferric MP11 (MP11-Fe(II) and MP11-Fe(III), respectively) with cyanide have been investigated from the kinetic and thermodynamic viewpoints, at pH 7.0 and 20.0 °C. Values of the second-order rate constant for cyanide binding to MP11-Fe(II) and MP11-Fe(III) are 4.5 M(-1) s(-1) and 8.9 × 10(3) M(-1) s(-1), respectively. Values of the first-order rate constant for cyanide dissociation from ligated MP11-Fe(II) and MP11-Fe(III) are 1.8 × 10(-1) s(-1) and 1.5 × 10(-3) s(-1), respectively. Values of the dissociation equilibrium constant for cyanide binding to MP11-Fe(II) and MP11-Fe(III) are 3.7 × 10(-2) and 1.7 × 10(-7) M, respectively, matching very well with those calculated from kinetic parameters so that no intermediate species seem to be involved in the ligand-binding process. The pH-dependence of cyanide binding to MP11-Fe(III) indicates that CN(-) is the only binding species. Present results have been analyzed in parallel with those of several heme-proteins, suggesting that (1) the ligand accessibility to the metal center and cyanide ionization may modulate the formation of heme-Fe-cyanide complexes, and (2) the general polarity of the heme pocket and/or hydrogen bonding of the heme-bound ligand may affect cyanide exit from the protein matrix. Microperoxidase-11 (MP11) is an undecapeptide derived from horse heart cytochrome c. Penta-coordinated MP11 displays a very high reactivity towards cyanide, whereas the reactivity of hexa-coordinated horse heart cytochrome c is very low.

Extractive properties of benzohydroxamic and N-benzoyl-benzohydroxamic acids as analytical reagents towards six transition metal ions

International Nuclear Information System (INIS)

Mohamed, Mohamed Rafie Hamid

1999-06-01

Two hydroxamic acids were prepared: benzohydroxamic and N-benzoyl benzohydroxamic acids. The former was prepared by coupling the free hydrox amine with benzoyl chloride with the ratio 1:1 in alkaline medium, where as the latter by the same procedure with the ratio 1:2 respectively, they were identified by their melting points, elemental analysis of their nitrogen contents. infra-red spectrophotometry, as well as their nitrogen using elevation of boiling point and the titration method to determine their molecular weights. The two hydroxamic acids were used as analytical reagents for the extraction of the metals Cr(vi), Fe(III), Ti(iv), Co(II) and U(vi). Benzohydroxamic acid has a maximum extraction 99.55% for Cr.(vi) 3M H 2 SO 4 , of 90.16% for Ti(iv) at pH 2.0,of 80.56% for Co(II) at pH 8.0 and 98.01% for U(vi) at pH 6.0. N-benzoyl benzohydroxamic acid has a maximum extraction of 96.45% for Cr(vi) at 3M H 2 So 4 , of 90.82% for Fe(III) at pH 4.0, of 97.02% for V(v) at 3M H 2 So 4 , of 83.56% for Ti(iv) at pH 2.0, of 89.82% for Co(II) at pH 8.0 and of 97.16% for U(vi) at pH 6.0. at the same pH of maximum extraction using heavy matrix, synthetic sea-water, benzohydroxamic acid has maximum values of 91.08%, of 77.99%, of 91.39%, of 87.50 and of 93.17% for Cr(vi), Fe(III), V(v), Ti(iv), Co9II) and U(vi) respectively whereas n-benzoyl benzohydroxamic acid has maximum values of 86.17%, of 77.78%, of 89.61%, of 75.66%, of 79.63% and of 91.18% for Cr(vi), Fe(III), V(v), Ti(iv), Co(II) and U(vi) respectively. The ratio of metal to ligand was determined utilizing the continuous variation method. It was 1 :2, 1: 1, 1 : 1, 1 : 2, 1: 2 and 1 : 2 with respect to Cr(vi), fe(III), Ti(iv), Co(II) and U(vi) respectively.(Author)

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

Science.gov (United States)

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

2013-09-18

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

Synthesis, spectroscopic characterization, biological studies and DFT calculations on some transition metal complexes of NO donor ligand

Science.gov (United States)

Zordok, W. A.; Sadeek, S. A.

2018-04-01

Seven new complexes of2-oxo-4,6-diphenyl-1,2-dihyropyridine-3-carbonitrile (L) with Fe(III), Co(II), Cu(II), Zn(II), Y(III), Zr(IV) and La(III) were synthesized. The isolated solid compounds were elucidated from micro analytical, IR, electronic, mass, 1H NMR, magnetic susceptibility measurements and TG/DTG, DTA analyses. The intensity of ν(Ctbnd N) was changed to strong and shifted to around 2200 cm-1. Also, the ν(Cdbnd O) was shifted to higher frequency value (1644 cm-1). The spectra of the complexes indicate that the free ligand is coordinated to the metal ions via nitrogen of carbonitrile group and oxygen of keto group. From DFT calculations the Cu(II) and Fe(III) complexes behave as regular octahedral, while other complexes are distorted octahedral. The value of energy gap of the free ligand (ΔE = 0.3343 eV) is greater than all new complexes, so they are more reactive than free ligand, also the Fe(III) complex (ΔE = 0.0985 eV) is the most reactive complex, while Cu(II) complex (ΔE = 0.3219 eV) is the least reactive complex. The LMCT in case of Zr(IV) complex was resulted from transitions from HOMO-2 (62%), HOMO-1 (16%)and HOMO (25%), while the d-d transition in Fe(III) complex was resulted from HOMO-1(30%), HOMO-2(62%) and HOMO(30%). Also, the metal complexes exhibit antibacterial activity for Gram-positive and Gram-negative and antifungal activity. The Y(III) and Cu(II) complexes are highly significant for Escherichia coli and salmonella typhimurium.

Paramagnetic epoxy resin

Directory of Open Access Journals (Sweden)

E. C. Vazquez Barreiro

2017-01-01

Full Text Available This work illustrates that macrocycles can be used as crosslinking agents for curing epoxy resins, provided that they have appropriate organic functionalities. As macrocycles can complex metal ions in their structure, this curing reaction allows for the introduction of that metal ion into the resin network. As a result, some characteristic physical properties of the metallomacrocycle could be transferred to the new material. The bisphenol A diglycidyl ether (BADGE, n = 0 and hemin (a protoporphyrin IX containing the Fe(III ion, and an additional chloride ligand have been chosen. The new material has been characterized by differential scanning calorimetry (DSC, thermogravimetric analysis (TGA, Fourier Transform Infrared (FT-IR, Nuclear Magnetic Resonance (NMR, Transmission Electron Microscopy (TEM, and magnetic susceptibility measurements. Fe(III remains in the high-spin state during the curing process and, consequently, the final material exhibits the magnetic characteristics of hemin. The loss of the chlorine atom ligand during the cure of the resin allows that Fe(III can act as Lewis acid, catalyzing the crosslinking reactions. At high BADGE n = 0/hemin ratios, the formation of ether and ester bonds occurs simultaneously during the process.

Synthesis of Zn–Fe layered double hydroxides via an oxidation process and structural analysis of products

Energy Technology Data Exchange (ETDEWEB)

Morimoto, Kazuya, E-mail: kazuya.morimoto@aist.go.jp [Institute for Geo-Resources and Environment, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8567 (Japan); Tamura, Kenji [Environmental Remediation Materials Unit, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan); Anraku, Sohtaro [Graduate School of Engineering, Hokkaido University, Kita 13 Nishi 8, Kita-ku, Sapporo 060-8628 (Japan); Sato, Tsutomu [Faculty of Engineering, Hokkaido University, Kita 13 Nishi 8, Kita-ku, Sapporo 060-8628 (Japan); Suzuki, Masaya [Institute for Geo-Resources and Environment, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8567 (Japan); Yamada, Hirohisa [Environmental Remediation Materials Unit, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan)

2015-08-15

The synthesis of Zn–Fe(III) layered double hydroxides was attempted, employing different pathways using either Fe(II) or Fe(III) species together with Zn as the initial reagents. The product derived from the synthesis employing Fe(II) was found to transition to a Zn–Fe(III) layered double hydroxides phase following oxidation process. In contrast, the product obtained with Fe(III) did not contain a layered double hydroxides phase, but rather consisted of simonkolleite and hydrous ferric oxide. It was determined that the valency of the Fe reagent used in the initial synthesis affected the generation of the layered double hydroxides phase. Fe(II) species have ionic radii and electronegativities similar to those of Zn, and therefore are more likely to form trioctahedral hydroxide layers with Zn species. - Graphical abstract: The synthesis of Zn–Fe(III) layered double hydroxides was attempted, employing different pathways using either Fe(II) or Fe(III) species together with Zn as the initial reagents. - Highlights: • Iron valency affected the generation of Zn–Fe layered double hydroxides. • Zn–Fe layered double hydroxides were successfully synthesized using Fe(II). • Fe(II) species were likely to form trioctahedral hydroxide layers with Zn species.

[Influence of Dissimilatory Iron Reduction on the Speciation and Bioavailability of Heavy Metals in Soil].

Science.gov (United States)

Si, You-bin; Wang, Juan

2015-09-01

Fe(III) dissimilatory reduction by microbes is an important process of producing energy in the oxidation of organic compounds under anaerobic condition with Fe(III) as the terminal electron acceptor and Fe(II) as the reduction product. This process is of great significance in element biogeochemical cycle. Iron respiration has been described as one of the most ancient forms of microbial metabolism on the earth, which is bound up with material cycle in water, soil and sediments. Dissimilatory iron reduction plays important roles in heavy metal form transformation and the remediation of heavy metal and radionuclide contaminated soils. In this paper, we summarized the research progress of iron reduction in the natural environment, and discussed the influence and the mechanism of dissimilatory iron reduction on the speciation and bioavailability of heavy metals in soil. The effects of dissimilatory iron reduction on the speciation of heavy metals may be attributed to oxidation and reduction, methytation and immobilization of heavy metals in relation to their bioavailability in soils. The mechanisms of Fe(III) dissimilatory reduction on heavy metal form transformation contain biological and chemical interactions, but the mode of interaction remains to be further investigated.

Manganese and iron oxidation by fungi isolated from building stone.

Science.gov (United States)

de la Torre, M A; Gomez-Alarcon, G

1994-01-01

Acid and nonacid generating fungal strains isolated from weathered sandstone, limestone, and granite of Spanish cathedrals were assayed for their ability to oxidize iron and manganese. In general, the concentration of the different cations present in the mineral salt media directly affected Mn(IV) oxide formation, although in some cases, the addition of glucose and nitrate to the culture media was necessary. Mn(II) oxidation in acidogenic strains was greater in a medium containing the highest concentrations of glucose, nitrate, and manganese. High concentrations of Fe(II), glucose, and mineral salts were optimal for iron oxidation. Mn(IV) precipitated as oxides or hydroxides adhered to the mycelium. Most of the Fe(III) remained in solution by chelation with organic acids excreted by acidogenic strains. Other metabolites acted as Fe(III) chelators in nonacidogenic strains, although Fe(III) deposits around the mycelium were also detected. Both iron and manganese oxidation were shown to involve extracellular, hydrosoluble enzymes, with maximum specific activities during exponential growth. Strains able to oxidize manganese were also able to oxidize iron. It is concluded that iron and manganese oxidation reported in this work were biologically induced by filamentous fungi mainly by direct (enzymatic) mechanisms.

Redox behaviors of iron by absorption spectroscopy and redox potential measurement

International Nuclear Information System (INIS)

Oh, Jae Yong

2010-02-01

This work is performed to study the redox (reduction/oxidation) behaviors of iron in aqueous system by a combination of absorption spectroscopy and redox potential measurements. There are many doubts on redox potential measurements generally showing low accuracies and high uncertainties. In the present study, redox potentials are measured by utilizing various redox electrodes such as Pt, Au, Ag, and glassy carbon (GC) electrodes. Measured redox potentials are compared with calculated redox potentials based on the chemical oxidation speciation of iron and thermodynamic data by absorption spectroscopy, which provides one of the sensitive and selective spectroscopic methods for the chemical speciation of Fe(II/III). From the comparison analyses, redox potential values measured by the Ag redox electrode are fairly consistent with those calculated by the chemical aqueous speciation of iron in the whole system. In summary, the uncertainties of measured redox potentials are closely related with the total Fe concentration and affected by the formation of mixed potentials due to Fe(III) precipitates in the pH range of 6 ∼ 9 beyond the solubility of Fe(III), whilst being independent of the initially prepared concentration ratios between Fe(II) and Fe(III)

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

Directory of Open Access Journals (Sweden)

Vukojević Vanja

2004-01-01

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

Study on the removal of fluoride from drinking water and effluents

International Nuclear Information System (INIS)

Charbel, M.Y.

1990-01-01

A study for removal of excess fluoride from drinking water and aqueous effluents from nuclear power plants is presented. Inorganic and organic ion exchangers were used for this purpose: 1. Alumina microspheres form, granular alumina and zirconium oxide (powder or granular form with the aid of agglutinants) were experimented. 2. Strong cation exchange resins as Al-III, Fe-III, Zr-IV, RE-III, Ca-II and Mg-II salt form were examined. 3. Retention on hydrous oxide of Al-III, Fe-III, Zr-IV and RE-III supported on strong cation ion exchanger was performed. 4. Strong anion exchange resins in the form of OH sup(-), Cl sup(-), NO3 sup(-), CO3 sup(2-), SO4 sup(2-), ClO4 sup(-) and Zr(SO4)3 sup(2-) were examined. For the experiments pure fluoride solutions or dilute solutions containing the cations of Fe-III, Ca-II, Mn-II, Cu-II, Al-III, Cd-II and U-VI were used. Cation exchange resin loaded with zirconium, anion exchange resin as hydroxyl and zirconium sulfate complex form exhibited very good results, but the last performed best and we suggest it for industrial application. (author)

Design of Mixed Batch Reactor and Column Studies at Oak Ridge National Laboratory

International Nuclear Information System (INIS)

Wu, Weimin; Criddle, Craig S.

2015-01-01

We (the Stanford research team) were invited as external collaborators to contribute expertise in environmental engineering and field research at the ORNL IFRC, Oak Ridge, TN, for projects carried out at the Argonne National Laboratory and funded by US DOE. Specifically, we assisted in the design of batch and column reactors using ORNL IFRC materials to ensure the experiments were relevant to field conditions. During the funded research period, we characterized ORNL IFRC groundwater and sediments in batch microcosm and column experiments conducted at ANL, and we communicated with ANL team members through email and conference calls and face-to-face meetings at the annual ERSP PI meeting and national meetings. Microcosm test results demonstrated that U(VI) in sediments was reduced to U(IV) when amended with ethanol. The reduced products were not uraninite but unknown U(IV) complexes associated with Fe. Fe(III) in solid phase was only partially reduced. Due to budget reductions at ANL, Stanford contributions ended in 2011.

Monitoring Uranium Transformations Determined by the Evolution of Biogeochemical Processes: Design of Mixed Batch Reactor and Column Studies at Oak Ridge National Laboratory

Energy Technology Data Exchange (ETDEWEB)

Criddle, Craig S.; Wu, Weimin

2013-04-17

With funds provided by the US DOE, Argonne National Laboratory subcontracted the design of batch and column studies to a Stanford University team with field experience at the ORNL IFRC, Oak Ridge, TN. The contribution of the Stanford group ended in 2011 due to budget reduction in ANL. Over the funded research period, the Stanford research team characterized ORNL IFRC groundwater and sediments and set up microcosm reactors and columns at ANL to ensure that experiments were relevant to field conditions at Oak Ridge. The results of microcosm testing demonstrated that U(VI) in sediments was reduced to U(IV) with the addition of ethanol. The reduced products were not uraninite but were instead U(IV) complexes associated with Fe. Fe(III) in solid phase was only partially reduced. The Stanford team communicated with the ANL team members through email and conference calls and face to face at the annual ERSP PI meeting and national meetings.

Design of Mixed Batch Reactor and Column Studies at Oak Ridge National Laboratory

Energy Technology Data Exchange (ETDEWEB)

Wu, Weimin [Stanford Univ., CA (United States); Criddle, Craig S. [Stanford Univ., CA (United States)

2015-11-16

We (the Stanford research team) were invited as external collaborators to contribute expertise in environmental engineering and field research at the ORNL IFRC, Oak Ridge, TN, for projects carried out at the Argonne National Laboratory and funded by US DOE. Specifically, we assisted in the design of batch and column reactors using ORNL IFRC materials to ensure the experiments were relevant to field conditions. During the funded research period, we characterized ORNL IFRC groundwater and sediments in batch microcosm and column experiments conducted at ANL, and we communicated with ANL team members through email and conference calls and face-to-face meetings at the annual ERSP PI meeting and national meetings. Microcosm test results demonstrated that U(VI) in sediments was reduced to U(IV) when amended with ethanol. The reduced products were not uraninite but unknown U(IV) complexes associated with Fe. Fe(III) in solid phase was only partially reduced. Due to budget reductions at ANL, Stanford contributions ended in 2011.

Dynamics of arsenic adsorption in the targeted arsenic-safe aquifers in Matlab, south-eastern Bangladesh: Insight from experimental studies

Energy Technology Data Exchange (ETDEWEB)

Robinson, Clare, E-mail: crobinson@eng.uwo.ca [Department of Civil and Environmental Engineering, University of Western Ontario, London, N6A 5B9 (Canada)] [NGO Forum for Drinking Water Supply and Sanitation, Lalmatia, Dhaka 1207 (Bangladesh); Broemssen, Mattias von [KTH-International Groundwater Arsenic Research Group, Department of Land and Water Resources Engineering, Royal Institute of Technology, SE-100 44 Stockholm (Sweden)] [Ramboell Sweden AB, Box 4205, SE-102 65 Stockholm (Sweden); Bhattacharya, Prosun; Haeller, Sara; Biven, Annelie [KTH-International Groundwater Arsenic Research Group, Department of Land and Water Resources Engineering, Royal Institute of Technology, SE-100 44 Stockholm (Sweden); Hossain, Mohammed [NGO Forum for Drinking Water Supply and Sanitation, Lalmatia, Dhaka 1207 (Bangladesh)] [KTH-International Groundwater Arsenic Research Group, Department of Land and Water Resources Engineering, Royal Institute of Technology, SE-100 44 Stockholm (Sweden); Jacks, Gunnar [KTH-International Groundwater Arsenic Research Group, Department of Land and Water Resources Engineering, Royal Institute of Technology, SE-100 44 Stockholm (Sweden); Ahmed, Kazi Matin; Hasan, M. Aziz [Department of Geology, University of Dhaka, Dhaka 1000 (Bangladesh); Thunvik, Roger [KTH-International Groundwater Arsenic Research Group, Department of Land and Water Resources Engineering, Royal Institute of Technology, SE-100 44 Stockholm (Sweden)

2011-04-15

Research highlights: {yields} Adsorption behaviour of shallow oxidized sediments from Matlab Region in SE Bangladesh is investigated. {yields} Oxidized sediments have a high capacity to adsorb arsenic. {yields} Adsorption capacity will be reduced by high concentration of reactive organic C. {yields} Monitoring of groundwater quality over 5 year period shows relatively stable water chemistry. - Abstract: Targeting shallow low-As aquifers based on sediment colour may be a viable solution for supplying As-safe drinking water to rural communities in some regions of Bangladesh and West Bengal in India. The sustainability of this solution with regard to the long-term risk of As-safe oxidized aquifers becoming enriched with As needs to be assessed. This study focuses on the adsorption behaviour of shallow oxidized sediments from Matlab Region, Bangladesh, and their capacity to attenuate As if cross-contamination of the oxidized aquifers occurs. Water quality analyses of samples collected from 20 tube-wells in the region indicate that while there may be some seasonal variability, the groundwater chemistry in the reduced and oxidized aquifers was relatively stable from 2004 to 2009. Although sediment extractions indicate a relatively low amount of As in the oxidized sediments, below 2.5 mg kg{sup -1}, batch isotherm experiments show that the sediments have a high capacity to adsorb As. Simulations using a surface complexation model that considers adsorption to amorphous Fe(III) oxide minerals only, under-predict the experimental isotherms. This suggests that a large proportion of the adsorption sites in the oxidized sediments may be associated with crystalline Fe(III) oxides, Mn(IV) and Al(III) oxides, and clay minerals. Replicate breakthrough column experiments conducted with lactose added to the influent solution demonstrate that the high adsorption capacity of the oxidized sediments may be reduced if water drawn down into the oxidized aquifers contains high levels of

Microbial processes relevant for the long-term performance of radioactive waste repositories in clays

International Nuclear Information System (INIS)

Meleshyn, Artur

2012-01-01

metals. The time frame of their potential activity must be considered concomitantly, as in a space of several years a population of sulphate-reducing microbes confined in a relatively small bio-film encountering sub-micrometre concentrations of dissolved metal in a deep subsurface environment is able to immobilize the metal in precipitates in amounts which would correspond to its economic deposit if extrapolated to geologic scales. Structural Fe(III) of clay mineral layers represents the primary electron-accepting reactant in redox reactions driven by Fe(III)-reducing and methane-producing microbes as well as by sulphate-reducing microbes in the case of limited supply of sulphate. However, the product of their metabolism, hydrogen sulphide, reacts with structural Fe(III) in an abiotic redox reaction, which is facilitated by further, organic products of microbial metabolism. Accordingly, deterioration of clay properties accompanying destabilisation and transformation of clay structure as a result of microbial actions aimed at reducing Fe(III) to Fe(II) directly in the mineral structure or at dissolving Fe(III) and making it available for intracellular redox reactions can be considered as the primary microbial impact on clay. Clay half-lives in subsurface settings can vary between just under one hundred thousand years up to a few million years in the presence of millimolar concentrations of hydrogen sulphide. These timescales are comparable with the time frame of one million years relevant for safety analyses, for which an assessment of the safety of a potential DGR for HLW/SF after its closure should be carried out in accordance with regulatory requirements in many countries. Owing to the ability of reducing structural Fe(III) of clay directly or through production of hydrogen sulphide, activity of sulphate-reducing microbes can negatively influence eight safety-relevant properties of clay. This aspect was strongly underrepresented in previous experimental investigations

Assessing the mechanisms controlling the mobilization of arsenic in the arsenic contaminated shallow alluvial aquifer in the blackfoot disease endemic area

International Nuclear Information System (INIS)

Liao, Vivian Hsiu-Chuan; Chu, Yu-Ju; Su, Yu-Chen; Lin, Po-Cheng; Hwang, Yaw-Huei; Liu, Chen-Wuing; Liao, Chung-Min; Chang, Fi-John; Yu, Chan-Wei

2011-01-01

Highlights: ► Sedimentary microcosm showed simultaneous microbial reduction of Fe(III) and As(V). ► Addition of acetate caused a further increase in aqueous Fe(II) but not arsenic. ► An As(V)-reducing bacterium (ARS-3) native to aquifer sediments was isolated. ► ARS-3 showed microbial reduction of As(V) to As(III) in pore water in this aquifer. - Abstract: High levels of arsenic in groundwater and drinking water represent a major health problem worldwide. Drinking arsenic-contaminated groundwater is a likely cause of blackfoot disease (BFD) in Taiwan, but mechanisms controlling the mobilization of arsenic present at elevated concentrations within aquifers remain understudied. Microcosm experiments using sediments from arsenic contaminated shallow alluvial aquifers in the blackfoot disease endemic area showed simultaneous microbial reduction of Fe(III) and As(V). Significant soluble Fe(II) (0.23 ± 0.03 mM) in pore waters and mobilization of As(III) (206.7 ± 21.2 nM) occurred during the first week. Aqueous Fe(II) and As(III) respectively reached concentrations of 0.27 ± 0.01 mM and 571.4 ± 63.3 nM after 8 weeks. We also showed that the addition of acetate caused a further increase in aqueous Fe(II) but the dissolved arsenic did not increase. We further isolated an As(V)-reducing bacterium native to aquifer sediments which showed that the direct enzymatic reduction of As(V) to the potentially more-soluble As(III) in pore water is possible in this aquifer. Our results provide evidence that microorganisms can mediate the release of sedimentary arsenic to groundwater in this region and the capacity for arsenic release was not limited by the availability of electron donors in the sediments.

Assessing the mechanisms controlling the mobilization of arsenic in the arsenic contaminated shallow alluvial aquifer in the blackfoot disease endemic area

Energy Technology Data Exchange (ETDEWEB)

Liao, Vivian Hsiu-Chuan, E-mail: vivianliao@ntu.edu.tw [Department of Bioenvironmental Systems Engineering, National Taiwan University, 1 Roosevelt Road, Sec. 4, Taipei 106, Taiwan (China); Chu, Yu-Ju; Su, Yu-Chen; Lin, Po-Cheng [Department of Bioenvironmental Systems Engineering, National Taiwan University, 1 Roosevelt Road, Sec. 4, Taipei 106, Taiwan (China); Hwang, Yaw-Huei [Institute of Occupational Medicine and Industrial Hygiene, College of Public Health, National Taiwan University, 17 Xu-Zhou Road, Taipei 100, Taiwan (China); Liu, Chen-Wuing; Liao, Chung-Min; Chang, Fi-John; Yu, Chan-Wei [Department of Bioenvironmental Systems Engineering, National Taiwan University, 1 Roosevelt Road, Sec. 4, Taipei 106, Taiwan (China)

2011-12-15

Highlights: Black-Right-Pointing-Pointer Sedimentary microcosm showed simultaneous microbial reduction of Fe(III) and As(V). Black-Right-Pointing-Pointer Addition of acetate caused a further increase in aqueous Fe(II) but not arsenic. Black-Right-Pointing-Pointer An As(V)-reducing bacterium (ARS-3) native to aquifer sediments was isolated. Black-Right-Pointing-Pointer ARS-3 showed microbial reduction of As(V) to As(III) in pore water in this aquifer. - Abstract: High levels of arsenic in groundwater and drinking water represent a major health problem worldwide. Drinking arsenic-contaminated groundwater is a likely cause of blackfoot disease (BFD) in Taiwan, but mechanisms controlling the mobilization of arsenic present at elevated concentrations within aquifers remain understudied. Microcosm experiments using sediments from arsenic contaminated shallow alluvial aquifers in the blackfoot disease endemic area showed simultaneous microbial reduction of Fe(III) and As(V). Significant soluble Fe(II) (0.23 {+-} 0.03 mM) in pore waters and mobilization of As(III) (206.7 {+-} 21.2 nM) occurred during the first week. Aqueous Fe(II) and As(III) respectively reached concentrations of 0.27 {+-} 0.01 mM and 571.4 {+-} 63.3 nM after 8 weeks. We also showed that the addition of acetate caused a further increase in aqueous Fe(II) but the dissolved arsenic did not increase. We further isolated an As(V)-reducing bacterium native to aquifer sediments which showed that the direct enzymatic reduction of As(V) to the potentially more-soluble As(III) in pore water is possible in this aquifer. Our results provide evidence that microorganisms can mediate the release of sedimentary arsenic to groundwater in this region and the capacity for arsenic release was not limited by the availability of electron donors in the sediments.

Genetic characterization and role in virulence of the ribonucleotide reductases of Streptococcus sanguinis.

Science.gov (United States)

Rhodes, DeLacy V; Crump, Katie E; Makhlynets, Olga; Snyder, Melanie; Ge, Xiuchun; Xu, Ping; Stubbe, JoAnne; Kitten, Todd

2014-02-28

Streptococcus sanguinis is a cause of infective endocarditis and has been shown to require a manganese transporter called SsaB for virulence and O2 tolerance. Like certain other pathogens, S. sanguinis possesses aerobic class Ib (NrdEF) and anaerobic class III (NrdDG) ribonucleotide reductases (RNRs) that perform the essential function of reducing ribonucleotides to deoxyribonucleotides. The accompanying paper (Makhlynets, O., Boal, A. K., Rhodes, D. V., Kitten, T., Rosenzweig, A. C., and Stubbe, J. (2014) J. Biol. Chem. 289, 6259-6272) indicates that in the presence of O2, the S. sanguinis class Ib RNR self-assembles an essential diferric-tyrosyl radical (Fe(III)2-Y(•)) in vitro, whereas assembly of a dimanganese-tyrosyl radical (Mn(III)2-Y(•)) cofactor requires NrdI, and Mn(III)2-Y(•) is more active than Fe(III)2-Y(•) with the endogenous reducing system of NrdH and thioredoxin reductase (TrxR1). In this study, we have shown that deletion of either nrdHEKF or nrdI completely abolishes virulence in an animal model of endocarditis, whereas nrdD mutation has no effect. The nrdHEKF, nrdI, and trxR1 mutants fail to grow aerobically, whereas anaerobic growth requires nrdD. The nrdJ gene encoding an O2-independent adenosylcobalamin-cofactored RNR was introduced into the nrdHEKF, nrdI, and trxR1 mutants. Growth of the nrdHEKF and nrdI mutants in the presence of O2 was partially restored. The combined results suggest that Mn(III)2-Y(•)-cofactored NrdF is required for growth under aerobic conditions and in animals. This could explain in part why manganese is necessary for virulence and O2 tolerance in many bacterial pathogens possessing a class Ib RNR and suggests NrdF and NrdI may serve as promising new antimicrobial targets.

Genetic Characterization and Role in Virulence of the Ribonucleotide Reductases of Streptococcus sanguinis * ♦

Science.gov (United States)

Rhodes, DeLacy V.; Crump, Katie E.; Makhlynets, Olga; Snyder, Melanie; Ge, Xiuchun; Xu, Ping; Stubbe, JoAnne; Kitten, Todd

2014-01-01

Streptococcus sanguinis is a cause of infective endocarditis and has been shown to require a manganese transporter called SsaB for virulence and O2 tolerance. Like certain other pathogens, S. sanguinis possesses aerobic class Ib (NrdEF) and anaerobic class III (NrdDG) ribonucleotide reductases (RNRs) that perform the essential function of reducing ribonucleotides to deoxyribonucleotides. The accompanying paper (Makhlynets, O., Boal, A. K., Rhodes, D. V., Kitten, T., Rosenzweig, A. C., and Stubbe, J. (2014) J. Biol. Chem. 289, 6259–6272) indicates that in the presence of O2, the S. sanguinis class Ib RNR self-assembles an essential diferric-tyrosyl radical (FeIII2-Y•) in vitro, whereas assembly of a dimanganese-tyrosyl radical (MnIII2-Y•) cofactor requires NrdI, and MnIII2-Y• is more active than FeIII2-Y• with the endogenous reducing system of NrdH and thioredoxin reductase (TrxR1). In this study, we have shown that deletion of either nrdHEKF or nrdI completely abolishes virulence in an animal model of endocarditis, whereas nrdD mutation has no effect. The nrdHEKF, nrdI, and trxR1 mutants fail to grow aerobically, whereas anaerobic growth requires nrdD. The nrdJ gene encoding an O2-independent adenosylcobalamin-cofactored RNR was introduced into the nrdHEKF, nrdI, and trxR1 mutants. Growth of the nrdHEKF and nrdI mutants in the presence of O2 was partially restored. The combined results suggest that MnIII2-Y•-cofactored NrdF is required for growth under aerobic conditions and in animals. This could explain in part why manganese is necessary for virulence and O2 tolerance in many bacterial pathogens possessing a class Ib RNR and suggests NrdF and NrdI may serve as promising new antimicrobial targets. PMID:24381171

pH controls over methanogenesis and iron reduction along soil depth profile in Arctic tundra

Science.gov (United States)

Zheng, J.; Gu, B.; Wullschleger, S. D.; Graham, D. E.

2017-12-01

Increasing soil temperature in the Arctic is expected to accelerate rates of soil organic matter decomposition. However, the magnitude of this impact is uncertain due to the many physical, chemical, and biological processes that control the decomposition pathways. Varying soil redox conditions present a key control over pathways of organic matter decomposition by diverting the flow of reductants among different electron accepting processes and further driving acid-base reactions that alter soil pH. In this study we investigated the pH controls over anaerobic carbon mineralization, methanogenesis, Fe(III) reduction and the interplay between these processes across a range of pH and redox conditions. pH manipulation experiments were conducted by incubating soils representing organic, mineral, cryoturbated transitional layers and permafrost. In the experiments we sought to understand (1) if methanogenesis or Fe(III) reduction had similar pH optima; (2) if this pH response also occurs at `upstream' fermentation process; and (3) if pH alters organo-mineral association or organic matter sorption and desorption and its availability for microbial degradation. Our preliminary results suggest that the common bell-shaped pH response curve provides a good fit for both Fe(III) reduction and methanogenesis, with optimum pH at 6.0-7.0. Exceptions to this were found in transitional layer where methanogenesis rates positively correlated with increasing pH, with maximum rates measured at pH 8.5. It is likely that the transitional layer harbors distinct groups of methanogens that prefer a high pH. Variations in the optimum pH of Fe(III) reduction and methanogenesis may play a significant role in regulating organic matter decomposition pathways and thus greenhouse gas production in thawing soils. These results support biogeochemical modeling efforts to accurately simulate organic matter decomposition under changing redox and pH conditions.

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

Science.gov (United States)

Chebeir, Michelle; Liu, Haizhou

2018-05-17

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

Diel changes in metal concentrations in a geogenically acidic river: Rio Agrio, Argentina

Science.gov (United States)

Parker, Stephen R.; Gammons, Christopher H.; Pedrozo, Fernando L.; Wood, Scott A.

2008-12-01

Rio Agrio in Patagonia, Argentina is a geogenically acidic stream that derives its low-pH waters from condensation of acidic gases near its headwaters on the flanks of the active Copahue Volcano. This study reports the results of three diel (24-h) water samplings in three different pH regimes (3.2, 4.4 and 6.3) along the river. Changes in the concentration and speciation of Fe dominated the diel chemical changes at all three sites, although the timing and intensity of these cycles were different in each reach. At the two acidic sampling sites, total dissolved Fe and dissolved Fe(III) concentrations decreased during the day and increased at night, whereas dissolved Fe(II) showed the reverse pattern. These cycles are explained by Fe(III) photoreduction, as well as enhanced rates of precipitation of hydrous ferric oxide (HFO) during the warm afternoon hours. A strong correlation was observed between Fe(III) and As at the furthest upstream (pH 3.2) site, most likely due to co-precipitation of As with HFO. At the downstream (pH 6.3) location, Fe(II) concentrations increased at night, as did concentrations of rare earth elements and dissolved Al. Photoreduction does not appear to be an important process at pH 6.3, although it may be indirectly responsible for the observed diel cycle of Fe(II) due to advection of photochemically produced Fe(II) from acidic upstream waters. The results of this study of a naturally-acidic river are very similar to diel trends recently obtained from mining-impacted streams receiving acid rock drainage. The results are also used to explore the link between geochemistry and microbiology in acidic eco-systems. For example, Fe(III) photoreduction produces chemical potential energy (in the form of metastable Fe 2+) that helps support the bacterial community in this unique extreme environment.

Column solid phase extraction and flame atomic absorption spectrometric determination of manganese(II) and iron(III) ions in water, food and biological samples using 3-(1-methyl-1H-pyrrol-2-yl)-1H-pyrazole-5-carboxylic acid on synthesized graphene oxide

International Nuclear Information System (INIS)

Pourjavid, Mohammad Reza; Sehat, Ali Akbari; Arabieh, Masoud; Yousefi, Seyed Reza; Hosseini, Majid Haji; Rezaee, Mohammad

2014-01-01

A modified, selective, highly sensitive and accurate procedure for the determination of trace amounts of manganese and iron ions is established in the presented work. 3-(1-Methyl-1H-pyrrol-2-yl)-1H-pyrazole-5-carboxylic acid (MPPC) and graphene oxide (GO) were used in a glass column as chelating reagent and as adsorbent respectively prior to their determination by flame atomic absorption spectrometry. The adsorption mechanism of titled metals complexes on GO was investigated by using computational chemistry approach based on PM6 semi-empirical potential energy surface (PES). The effect of some parameters including pH, flow rate and volume of sample and type, volume and concentration of eluent, as well as the adsorption capacity of matrix ions on the recovery of Mn(II) and Fe(III) was investigated. The limit of detection was 145 and 162 ng L −1 for Mn(II) and Fe(III), respectively. Calibration was linear over the range of 0.31–355 μg L −1 for Mn(II) and 0.34–380 μg L −1 for Fe(III) ions. The method was successfully applied for the determination of understudied ions in water, food and biological samples. - Highlights: • We use synthesized graphene oxide as adsorbent for SPE of Mn(II) and Fe(III) ions. • Adsorption mechanism was investigated by PM6 semi-empirical potential energy surface. • Detection limits were 145 and 162 ng L −1 for Mn and Fe, respectively. • The preconcentration factor was 325 and sample flow rate is 8 mL min −1 . • It was successfully applied to the determination of Mn and Fe ions in real samples

Mechanism of Selenite Removal by a Mixed Adsorbent Based on Fe–Mn Hydrous Oxides Studied Using X-ray Absorption Spectroscopy

KAUST Repository

Chubar, Natalia

2014-11-18

© 2014 American Chemical Society. Selenium cycling in the environment is greatly controlled by various minerals, including Mn and Fe hydrous oxides. At the same time, such hydrous oxides are the main inorganic ion exchangers suitable (on the basis of their chemical nature) to sorb (toxic) anions, separating them from water solutions. The mechanism of selenite adsorption by the new mixed adsorbent composed of a few (amorphous and crystalline) phases [maghemite, MnCO3, and X-ray amorphous Fe(III) and Mn(III) hydrous oxides] was studied by extended X-ray absorption fine structure (EXAFS) spectroscopy [supported by Fourier transform infrared (FTIR) and X-ray diffraction (XRD) data]. The complexity of the porous adsorbent, especially the presence of the amorphous phases of Fe(III) and Mn(III) hydrous oxides, is the main reason for its high selenite removal performance demonstrated by batch and column adsorption studies shown in the previous work. Selenite was bound to the material via inner-sphere complexation (via oxygen) to the adsorption sites of the amorphous Fe(III) and Mn(III) oxides. This anion was attracted via bidentate binuclear corner-sharing coordination between SeO3 2- trigonal pyramids and both FeO6 and MnO6 octahedra; however, the adsorption sites of Fe(III) hydrous oxides played a leading role in selenite removal. The contribution of the adsorption sites of Mn(III) oxide increased as the pH decreased from 8 to 6. Because most minerals have a complex structure (they are seldom based on individual substances) of various crystallinity, this work is equally relevant to environmental science and environmental technology because it shows how various solid phases control cycling of chemical elements in the environment.

Mechanism of Selenite Removal by a Mixed Adsorbent Based on Fe–Mn Hydrous Oxides Studied Using X-ray Absorption Spectroscopy

KAUST Repository

Chubar, Natalia; Gerda, Vasyl; Szlachta, Małgorzata

2014-01-01

© 2014 American Chemical Society. Selenium cycling in the environment is greatly controlled by various minerals, including Mn and Fe hydrous oxides. At the same time, such hydrous oxides are the main inorganic ion exchangers suitable (on the basis of their chemical nature) to sorb (toxic) anions, separating them from water solutions. The mechanism of selenite adsorption by the new mixed adsorbent composed of a few (amorphous and crystalline) phases [maghemite, MnCO3, and X-ray amorphous Fe(III) and Mn(III) hydrous oxides] was studied by extended X-ray absorption fine structure (EXAFS) spectroscopy [supported by Fourier transform infrared (FTIR) and X-ray diffraction (XRD) data]. The complexity of the porous adsorbent, especially the presence of the amorphous phases of Fe(III) and Mn(III) hydrous oxides, is the main reason for its high selenite removal performance demonstrated by batch and column adsorption studies shown in the previous work. Selenite was bound to the material via inner-sphere complexation (via oxygen) to the adsorption sites of the amorphous Fe(III) and Mn(III) oxides. This anion was attracted via bidentate binuclear corner-sharing coordination between SeO3 2- trigonal pyramids and both FeO6 and MnO6 octahedra; however, the adsorption sites of Fe(III) hydrous oxides played a leading role in selenite removal. The contribution of the adsorption sites of Mn(III) oxide increased as the pH decreased from 8 to 6. Because most minerals have a complex structure (they are seldom based on individual substances) of various crystallinity, this work is equally relevant to environmental science and environmental technology because it shows how various solid phases control cycling of chemical elements in the environment.

Column solid phase extraction and flame atomic absorption spectrometric determination of manganese(II) and iron(III) ions in water, food and biological samples using 3-(1-methyl-1H-pyrrol-2-yl)-1H-pyrazole-5-carboxylic acid on synthesized graphene oxide

Energy Technology Data Exchange (ETDEWEB)

Pourjavid, Mohammad Reza, E-mail: pourjavid@gmail.com [NFCRS, Nuclear Science and Technology Research Institute, P.O. Box 11365-8486, Tehran (Iran, Islamic Republic of); Sehat, Ali Akbari [Department of Analytical Chemistry, Faculty of Chemistry, University College of Science, University of Tehran, P.O. Box 14155-6455, Tehran (Iran, Islamic Republic of); Arabieh, Masoud; Yousefi, Seyed Reza; Hosseini, Majid Haji; Rezaee, Mohammad [NFCRS, Nuclear Science and Technology Research Institute, P.O. Box 11365-8486, Tehran (Iran, Islamic Republic of)

2014-02-01

A modified, selective, highly sensitive and accurate procedure for the determination of trace amounts of manganese and iron ions is established in the presented work. 3-(1-Methyl-1H-pyrrol-2-yl)-1H-pyrazole-5-carboxylic acid (MPPC) and graphene oxide (GO) were used in a glass column as chelating reagent and as adsorbent respectively prior to their determination by flame atomic absorption spectrometry. The adsorption mechanism of titled metals complexes on GO was investigated by using computational chemistry approach based on PM6 semi-empirical potential energy surface (PES). The effect of some parameters including pH, flow rate and volume of sample and type, volume and concentration of eluent, as well as the adsorption capacity of matrix ions on the recovery of Mn(II) and Fe(III) was investigated. The limit of detection was 145 and 162 ng L{sup −1} for Mn(II) and Fe(III), respectively. Calibration was linear over the range of 0.31–355 μg L{sup −1} for Mn(II) and 0.34–380 μg L{sup −1} for Fe(III) ions. The method was successfully applied for the determination of understudied ions in water, food and biological samples. - Highlights: • We use synthesized graphene oxide as adsorbent for SPE of Mn(II) and Fe(III) ions. • Adsorption mechanism was investigated by PM6 semi-empirical potential energy surface. • Detection limits were 145 and 162 ng L{sup −1} for Mn and Fe, respectively. • The preconcentration factor was 325 and sample flow rate is 8 mL min{sup −1}. • It was successfully applied to the determination of Mn and Fe ions in real samples.

Preconcentration, determination and speciation of iron by solid-phase extraction using dimethyl (E)-2-[(Z)-1-acetyl)-2-hydroxy-1-propenyl]-2-butenedioate

Energy Technology Data Exchange (ETDEWEB)

Khayatian, Gholamreza; Hassanpoor, Shahed; Nasiri, Farough; Zolali, Amin [Chemistry Department, Faculty of Science, University of Kurdistan, Sanandaj (Iran, Islamic Republic of)

2012-07-01

A new sensitive and selective procedure for speciation of trace dissolved Fe(III) and Fe(II), using modified octadecyl silica membrane disks and determination by flame atomic absorption spectrometry was developed. A ML{sub 3} complex is formed between the ligand and Fe(III) responsible for extraction of metal ion on the disk. Various factors influencing the separation of iron were investigated and the optimized operation conditions were established. Under optimum conditions, an enrichment factor of 166 was obtained for Fe{sup 3+}ions. The calibration graph using the preconcentration system for Fe{sup 3+} was linear between 40.0 and 1000.0 {sup m}u{sup g} L{sup -1}. (author)

Electrochemical and spectroscopie behaviour of iron in the molten NaCl-K2SO4 mixture

DEFF Research Database (Denmark)

Bjerrum, Niels; Petruchina, Irina; Volkov, S.V.

1996-01-01

The chemical and electrochemical dissolving of Armco iron in the NaCl-K2SO4 melt has been studied. In the case of the chemical dissolution, a sample becomes coated, as time goes on, with a dense film consisting of FeO, FeS and Fe3O4; precipitation in the melt is observed, the precipitate consisting...... not detect Fe(III) by electronic absorption spectra, possibly due to the superimposition of the charge transfer bands edge on low-intensity Fe(III) bands of the 5d electronic configuration. The solubility of Fe2O3 in the NaCl-K2SO4 melt is low and was determined to 2 x 10(-3) wt%....

Synthesis and characterization of some metal complexes of a Schiff base derived from ninhydrin and α,L-alanine

Directory of Open Access Journals (Sweden)

Mehabaw Getahun Derebe

2002-06-01

Full Text Available Complexes of Mn(II, Fe(III, Co(II, Ni(II and Zn(II with an intermediate Schiff base derived from ninhydrin and α,L-alanine (indane-1,3-dione-2-imine-N-2-propionate, IDIP were successfully synthesized. All complexes were distinctly colored and were characterized by elemental analysis, molar conductance, magnetic susceptibility, infrared and electronic spectral studies. The ligand (Schiff base was shown to behave as a monobasic tridentate ONO donor. The Mn(II and Fe(III complexes contain only one ligand molecule plus water and chloride(s per metal ion, while all the others contain two ligand molecules per metal ion. An octahedral geometry is proposed for the metal complexes.

Preparation of chitosan-stabilized Fe{sup 0} nanoparticles for removal of hexavalent chromium in water

Energy Technology Data Exchange (ETDEWEB)

Geng, Bing [Key Laboratory of Pollution Processes and Environmental Criteria, Ministry of Education, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Jin, Zhaohui, E-mail: jinzh@nankai.edu.cn [Key Laboratory of Pollution Processes and Environmental Criteria, Ministry of Education, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Li, Tielong; Qi, Xinhua [Key Laboratory of Pollution Processes and Environmental Criteria, Ministry of Education, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China)

2009-09-01

Chitosan-stabilized Fe{sup 0} nanoparticles (CTO-Fe{sup 0}) and Fe{sup 0} nanoparticles synthesized in ethanol-water mixed system (EW-Fe{sup 0}) were tested for reduction of Cr(VI) in water. Fourier transform infrared (FTIR) study suggested that nitrogen and oxygen atoms are the binding sites for chitosan on iron which was accountable for the stability of Fe{sup 0} nanoparticles. While the EW-Fe{sup 0} ignites spontaneously when exposed to air, the CTO-Fe{sup 0} was still in zero valence state after exposure to air over 2-month period as shown by X-ray powder diffraction patterns. Batch experiments demonstrated that the maximum Cr(VI) reduction rates for CTO-Fe{sup 0} was about 3 times higher than EW-Fe{sup 0}. Characterizations with high-resolution X-ray photoelectron spectroscopy (HR-XPS) revealed that Cr(VI) was reduced to Cr(III) and Fe(III) was the only component present on the Fe{sup 0} nanoparticles surface. Additionally, chitosan can inhibited the formation of Fe(III)-Cr(III) precipitation due to its high ability to chelate Fe(III) which resulted in k{sub obs} for CTO-Fe{sup 0} was about 1-3 times higher than EW-Fe{sup 0}. Due to the fast reaction kinetics and good stability against oxidation in air, the chitosan-stabilized Fe{sup 0} nanoparticles have the potential to become an effective agent for in situ subsurface environment remediation.

Microbially-accelerated consolidation of oil sands tailings. Pathway II: solid phase biogeochemistry

Directory of Open Access Journals (Sweden)

Tariq eSiddique

2014-03-01

Full Text Available Consolidation of clay particles in aqueous tailings suspensions is a major obstacle to effective management of oil sands tailings ponds in northern Alberta, Canada. We have observed that microorganisms indigenous to the tailings ponds accelerate consolidation of mature fine tailings (MFT during active metabolism by using two biogeochemical pathways. In Pathway I, microbes alter porewater chemistry to indirectly increase consolidation of MFT. Here, we describe Pathway II comprising significant, direct and complementary biogeochemical reactions with MFT mineral surfaces. An anaerobic microbial community comprising Bacteria (predominantly Clostridiales, Synergistaceae and Desulfobulbaceae and Archaea (Methanolinea/Methanoregula and Methanosaeta transformed FeIII minerals in MFT to amorphous FeII minerals during methanogenic metabolism of an added organic substrate. Synchrotron analyses suggested that ferrihydrite (5Fe2O3. 9H2O and goethite (α-FeOOH were the dominant FeIII minerals in MFT. The formation of amorphous iron sulfide (FeS and possibly green rust entrapped and masked electronegative clay surfaces in amended MFT. Both Pathways I and II reduced the surface charge potential (repulsive forces of the clay particles in MFT, which aided aggregation of clays and formation of networks of pores, as visualized using cryo-scanning electron microscopy. These reactions facilitated the egress of porewater from MFT and increased consolidation of tailings solids. These results have large-scale implications for management and reclamation of oil sands tailings ponds, a burgeoning environmental issue for the public and government regulators.

Microbially-accelerated consolidation of oil sands tailings. Pathway II: solid phase biogeochemistry.

Science.gov (United States)

Siddique, Tariq; Kuznetsov, Petr; Kuznetsova, Alsu; Li, Carmen; Young, Rozlyn; Arocena, Joselito M; Foght, Julia M

2014-01-01

Consolidation of clay particles in aqueous tailings suspensions is a major obstacle to effective management of oil sands tailings ponds in northern Alberta, Canada. We have observed that microorganisms indigenous to the tailings ponds accelerate consolidation of mature fine tailings (MFT) during active metabolism by using two biogeochemical pathways. In Pathway I, microbes alter porewater chemistry to indirectly increase consolidation of MFT. Here, we describe Pathway II comprising significant, direct and complementary biogeochemical reactions with MFT mineral surfaces. An anaerobic microbial community comprising Bacteria (predominantly Clostridiales, Synergistaceae, and Desulfobulbaceae) and Archaea (Methanolinea/Methanoregula and Methanosaeta) transformed Fe(III) minerals in MFT to amorphous Fe(II) minerals during methanogenic metabolism of an added organic substrate. Synchrotron analyses suggested that ferrihydrite (5Fe2O3. 9H2O) and goethite (α-FeOOH) were the dominant Fe(III) minerals in MFT. The formation of amorphous iron sulfide (FeS) and possibly green rust entrapped and masked electronegative clay surfaces in amended MFT. Both Pathways I and II reduced the surface charge potential (repulsive forces) of the clay particles in MFT, which aided aggregation of clays and formation of networks of pores, as visualized using cryo-scanning electron microscopy (SEM). These reactions facilitated the egress of porewater from MFT and increased consolidation of tailings solids. These results have large-scale implications for management and reclamation of oil sands tailings ponds, a burgeoning environmental issue for the public and government regulators.

Separation of some ionic species from solutions by membrane and centrifugation methods

International Nuclear Information System (INIS)

Toropov, I.G.; Toropova, V.V.; Davydov, Yu.P.; Zemskova, L.M.

2003-01-01

Present work is dedicated to investigation of influence on iron ion hydrolytic behavior of some anions. On the basis of this research one can propose new, quite effective ways for liquid water solution purification. This paper has shown how the knowledge of iron ions behavior in solution can be applied to solve practical tasks. The conditions of formation of Fe(III) polynuclear forms, which are detained by semipermeable membranes have been considered in this research. The influence of a range of anions, some oxidants and reducing agents, affecting the formation of polynuclear hydroxo-forms of iron in solutions, has been studied during this research. It has been demonstrated that multinuclear forms of Fe(III) can interact with an ion of the medium. In this instance anion behaves as a multinuclear particle. In this work the behaviour of iodine during dialysis of solution was investigated. Additionally, it appeared that in the presence of iron polynuclear forms phosphate ion was detained by cellophane membrane. The data show that phosphate ion interacts strongly with the polynuclear forms of iron in aqueous solution. The formation of rather coarse forms of iron takes place at the phosphate ion presence which can be sedimented by centrifugation, and increasing either phosphate ion concentration or pH of solutions results in increase of percentage of the iron sedimented. According to these data phosphate ion can be separated from water solution by way of centrifugation with polynuclear hydroxo particles of iron. (authors)

Modelling CEC variations versus structural iron reduction levels in dioctahedral smectites. Existing approaches, new data and model refinements.

Science.gov (United States)

Hadi, Jebril; Tournassat, Christophe; Ignatiadis, Ioannis; Greneche, Jean Marc; Charlet, Laurent

2013-10-01

A model was developed to describe how the 2:1 layer excess negative charge induced by the reduction of Fe(III) to Fe(II) by sodium dithionite buffered with citrate-bicarbonate is balanced and applied to nontronites. This model is based on new experimental data and extends structural interpretation introduced by a former model [36-38]. The 2:1 layer negative charge increase due to Fe(III) to Fe(II) reduction is balanced by an excess adsorption of cations in the clay interlayers and a specific sorption of H(+) from solution. Prevalence of one compensating mechanism over the other is related to the growing lattice distortion induced by structural Fe(III) reduction. At low reduction levels, cation adsorption dominates and some of the incorporated protons react with structural OH groups, leading to a dehydroxylation of the structure. Starting from a moderate reduction level, other structural changes occur, leading to a reorganisation of the octahedral and tetrahedral lattice: migration or release of cations, intense dehydroxylation and bonding of protons to undersaturated oxygen atoms. Experimental data highlight some particular properties of ferruginous smectites regarding chemical reduction. Contrary to previous assumptions, the negative layer charge of nontronites does not only increase towards a plateau value upon reduction. A peak is observed in the reduction domain. After this peak, the negative layer charge decreases upon extended reduction (>30%). The decrease is so dramatic that the layer charge of highly reduced nontronites can fall below that of its fully oxidised counterpart. Furthermore, the presence of a large amount of tetrahedral Fe seems to promote intense clay structural changes and Fe reducibility. Our newly acquired data clearly show that models currently available in the literature cannot be applied to the whole reduction range of clay structural Fe. Moreover, changes in the model normalising procedure clearly demonstrate that the investigated low

The biogeochemical behaviour of U(VI) in the simulated near-field of a low-level radioactive waste repository

International Nuclear Information System (INIS)

Fox, James R.; Mortimer, Robert J.G.; Lear, Gavin; Lloyd, Jonathan R.; Beadle, Ian; Morris, Katherine

2006-01-01

Microbial processes have the potential to affect the mobility of radionuclides, including U in radioactive wastes. A range of geochemical, molecular biological and mineralogical techniques were applied to investigate stable element biogeochemistry and U solubility in the simulated 'near-field' (or local environment) of a low-level radioactive waste (LLW) repository. The experiments used a microbial inoculum from the trench disposal area of the UK LLW repository at Drigg, Cumbria, England, in combination with a synthetic trench leachate representing the local environment at the Drigg site. In batch culture experiments in the absence of U, a classic redox progression of terminal electron accepting processes (TEAPs) occurred in the order NO 3 - , Fe(III) and SO 4 2- reduction. When 126μM U was added to the system as U(VI) aq , up to 80% was reduced to U(IV) by the indigenous microbial consortium. The U(IV) was retained in solution in these experiments, most likely by complexation with citrate present in the experimental medium. No U(VI) aq was reduced in sterile cultures, confirming that U(VI) aq reduction was microbially mediated. Interestingly, when U(VI) aq was present, the progression of TEAPs was altered. The rate of Fe(III) reduction slowed compared to experiments without U(VI) aq , and SO 4 reduction occurred at the same time as U(VI) reduction. Finally, an experiment where SO 4 2- -reducing microorgansisms were inhibited by Na molybdate showed no ingrowth of sulfide minerals, but U(VI) reduction continued in this experiment. This suggested that sulfide minerals did not play a significant role in abiotically reducing U(VI) in these systems, and that metal-reducing microorganisms were dominant in mediating U(VI) reduction. Bacteria closely related to microorganisms found in engineered and U-contaminated environments dominated in the experiments. Denaturing gradient gel electrophoresis (DGGE) on 16SrRNA products amplified from broad specificity primers showed

Treatment of shower and laundry liquid radwaste by foam flotation

Energy Technology Data Exchange (ETDEWEB)

Jeong, In Ha; Lee, Jeong Won; Park, Hee Seong; Lee, Chul Yong; Kang, Kwon Ho [Korea Atomic Energy Research Institute, Taejon (Korea)

1998-06-01

Shower and laundry water containing surfactant were treated by precipitate flotation and adsorbing colloidal flotation. In precipitate flotation, 99.8% of removal efficiency was attained at cobalt ion concentration 50ppm, pH 9.5, gas flow rate 70ml/min and flotation time 30min. In adsorbing colloidal flotation using Fe(III) as a collector, 99.8% removal efficiency was attained at initial cobalt ion concentration 50ppm, pH 8.5, gas flow rate 70ml/min and flotation time 15 min. By adding Al(III) 20ppm after coprecipitating cobalt ion with Fe(III), operation pH range was more enlarged than using Fe(III) or Al(III) each. NaNO{sub 3}, Na{sub 2}SO{sub 4}, NaCl, CaCl{sub 2} were added as foreign ions. Removal efficiency by precipitate flotation and adsorbing colloidal flotation for the cobalt solution containing 0.1M Na{sub 2}SO{sub 4} were about 90% and 72% due to the decreased Zeta potential and the interruption of precipitation. Using Al(III) as a activator at solution containing 0.1M Na{sub 2}SO{sub 4}, the removal efficiency was increased up to 99%. (author). 24 refs., 25 figs., 1 tab.

Synthesis, characterization and thermal study of some transition metal complexes of an asymmetrical tetradentate Schiff base ligand

Directory of Open Access Journals (Sweden)

ACHUT S. MUNDE

2010-03-01

Full Text Available Complexes of Cu(II, Ni(II, Co(II, Mn(II and Fe(III with an asymmetric tetradentate Schiff base ligand derived from dehydroacetic acid, 4-methyl-o-phenylenediamine and salicylic aldehyde were synthesized and characterized by elemental analysis, conductometry, magnetic susceptibility, UV–Vis, IR, 1H-NMR spectroscopy, X-ray diffraction analysis of powdered samples and thermal analysis, and screened for antimicrobial activity. The IR spectral data suggested that the ligand behaves as a dibasic tetadentate ligand towards the central metal ion with an ONNO donor atoms sequence. From the microanalytical data, the stoichiometry of the complexes 1:1 (metal:ligand was found. The physico-chemical data suggested square planar geometry for the Cu(II and Ni(II complexes and octahedral geometry for the Co(II, Mn(II and Fe(III complexes. The thermal behaviour (TGA/DTA of the complexes was studied and kinetic parameters were determined by Horowitz–Metzger and Coats–Redfern methods. The powder X-ray diffraction data suggested a monoclinic crystal system for the Co(II, Mn(II and Fe(III complexes. The ligand and their metal complexes were screened for antibacterial activity against Staphylococcus aureus and Escherichia coli and fungicidal activity against Aspergillus niger and Trichoderma viride.

The metal binding potential of a dairy isolate

Directory of Open Access Journals (Sweden)

K. Ramyakrishna

2017-12-01

Full Text Available Excess iron in water resources can lead to health hazards and problems. The ability of lactic acid bacteria to bind iron has not yet been widely studied. In the present study, sorption of iron ions from aqueous solutions onto lactic acid bacterium was determined. Elemental analyses were carried out by inductively coupled plasma optical emission spectrometry. The kinetics of Fe(III biosorption was investigated at different initial concentrations of metal ion. The highest uptake capacity was found to be 16 mg of Fe(III per gram of adsorbent with a contact time of 24 hr and at initial metal ion concentration of 34 mg/L. The uptake capacity of Fe(III ion varied from 83.2 to 46.7% across the range of initial metal ion concentrations. The equilibrium data were evaluated by Langmuir and Freundlich isotherms, and were found to fit better with the latter (R2 = 0.9999. The surface morphology of the biomass and percentage of metal was characterized by using a scanning electron microscope equipped with energy dispersive X-ray spectroscopy. The functional groups on the cell wall surface of biomass involved in biosorption of heavy metals were studied by Fourier transform infrared spectroscopy spectrum.

Impurity effect of iron(III) on the growth of potassium sulfate crystal in aqueous solution

Science.gov (United States)

Kubota, Noriaki; Katagiri, Ken-ichi; Yokota, Masaaki; Sato, Akira; Yashiro, Hitoshi; Itai, Kazuyoshi

1999-01-01

Growth rates of the {1 1 0} faces of a potassium sulfate crystal were measured in a flow cell in the presence of traces of impurity Fe(III) (up to 2 ppm) over the range of pH=2.5-6.0. The growth rate was significantly suppressed by the impurity. The effect became stronger as the impurity concentration was increased and at pH5 it finally disappeared completely. The concentration and supersaturation effects on the impurity action were reasonably explained with a model proposed by Kubota and Mullin [J. Crystal Growth, 152 (1995) 203]. The surface coverage of the active sites by Fe(III) is estimated to increase linearly on increasing its concentration in solution in the range examined by growth experiments. The impurity effectiveness factor is confirmed to increase inversely proportional to the supersaturation as predicted by the model. Apart from the discussion based on the model, the pH effect on the impurity action is qualitatively explained by assuming that the first hydrolysis product of aqua Fe(III) complex compound, [Fe(H 2O) 5(OH)] 2+, is both growth suppression and adsorption active, but the second hydrolysis product, [Fe(H 2O) 4(OH) 2] +, is only adsorption active.

Combining Ferric Salt and Cactus Mucilage for Arsenic Removal from Water.

Science.gov (United States)

Fox, Dawn I; Stebbins, Daniela M; Alcantar, Norma A

2016-03-01

New methods to remediate arsenic-contaminated water continue to be studied, particularly to fill the need for accessible methods that can significantly impact developing communities. A combination of cactus mucilage and ferric (Fe(III)) salt was investigated as a flocculation-coagulation system to remove arsenic (As) from water. As(V) solutions, ferric nitrate, and mucilage suspensions were mixed and left to stand for various periods of time. Visual and SEM observations confirmed the flocculation action of the mucilage as visible flocs formed and settled to the bottom of the tubes within 3 min. The colloidal suspensions without mucilage were stable for up to 1 week. Sample aliquots were tested for dissolved and total arsenic by ICP-MS and HGAFS. Mucilage treatment improved As removal (over Fe(III)-only treatment); the system removed 75-96% As in 30 min. At neutral pH, removal was dependent on Fe(III) and mucilage concentration and the age of the Fe(III) solution. The process is fast, achieving maximum removal in 30 min, with the majority of As removed in 10-15 min. Standard jar tests with 1000 μg/L As(III) showed that arsenic removal and settling rates were pH-dependent; As removal was between 52% (high pH) and 66% (low pH).

Reduced Rank Regression

DEFF Research Database (Denmark)

Johansen, Søren

2008-01-01

The reduced rank regression model is a multivariate regression model with a coefficient matrix with reduced rank. The reduced rank regression algorithm is an estimation procedure, which estimates the reduced rank regression model. It is related to canonical correlations and involves calculating...

How different oxidation states of crystalline myoglobin are influenced by X-rays.

Science.gov (United States)

Hersleth, Hans-Petter; Andersson, K Kristoffer

2011-06-01

X-ray induced radiation damage of protein crystals is well known to occur even at cryogenic temperatures. Redox active sites like metal sites seem especially vulnerable for these radiation-induced reductions. It is essential to know correctly the oxidation state of metal sites in protein crystal structures to be able to interpret the structure-function relation. Through previous structural studies, we have tried to characterise and understand the reactions between myoglobin and peroxides. These reaction intermediates are relevant because myoglobin is proposed to take part as scavenger of reactive oxygen species during oxidative stress, and because these intermediates are similar among the haem peroxidases and oxygenases. We have in our previous studies shown that these different myoglobin states are influenced by the X-rays used. In this study, we have in detail investigated the impact that X-rays have on these different oxidation states of myoglobin. An underlying goal has been to find a way to be able to determine mostly unreduced states. We have by using single-crystal light absorption spectroscopy found that the different oxidation states of myoglobin are to a different extent influenced by the X-rays (e.g. ferric Fe(III) myoglobin is faster reduced than ferryl Fe(IV)═O myoglobin). We observe that the higher oxidation states are not reduced to normal ferrous Fe(II) or ferric Fe(III) states, but end up in some intermediate and possibly artificial states. For ferric myoglobin, it seems that annealing of the radiation-induced/reduced state can reversibly more or less give the starting point (ferric myoglobin). Both scavengers and different dose-rates might influence to which extent the different states are affected by the X-rays. Our study shows that it is essential to do a time/dose monitoring of the influence X-rays have on each specific redox-state with spectroscopic techniques like single-crystal light absorption spectroscopy. This will determine to which

Review of pump suction reducer selection: Eccentric or concentric reducers

OpenAIRE

Mahaffey, R M; van Vuuren, S J

2014-01-01

Eccentric reducers are traditionally recommended for the pump suction reducer fitting to allow for transportation of air through the fitting to the pump. The ability of a concentric reducer to provide an improved approach flow to the pump while still allowing air to be transported through the fitting is investigated. Computational fluid dynamics (CFD) were utilised to analyse six concentric and six eccentric reducer geometries at four different inlet velocities to determine the flow velocity ...

2 : 2 Fe(III): ligand and "adamantane core" 4 : 2 Fe(III): ligand (hydr)oxo complexes of an acyclic ditopic ligand

DEFF Research Database (Denmark)

Ghiladi, Morten; Larsen, Frank B.; McKenzie, Christine J.

2005-01-01

A bis-hydroxo-bridged diiron(III) complex and a bis-mu-oxo-bis-mu-hydroxo-bridged tetrairon( III) complex are isolated from the reaction of 2,6-bis((N, N'-bis-(2-picolyl) amino) methyl)-4-tert-butylphenol (Hbpbp) with iron perchlorate in acidic and neutral solutions respectively. The X-ray struct......A bis-hydroxo-bridged diiron(III) complex and a bis-mu-oxo-bis-mu-hydroxo-bridged tetrairon( III) complex are isolated from the reaction of 2,6-bis((N, N'-bis-(2-picolyl) amino) methyl)-4-tert-butylphenol (Hbpbp) with iron perchlorate in acidic and neutral solutions respectively. The X...

Sulphate analysis in uranium leach iron(III) chloride solutions by inductively coupled argon plasma spectrometry

International Nuclear Information System (INIS)

Nirdosh, I.; Lakhani, S.; Yunus, M.Z.M.

1993-01-01

Inductively coupled Argon Plasma Spectrometry is used for the indirect determination of sulphate in iron(III) chloride leach solution of Elliot Lake uranium ores via addition of a known amount of barium ions and analyzing for excess of barium. The ore contains ∼ 7 wt% pyrite, FeS 2 , as the major mineral which oxidizes to generate sulphate during leaching with Fe(III). The effects of pH, the concentrations of Fe(III) and chloride ions and for presence of ethanol in the test samples on the accuracy of analysis are studied. It is found that unlike the Rhodizonate method, removal of iron(III) from or addition of ethanol to the test sample prior to analysis are not required. Linear calibration curves are obtained. (author)

Synthesis, characterization, antiplasmodial and antitrypanosomal activity of some metal(III complexes of sulfadiazine

Directory of Open Access Journals (Sweden)

P.A. Ajibade

2008-08-01

Full Text Available The Fe(III, Ru(III, Rh(III, and Cr(III complexes of 4-amino-N-(2-pyrimidinylbenzene sulfonamide (sulfadiazine have been synthesized and characterized by elemental analysis, electronic and IR spectroscopy, conductance and room temperature magnetic susceptibility measurements. Sulfadiazine acts as a bidentate ligand through the sulfonamido and the pyrimidinic N-atoms. The compounds are non-electrolytes and the electronic spectra are consistent with the proposed octahedral geometry around the metal ions. The complexes were tested for in vitro activity against cultures of the resistant strains of Plasmodium falciparum, tripamastigotes T. b. rhodesiense and amastigotes L. donovani to determine their antiprotozoal activities. The Fe(III complex is more active than the other complexes against the parasitic protozoa.

Iron(II) and Iron(III) Spin Crossover: Toward an Optimal Density Functional

DEFF Research Database (Denmark)

Siig, Oliver S; Kepp, Kasper P.

2018-01-01

Spin crossover (SCO) plays a major role in biochemistry, catalysis, materials, and emerging technologies such as molecular electronics and sensors, and thus accurate prediction and design of SCO systems is of high priority. However, the main tool for this purpose, density functional theory (DFT......), is very sensitive to applied methodology. The most abundant SCO systems are Fe(II) and Fe(III) systems. Even with average good agreement, a functional may be significantly more accurate for Fe(II) or Fe(III) systems, preventing balanced study of SCO candidates of both types. The present work investigates....../precise, inaccurate/imprecise) are observed. More generally, our work illustrates the importance not only of overall accuracy but also of balanced accuracy for systems likely to occur in context....

Subsurface clade of Geobacteraceae that predominates in a diversity of Fe(III)-reducing subsurface environments

Science.gov (United States)

Holmes, Dawn E.; O'Neil, Regina A.; Vrionis, Helen A.; N'Guessan, Lucie A.; Ortiz-Bernad, Irene; Larrahondo, Maria J.; Adams, Lorrie A.; Ward, Joy A.; Nicoll , Julie S.; Nevin, Kelly P.; Chavan, Milind A.; Johnson, Jessica P.; Long, Philip E.; Lovely, Derek R.

2007-01-01

There are distinct differences in the physiology of Geobacter species available in pure culture. Therefore, to understand the ecology of Geobacter species in subsurface environments, it is important to know which species predominate. Clone libraries were assembled with 16S rRNA genes and transcripts amplified from three subsurface environments in which Geobacter species are known to be important members of the microbial community: (1) a uranium-contaminated aquifer located in Rifle, CO, USA undergoing in situ bioremediation; (2) an acetate-impacted aquifer that serves as an analog for the long-term acetate amendments proposed for in situ uranium bioremediation and (3) a petroleum-contaminated aquifer in which Geobacter species play a role in the oxidation of aromatic hydrocarbons coupled with the reduction of Fe(III). The majority of Geobacteraceae 16S rRNA sequences found in these environments clustered in a phylogenetically coherent subsurface clade, which also contains a number of Geobacter species isolated from subsurface environments. Concatamers constructed with 43 Geobacter genes amplified from these sites also clustered within this subsurface clade. 16S rRNA transcript and gene sequences in the sediments and groundwater at the Rifle site were highly similar, suggesting that sampling groundwater via monitoring wells can recover the most active Geobacter species. These results suggest that further study of Geobacter species in the subsurface clade is necessary to accurately model the behavior of Geobacter species during subsurface bioremediation of metal and organic contaminants.

Distinguishing iron-reducing from sulfate-reducing conditions

Science.gov (United States)

Chapelle, F.H.; Bradley, P.M.; Thomas, M.A.; McMahon, P.B.

2009-01-01

Ground water systems dominated by iron- or sulfate-reducing conditions may be distinguished by observing concentrations of dissolved iron (Fe2+) and sulfide (sum of H2S, HS-, and S= species and denoted here as "H2S"). This approach is based on the observation that concentrations of Fe2+ and H2S in ground water systems tend to be inversely related according to a hyperbolic function. That is, when Fe2+ concentrations are high, H2S concentrations tend to be low and vice versa. This relation partly reflects the rapid reaction kinetics of Fe2+ with H2S to produce relatively insoluble ferrous sulfides (FeS). This relation also reflects competition for organic substrates between the iron- and the sulfate-reducing microorganisms that catalyze the production of Fe2+ and H 2S. These solubility and microbial constraints operate in tandem, resulting in the observed hyperbolic relation between Fe2+ and H 2S concentrations. Concentrations of redox indicators, including dissolved hydrogen (H2) measured in a shallow aquifer in Hanahan, South Carolina, suggest that if the Fe2+/H2S mass ratio (units of mg/L) exceeded 10, the screened interval being tapped was consistently iron reducing (H2 ???0.2 to 0.8 nM). Conversely, if the Fe 2+/H2S ratio was less than 0.30, consistent sulfate-reducing (H2 ???1 to 5 nM) conditions were observed over time. Concomitantly high Fe2+ and H2S concentrations were associated with H2 concentrations that varied between 0.2 and 5.0 nM over time, suggesting mixing of water from adjacent iron- and sulfate-reducing zones or concomitant iron and sulfate reduction under nonelectron donor-limited conditions. These observations suggest that Fe2+/H2S mass ratios may provide useful information concerning the occurrence and distribution of iron and sulfate reduction in ground water systems. ?? 2009 National Ground Water Association.

Learning to REDUCE: A Reduced Electricity Consumption Prediction Ensemble

Energy Technology Data Exchange (ETDEWEB)

Aman, Saima; Chelmis, Charalampos; Prasanna, Viktor

2016-02-12

Utilities use Demand Response (DR) to balance supply and demand in the electric grid by involving customers in efforts to reduce electricity consumption during peak periods. To implement and adapt DR under dynamically changing conditions of the grid, reliable prediction of reduced consumption is critical. However, despite the wealth of research on electricity consumption prediction and DR being long in practice, the problem of reduced consumption prediction remains largely un-addressed. In this paper, we identify unique computational challenges associated with the prediction of reduced consumption and contrast this to that of normal consumption and DR baseline prediction.We propose a novel ensemble model that leverages different sequences of daily electricity consumption on DR event days as well as contextual attributes for reduced consumption prediction. We demonstrate the success of our model on a large, real-world, high resolution dataset from a university microgrid comprising of over 950 DR events across a diverse set of 32 buildings. Our model achieves an average error of 13.5%, an 8.8% improvement over the baseline. Our work is particularly relevant for buildings where electricity consumption is not tied to strict schedules. Our results and insights should prove useful to the researchers and practitioners working in the sustainable energy domain.

Model compounds of iron gall inks – a Mössbauer study

Energy Technology Data Exchange (ETDEWEB)

Lerf, A. [Bavarian Academy of Sciences, Walther Meißner Institute (Germany); Wagner, F. E., E-mail: fwagner@tum.de [Technical University of Munich, Physics Department E15 (Germany)

2016-12-15

Ferrogallic inks were used for at least two millennia before they became obsolete in the 20{sup th} century. The chemistry of such inks is, however, still largely unclear. Today it is of particular interest for the conservation of old manuscripts. {sup 57}Fe Mössbauer spectra of the ink on historical documents showed the presence of Fe(II) oxalate and of Fe(III) sites presumably representing iron oxihydroxides. To obtain more information on the behaviour of ink on paper we have performed Mössbauer studies at 300 and 4.2 K on iron gall inks prepared from FeSO{sub 4}⋅7H{sub 2}O and tannin. These inks were either written on paper or isolated as a precipitate by centrifugation. In the dried precipitate there is still a strong contribution of the FeSO{sub 4}⋅7H{sub 2}O which is absent in the same ink written on paper, for which a broad ferrous component with a quadrupole splitting (QS) of about 2.5 mm/s was found. The dominant Fe(III) site present in all inks on paper with QS ≈ 0.82 mm/s is not Fe(III) gallate and different from the precipitates. We propose that nanoparticulate oxidic clusters or molecular composites covered by a shell of polymerized oxidation products of the phenols are formed on the paper.

Model compounds of iron gall inks – a Mössbauer study

International Nuclear Information System (INIS)

Lerf, A.; Wagner, F. E.

2016-01-01

Ferrogallic inks were used for at least two millennia before they became obsolete in the 20 th century. The chemistry of such inks is, however, still largely unclear. Today it is of particular interest for the conservation of old manuscripts. 57 Fe Mössbauer spectra of the ink on historical documents showed the presence of Fe(II) oxalate and of Fe(III) sites presumably representing iron oxihydroxides. To obtain more information on the behaviour of ink on paper we have performed Mössbauer studies at 300 and 4.2 K on iron gall inks prepared from FeSO 4 ⋅7H 2 O and tannin. These inks were either written on paper or isolated as a precipitate by centrifugation. In the dried precipitate there is still a strong contribution of the FeSO 4 ⋅7H 2 O which is absent in the same ink written on paper, for which a broad ferrous component with a quadrupole splitting (QS) of about 2.5 mm/s was found. The dominant Fe(III) site present in all inks on paper with QS ≈ 0.82 mm/s is not Fe(III) gallate and different from the precipitates. We propose that nanoparticulate oxidic clusters or molecular composites covered by a shell of polymerized oxidation products of the phenols are formed on the paper.

Synthesis and characterization of sulfate and dodecylbenzenesulfonate intercalated zinc iron layered double hydroxides by one-step coprecipitation route

Science.gov (United States)

Zhang, Hui; Wen, Xing; Wang, Yingxia

2007-05-01

Inorganic sulfate- and organic dodecylbenzenesulfonate (DBS)-intercalated zinc-iron layered double hydroxides (LDHs) materials were prepared by one-step coprecipitation method from a mixed salt solutions containing Zn(II), Fe(II) and Fe(III) salts. The as-prepared samples have been characterized by X-ray powder diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), low-temperature nitrogen adsorption, scanning electron microscopy (SEM), inductively coupled plasma emission spectroscopy (ICP), and Mössbauer spectroscopy (MS). The XRD analyses demonstrate the typical LDH-like layered structural characteristics of both products. The room temperature MS results reveal the characteristics of both the Fe(II) and Fe(III) species for SO 42--containing product, while only the Fe(III) characteristic for DBS-containing one. The combination characterization results and Rietveld analysis illustrate that the SO 42--containing product possesses the Green Rust two (GR2)-like crystal structure with an approximate chemical composition of [Zn 0.435·Fe II0.094·Fe III0.470·(OH) 2]·(SO 42-) 0.235·1.0H 2O, while the DBS-containing one exhibits the common LDH compound-like structure. The contact angle measurement indicates the evident hydrophobic properties of DBS-containing nanocomposite, compared with SO 42--containing product, due to the modification of the internal and external surface of LDHs by the organic hydrophobic chain of DBS.

Mössbauer investigations to characterize Fe lattice sites in sheet silicates and Peru Basin deep-sea sediments

Science.gov (United States)

Lougear, André; König, Iris; Trautwein, Alfred X.; Suess, Erwin

A procedure to classify different Fe lattice sites, i.e., OH-group geometries, in the clay mineral content of deep-sea sediments was developed using Mössbauer spectroscopy at low temperature (77 K). This speciation is of interest with regard to the redox behavior, reactivity and color of marine sediments, since substantial iron redox transitions (associated with sediment color change) have been documented for the structural sheet silicate iron. Lattice site classification was achieved for the Fe(II) fraction, all of which is structural clay Fe(II) in the sediments under investigation. Whereas the major part of the Fe(III) is structural clay iron as well, there is a small Fe(III) fraction in oxide minerals. Therefore, further elaboration of the procedure would be required to also achieve lattice site classification for the Fe(III) fraction. Analysis of the Mössbauer spectra is based on computer fits, the input parameters of which were derived from a separate study of Fe(II)-rich pure chlorites. The procedure of classification is qualified to investigate, e.g., in laboratory experiments, the site-specific reaction rates and the effects on sediment color of iron redox transitions in the sheet silicate content of sediments. The new skills were successfully applied in environmental impact studies on the mining of polymetallic nodules from the Peru Basin deep-sea floor.

Reactivity of catecholamine-driven Fenton reaction and its relationships with iron(III) speciation.

Science.gov (United States)

Melin, Victoria; Henríquez, Adolfo; Freer, Juanita; Contreras, David

2015-03-01

Fenton reaction is the main source of free radicals in biological systems. The reactivity of this reaction can be modified by several factors, among these iron ligands are important. Catecholamine (dopamine, epinephrine, and norepinephrine) are able to form Fe(III) complexes whose extension in the coordination number depends upon the pH. Fe(III)-catecholamine complexes have been related with the development of several pathologies. In this work, the ability of catecholamines to enhance the oxidative degradation of an organic substrate (veratryl alcohol, VA) through Fenton and Fenton-like reactions was studied. The initial VA degradation rate at different pH values and its relationship to the different iron species present in solution were determined. Furthermore, the oxidative degradation of VA after 24 hours of reaction and its main oxidation products were also determined. The catecholamine-driven Fenton and Fenton-like systems showed higher VA degradation compared to unmodified Fenton or Fenton-like systems, which also showed an increase in the oxidation state of the VA degradation product. All of this oxidative degradation takes place at pH values lower than 5.50, where the primarily responsible species would be the Fe(III) mono-complex. The presence of Fe(III) mono-complex is essential in the ability of catecholamines to increase the oxidative capacity of Fenton systems.

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

International Nuclear Information System (INIS)

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

1987-01-01

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

Application and equivalence assessment for determining ethamsylate by using potassium ferricyanide as spectroscopic probe reagent.

Science.gov (United States)

Liu, Litao; Li, Jing; Li, Quanmin

2010-01-01

In this paper, a novel method has been established to determine ethamsylate using potassium ferricyanide as a spectroscopic probe reagent. It has been demonstrated that Fe(III) is reduced to Fe(II) by ethamsylate, and that the formed Fe(II) reacts with potassium ferricyanide to form soluble prussian blue (KFe(III)[Fe(II)(CN)(6)]). Beer's law is obeyed in the range of 0.16 - 24.00 µg mL(-1) with the molar absorption coefficient of 2.1 × 10(4) L mol(-1) cm(-1). The detection limit (3 σ/k) is 0.11 µg mL(-1). This method has been successfully applied to determine ethamsylate in pharmaceutical and serum samples with satisfactory results, and presented quite satisfactory credibility during method equivalence assessment.

NMR study of the molecular nanomagnet [Fe8(N3C6H15)6O2(OH)12]·[Br8·9H2O] in the high-spin magnetic ground state

International Nuclear Information System (INIS)

Furukawa, Y.; Kumagai, K.; Lascialfari, A.; Aldrovandi, S.; Borsa, F.; Sessoli, R.; Gatteschi, D.

2001-01-01

The magnetic molecular cluster [Fe 8 (N 3 C 6 H 15 ) 6 O 2 (OH) 12 ] 8+ [Br 8 ·9H 2 O] 8- , in short Fe8, has been investigated at low temperature by 1 H-NMR and relaxation measurements. Some measurements of 2 D-NMR in partially deuterated Fe8 clusters will also be reported. Upon decreasing temperature the NMR spectra display a very broad and structured signal which is the result of the internal local fields at the proton sites due to the local moments of the Fe(III) ions in the total S=10 magnetic ground state. The proton and deuteron NMR spectra have been analyzed and the different resonance peaks have been attributed to the different proton groups in the molecule. The simulation of the spectra by using a dipolar hyperfine field and the accepted model for the orientation of the Fe(III) local moments do not agree with the experiments even when the magnitude of the local Fe(III) moments is allowed to vary. It is concluded that a positive contact hyperfine interaction of the same order of magnitude as the dipolar interaction is present for all proton sites except the water molecules. The temperature and magnetic field dependence of the nuclear spin-lattice relaxation rate is ascribed to the fluctuations of the local Fe(III) moments, which follow rigidly the fluctuations of the total ground state magnetization of the nanomagnet. By using a simple model already utilized for the Mn12 cluster, we derive the value of the spin phonon coupling constant which determines the lifetime broadening of the different magnetic quantum number m substates of the S=10 ground state. It is shown that the lifetime broadening decreases rapidly on lowering the temperature. When the lifetime becomes longer than the reciprocal of the frequency shift of the proton lines a structure emerges in the NMR spectrum reflecting the ''frozen'' local moment configuration

Siderophore-mediated iron dissolution from nontronites is controlled by mineral cristallochemistry

Directory of Open Access Journals (Sweden)

Damien eParrello

2016-03-01

Full Text Available Bacteria living in oxic environments experience iron deficiency due to limited solubility and slow dissolution kinetics of iron-bearing minerals. To cope with iron deprivation, aerobic bacteria have evolved various strategies, including release of siderophores or other organic acids that scavenge external Fe(III and deliver it to the cells. This research investigated the role of siderophores produced by Pseudomonas aeruginosa in the acquisition of Fe(III from two iron-bearing colloidal nontronites (NAu-1 and NAu-2, comparing differences in bioavailability related with site occupancy and distribution of Fe(III in the two lattices. To avoid both the direct contact of the mineral colloids with the bacterial cells and the uncontrolled particle aggregation, nontronite suspensions were homogenously dispersed in a porous silica gel before the dissolution experiments. A multiparametric approach coupling UV-vis spectroscopy and spectral decomposition algorithm was implemented to monitor simultaneously the solubilisation of Fe and the production of pyoverdine in microplate-based batch experiments. Both nontronites released Fe in a particle concentration-dependent manner when incubated with the wild-type P. aeruginosa strain, however iron released from NAu-2 was substantially greater than from NAu-1. The profile of organic acids produced in both cases was similar and may not account for the difference in the iron dissolution efficiency. In contrast, a pyoverdine-deficient mutant was unable to mobilise Fe(III from either nontronite, whereas iron dissolution occurred in abiotic experiments conducted with purified pyoverdine. Overall, our data provide evidence that P. aeruginosa indirectly mobilise Fe from nontronites primarily through the production of pyoverdine. The structural Fe present on the edges of Nau-2 rather than Nau-1 particles appears to be more bio-accessible, indicating that the distribution of Fe, in the tetrahedron and/or in the octahedron

Study on reduction reactions of neptunium(V) on magnetite surface

International Nuclear Information System (INIS)

Kitamura, Akira; Kamei, Gento; Nakata, Kotaro; Tanaka, Satoru; Tomura, Tsutomu

2004-01-01

Redox reactions between neptunium(V) (Np(V)) and magnetite (Fe(II) 1 Fe(III) 2 O 4 ) surface were investigated in N 2 gas atmosphere. A batch method was applied to the experiment. A magnetite sample and a 0.1 M NaCl solution were mixed in a polypropylene tube, and pH, redox potential and concentration of dissolved neptunium were measured as a function of shaking time, temperature and liquid/solid ratio. The concentration of dissolved neptunium was reduced rapidly within a day, due to the reducing reaction of Np(V) to Np(IV) and the precipitation of Np(IV). The rate constant of the redox reaction and the activation energy for the rate constant were preliminarily obtained. On the other hand, redox reactions between Np(V) and aqueous Fe(II) were hardly observed. Considering the number of transferred electrons, it was suggested that the redox reaction was promoted by not only Fe(II) on the magnetite surface, but also Fe(II) inside the magnetite. (author)

Comparative biochemistry and physiology of iron-respiring bacteria from acidic and neutral-pH environments: Final Technical Report

Energy Technology Data Exchange (ETDEWEB)

Magnuson, T S

2009-04-07

Acidophilic dissimilatory iron-reducing bacteria (DIRB) are now being detected in a variety of ‘extreme’ low-pH, radionuclide- and heavy-metal contaminated habitats where Fe(III) reduction is taking place, and may represent a significant proportion of metal-transforming organisms in these environments. Acidiphilium cryptum is our model organism, a facultative iron-respiring Alphaproteobacterium. Major findings of this project have been 1) Discovery of novel outer-membrane and periplasmic cytochromes c in acidophiles that are reactive with Fe and Cr, 2) Discovery of Cr(VI) reduction mechanisms in acidophiles, mediated by c-type cytochromes and other reductase activity, 3) Development of enzyme detection methods specific for Cr-reducing enzymes, 4) Characterization of biofilm formation in A. cryptum, and 5) Annotation of the Acidiphilium cryptum genome (Magnuson, Kusel, and Cummings, DOE-JGI 2005-2006). Two manuscripts and one book chapter have been published, and several more mauscripts are prepared for submission.

Antioxidant potential of bitter cumin (Centratherum anthelminticum (L. Kuntze seeds in in vitro models

Directory of Open Access Journals (Sweden)

Naidu Kamatham A

2011-05-01

Full Text Available Abstract Background Bitter cumin (Centratherum anthelminticum (L. Kuntze, is a medicinally important plant. Earlier, we have reported phenolic compounds, antioxidant, and anti-hyperglycemic, antimicrobial activity of bitter cumin. In this study we have further characterized the antioxidative activity of bitter cumin extracts in various in vitro models. Methods Bitter cumin seeds were extracted with a combination of acetone, methanol and water. The antioxidant activity of bitter cumin extracts were characterized in various in vitro model systems such as DPPH radical, ABTS radical scavenging, reducing power, oxidation of liposomes and oxidative damage to DNA. Results The phenolic extracts of bitter cumin at microgram concentration showed significant scavenging of DPPH and ABTS radicals, reduced phosphomolybdenum (Mo(VI to Mo(V, ferricyanide Fe(III to Fe(II, inhibited liposomes oxidation and hydroxyl radical induced damage to prokaryotic genomic DNA. The results showed a direct correlation between phenolic acid content and antioxidant activity. Conclusion Bitter cumin is a good source of natural antioxidants.

Pipeline Drag Reducers

International Nuclear Information System (INIS)

Marawan, H.

2004-01-01

Pipeline drag reducers have proven to be an extremely powerful tool in fluid transportation. High molecular weight polymers are used to reduce the frictional pressure loss ratio in crude oil pipelines, refined fuel and aqueous pipelines. Chemical structure of the main used pipeline drag reducers is one of the following polymers and copolymers classified according to the type of fluid to ; low density polyethylene, copolymer of I-hexane cross linked with divinyl benzene, polyacrylamide, polyalkylene oxide polymers and their copolymers, fluorocarbons, polyalkyl methacrylates and terpolymer of styrene, alkyl acrylate and acrylic acid. Drag reduction is the increase in pump ability of a fluid caused by the addition of small amounts of an additive to the fluid. The effectiveness of a drag reducer is normally expressed in terms of percent drag reduction. Frictional pressure loss in a pipeline system is a waste of energy and it costly. The drag reducing additive minimizes the flow turbulence, increases throughput and reduces the energy costs. The Flow can be increased by more than 80 % with existing assets. The effectiveness of the injected drag reducer in Mostorod to Tanta crude oil pipeline achieved 35.4 % drag reduction and 23.2 % flow increase of the actual performance The experimental application of DRA on Arab Petroleum Pipeline Company (Summed) achieved a flow increase ranging from 9-32 %

Oxidative dissolution potential of biogenic and abiogenic TcO2 in subsurface sediments

International Nuclear Information System (INIS)

Fredrickson, J.K.; Zachara, J.M.; Plymale, A.E.; Heald, S.M.; McKinley, J.P.; Kennedy, D.W.; Liu, C.; Nachimuthu, P.

2009-01-01

Technetium-99 (Tc) is an important fission product contaminant associated with sites of nuclear fuels reprocessing and geologic nuclear waste disposal. Tc is highly mobile in its most oxidized state (Tc(VII)O 4 - ) and less mobile in the reduced form (Tc(IV)O 2 · nH 2 O). Here we investigate the potential for oxidation of Tc(IV) that was heterogeneously reduced by reaction with biogenic Fe(II) in two sediments differing in mineralogy and aggregation state; unconsolidated Pliocene-age fluvial sediment from the upper Ringold (RG) Formation at the Hanford Site and a clay-rich saprolite from the Field Research Center (FRC) background site on the Oak Ridge Site. Both sediments contained Fe(III) and Mn(III/IV) as redox active phases, but FRC also contained mass-dominant Fe-phyllosilicates of different types. Shewanella putrefaciens CN32 reduced Mn(III/IV) oxides and generated Fe(II) that was reactive with Tc(VII) in heat-killed, bioreduced sediment. After bioreduction and heat-killing, biogenic Fe(II) in the FRC exceeded that in RG by a factor of two. More rapid reduction rates were observed in the RG that had lower biogenic Fe(II), and less particle aggregation. EXAFS measurements indicated that the primary reduction product was a TcO 2 -like phase in both sediments. The biogenic redox product Tc(IV) oxidized rapidly and completely in RG when contacted with air. Oxidation, in contrast, was slow and incomplete in the FRC, in spite of similar molecular scale speciation of Tc compared to RG. X-ray microprobe, electron microprobe, X-ray absorption spectroscopy, and micro X-ray diffraction were applied to the whole sediment and isolated Tc-containing particles. These analyses revealed that non-oxidizable Tc(IV) in the FRC existed as complexes with octahedral Fe(III) within intra-grain domains of 50-100 (micro)m-sized, Fe-containing micas presumptively identified as celadonite. The markedly slower oxidation rates in FRC as compared to RG were attributed to mass

Oxidative dissolution potential of biogenic and abiogenic TcO 2 in subsurface sediments

Science.gov (United States)

Fredrickson, James K.; Zachara, John M.; Plymale, Andrew E.; Heald, Steve M.; McKinley, James P.; Kennedy, David W.; Liu, Chongxuan; Nachimuthu, Ponnusamy

2009-04-01

Technetium-99 (Tc) is an important fission product contaminant associated with sites of nuclear fuels reprocessing and geologic nuclear waste disposal. Tc is highly mobile in its most oxidized state [Tc(VII)O4-] and less mobile in the reduced form [Tc(IV)O 2· nH 2O]. Here we investigate the potential for oxidation of Tc(IV) that was heterogeneously reduced by reaction with biogenic Fe(II) in two sediments differing in mineralogy and aggregation state; unconsolidated Pliocene-age fluvial sediment from the upper Ringold (RG) Formation at the Hanford Site and a clay-rich saprolite from the Field Research Center (FRC) background site on the Oak Ridge Site. Both sediments contained Fe(III) and Mn(III/IV) as redox active phases, but FRC also contained mass-dominant Fe-phyllosilicates of different types. Shewanella putrefaciens CN32 reduced Mn(III/IV) oxides and generated Fe(II) that was reactive with Tc(VII) in heat-killed, bioreduced sediment. After bioreduction and heat-killing, biogenic Fe(II) in the FRC exceeded that in RG by a factor of two. More rapid reduction rates were observed in the RG that had lower biogenic Fe(II), and less particle aggregation. EXAFS measurements indicated that the primary reduction product was a TcO 2-like phase in both sediments. The biogenic redox product Tc(IV) oxidized rapidly and completely in RG when contacted with air. Oxidation, in contrast, was slow and incomplete in the FRC, in spite of similar molecular scale speciation of Tc compared to RG. X-ray microprobe, electron microprobe, X-ray absorption spectroscopy, and micro X-ray diffraction were applied to the whole sediment and isolated Tc-containing particles. These analyses revealed that non-oxidizable Tc(IV) in the FRC existed as complexes with octahedral Fe(III) within intra-grain domains of 50-100 μm-sized, Fe-containing micas presumptively identified as celadonite. The markedly slower oxidation rates in FRC as compared to RG were attributed to mass

Enhancing the Process of Anaerobic Ammonium Oxidation Coupled to Iron Reduction in Constructed Wetland Mesocosms with Supplementation of Ferric Iron Hydroxides

Science.gov (United States)

Shuai, W.; Jaffe, P. R.

2017-12-01

Effective ammonium (NH4+) removal has been a challenge in wastewater treatment processes. Aeration, which is required for the conventional NH4+ removal approach by ammonium oxidizing bacteria, is an energy intensive process during the operation of wastewater treatment plant. The efficiency of NH4+ oxidation in natural systems is also limited by oxygen transfer in water and sediments. The objective of this study is to enhance NH4+ removal by applying a novel microbial process, anaerobic NH4+ oxidation coupled to iron (Fe) reduction (also known as Feammox), in constructed wetlands (CW). Our studies have shown that an Acidimicrobiaceae bacterium named A6 can carry out the Feammox process using ferric Fe (Fe(III)) minerals like ferrihydrite as their electron acceptor. To investigate the properties of the Feammox process in CW as well as the influence of electrodes, Feammox bacterium A6 was inoculated in planted CW mesocosms with electrodes installed at multiple depths. CW mesocosms were operated using high NH4+ nutrient solution as inflow under high or low sediment Fe(III) level. During the operation, NH4+ and ferrous Fe concentration, pore water pH, voltages between electrodes, oxidation reduction potential and dissolved oxygen were measured. At the end of the experiment, CW sediment samples at different depths were taken, DNAs were extracted and quantitative polymerase chain reaction and pyrosequencing were performed to analyze the microbial communities. The results show that the high Fe level CW mesocosm has much higher NH4+ removal ability than the low Fe level CW mesocosm after Fe-reducing conditions are developed. This indicates the enhanced NH4+ removal can be attributed to elevated Feammox activity in high Fe level CW mesocosm. The microbial community structures are different in high or low Fe level CW mesocosms and on or away from the installed electrodes. The voltages between cathode and anode increased after the injection of A6 enrichment culture in low Fe

Studies on the turnover and properties of dump groundwaters in brown coal mining areas and possibilities of influencing them. Final report; Untersuchungen zum Stoffumsatz und zur Beschaffenheit der Kippengrundwaesser in Braunkohlebergbaugebieten und Moeglichkeiten zu deren Beeinflussung. Abschlussbericht

Energy Technology Data Exchange (ETDEWEB)

Katzur, J.; Liebner, F.; Liebner, C.; Welzel, H.P.; Hettrich, K.

2001-07-01

Only 6 days after the increase in pH with water saturation the concentration of iron in the pore water of the T1 sediment had dropped to a low value, 70% of which was accounted for by Fe(II). This is probably due to the almost complete precipitation of Fe(III) caused by the high pH values. Compared with the untreated variant the lowering of pH in the further course of the experiment led to a slight Fe(III) mobilisation and hence, through interaction with other reduction processes, to erratic changes in the share of Fe(II) in total Fe. Although this sediment showed a relatively low iron concentration a comparison showed that higher pH values and incubation temperatures have an influence on microbial iron reduction. [German] Im Porenwasser des Sedimentes T1 lag Eisen bereits 6 Tage nach pH-Erhoehung und Wassersaettigung nur noch in geringer Konzentration und zu ueber 70% als Fe(II) vor. Dies ist vermutlich in erster Linie auf die nahezu vollstaendige Ausfaellung von Fe(III) infolge der hohen pH-Werte zurueckzufuehren. Im weiteren Versuchsverlauf fuehrte das Absinken der pH-Werte zu einer im Vergleich zur unbehandelten Variante geringfuegigen Fe(III)-Mobilisierung und damit in Wechselwirkung mit ablaufenden Reduktionsprozessen zu unstetigen Veraenderungen in den Anteilen Fe(II) an Fe{sub ges}. Obwohl in diesem Sediment nur vergleichsweise niedrige Eisenkonzentrationen vorliegen, ergab ein Vergleich, dass hoehere pH-Werte und Inkubationtemperaturen die mikrobielle Eisenreduktion beeinflussen. (orig.)

Controlled swelling and adsorption properties of polyacrylate/montmorillonite composites

Energy Technology Data Exchange (ETDEWEB)

Natkanski, Piotr [Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow (Poland); Kustrowski, Piotr, E-mail: kustrows@chemia.uj.edu.pl [Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow (Poland); Bialas, Anna; Piwowarska, Zofia [Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow (Poland); Michalik, Marek [Institute of Geological Sciences, Jagiellonian University, Oleandry 2a, 30-063 Krakow (Poland)

2012-10-15

A series of novel polyacrylate/montmorillonite composites was synthesized by in situ polymerization in aqueous slurry of clay. Dissociated (obtained by adding ammonium or sodium hydroxide) and undissociated forms of acrylic acid were used as monomers in the hydrogel synthesis. The structure and composition of the samples were studied by powder X-ray diffraction, diffuse reflectance infra-red Fourier transform spectroscopy, thermogravimetry and elemental analysis. It has been found that the kind of monomer influences strongly the location of a polymer chain in the formed composite. Complete intercalation of hydrogel into the interlayer space of montmorillonite was observed for sodium polyacrylate, whereas polyacrylic acid and ammonium polyacrylate mainly occupied the outer surface of the clay. The position of hydrogel determined the swelling and adsorption properties of the studied composites. The important factor influencing the kinetics of Fe(III) cation adsorption was pH. The analysis of adsorption isotherms allowed to propose the mechanism of Fe(III) cation adsorption. Highlights: Black-Right-Pointing-Pointer Polyacrylate hydrogels can be introduced into the interlayers of clay. Black-Right-Pointing-Pointer The position of hydrogel in the composite depends on the polymer type. Black-Right-Pointing-Pointer Ammonium polyacrylate places outside the clay, sodium one is intercalated into it. Black-Right-Pointing-Pointer Swelling and adsorption capacities can be controlled by the polymer position. Black-Right-Pointing-Pointer High adsorption efficiency in Fe(III) removal was observed.

Synthesis, iron(III) complexation properties, molecular dynamics simulations and P. aeruginosa siderophore-like activity of two pyoverdine analogs.

Science.gov (United States)

Antonietti, Viviane; Boudesocque, Stéphanie; Dupont, Laurent; Farvacques, Natacha; Cézard, Christine; Da Nascimento, Sophie; Raimbert, Jean-François; Socrier, Larissa; Robin, Thierry-Johann; Morandat, Sandrine; El Kirat, Karim; Mullié, Catherine; Sonnet, Pascal

2017-09-08

P. aeruginosa ranks among the top five organisms causing nosocomial infections. Among the many novel strategies for developing new therapeutics against infection, targeting iron uptake mechanism seems promising as P. aeruginosa needs iron for its growth and survival. To scavenge iron, the bacterium produces siderophores possessing a very high affinity towards Fe(III) ions such as pyoverdines. In this work, we decided to study two pyoverdine analogs, aPvd2 and aPvd3, structurally close to the endogen pyoverdine. The pFe constants calculated with the values of formation showed a high affinity of aPvd3 towards Fe(III). Molecular dynamics calculations demonstrated that aPvd3-Fe forms with Fe(III) stable 1:1 complexes in water, whereas aPvd2 does not. Only aPvd3 is able to increase the bacterial growth and represents thus an alternative to pyoverdine for iron acquisition by the bacterium. The aPvd2-3 interaction studies with a lipid membrane indicated that they were unable to interact and to cross the plasma membrane of bacteria by passive diffusion. Consequently, the penetration of aPvd3 is ruled by a transport membrane protein. These results showed that aPvd3 may be used to inhibit pyoverdine uptake or to promote the accumulation and release of antibiotics into the cell following a Trojan horse strategy. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

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.

Mild hydrothermal synthesis, crystal structure, thermal behaviour, spectroscopic and magnetic properties of (NH4)0.80Li0.20[Fe(AsO4)F

International Nuclear Information System (INIS)

Berrocal, Teresa; Mesa, Jose L.; Larrea, Edurne S.; Bazan, Begona; Pizarro, Jose L.; Lezama, Luis; Rojo, Teofilo; Arriortua, Maria I.

2011-01-01

The (NH 4 ) 0.80 Li 0.20 [Fe(AsO 4 )F] compound has been synthesized under mild hydrothermal conditions. The compound crystallize in the orthorhombic Pna2 1 space group, with cell parameters a=13.352(9), b=6.7049(9), c=10.943(2) A and Z=8. The compound belongs to the KTiO(PO 4 ) structure type, with chains alternating FeO 4 F 2 octahedra and AsO 4 tetrahedra, respectively, running along the 'a' and 'b' crystallographic axes. The diffuse reflectance spectrum in the visible region shows the forbidden electronic transitions characteristic of the Fe(III) d 5 -high spin cation in slightly distorted octahedral geometry. The Moessbauer spectrum at room temperature is characteristic of iron (III) cations. The ESR spectra, carried out from room temperature to 200 K, remain isotropic with variation in temperature; the g-value being 1.99(1). Magnetic measurements indicate the predominance of strong antiferromagnetic interactions. - Graphical Abstract: Three-dimensional structure of (NH 4 ) 0.80 Li 0.20 [Fe(AsO 4 )F], a fluoroarsenate containing lithium and ammonium in the structural cavities. Highlights: → (NH 4 ) 0.80 Li 0.20 [Fe(AsO 4 )F] has been synthesized by mild hydrothermal technique. → The compound exhibits a three-dimensional structure. → Moessbauer spectrum indicates the existence of Fe(III) cations. → Visible spectroscopy confirms the hexacoordination of Fe(III). → Magnetic measurements indicate the existence of a global antiferromagnetic ordering.

Synthesis and characterization of anionic/nonionic surfactant-interceded iron-doped TiO{sub 2} to enhance sorbent/photo-catalytic properties

Energy Technology Data Exchange (ETDEWEB)

Sharma, Ajit; Lee, Byeong-Kyu, E-mail: bklee@ulsan.ac.kr

2015-09-15

We investigated the synthesis, characterization, and application of surfactant-interceded Fe nanoparticle-doped TiO{sub 2} (TiO{sub 2}/Fe-S1 and TiO{sub 2}/Fe-S2) that were used as adsorbents and photo-catalysts for the removal of As(V) ions from aqueous media. Two types of surfactant (anionic (sodium dodecyl sulfate), S1 and non-ionic (Triton X-100), S2) were used to obtain the separation and mono-dispersion of Fe(III) ions in the reaction solution. The nanocomposites were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), UV–vis, scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX) and elemental mapping analysis before and after As(V) removal. The Langmuir capacities (q{sub e}, mg/g) of the sodium dodecyl sulfate (SDS) and Triton X-100 interceded nanocomposites (TiO{sub 2}/Fe-S1 and TiO{sub 2}/Fe-S2, respectively) for arsenic removal were determined to be 65.79 and 50.76 mg/g, respectively, in aqueous media with As(V) concentration ranges of 0–10 mg/L at pH 6.5. - Highlights: • Fe(III) doped TiO{sub 2} nanocomposite was prepared with surfactant. • Anionic surfactant SDS enhanced the transfer of Fe(III) ions to TiO{sub 2}. • Surfactant-interceded nanocomposite enhanced As(V) removal. • Arsenic removal efficiency was as follows: dark phase>visible phase>UV region.

Desultovibrio frigidus sp nov and Desulfovibrio ferfireducens sp nov., psychrotolerant bacteria isolated from Arctic fiord sediments (Svalbard) with the ability to reduce Fe(III)

DEFF Research Database (Denmark)

Vandieken, V.; Knoblauch, C.; Jørgensen, BB

2006-01-01

(.)0-95(.)7% 16S rRNA gene sequence similarity), Strains 18(T) and 77, exhibiting 99(.)9% sequence similarity, represent a novel species for which the name Desulfovibrio frigidus sp. nov. is proposed. The type strain is strain 18(T) (=DSM 17176(T)=jCM 12924(T)). Strain 61(T) was closely related to strains 18(T...

Synthesis and characterization of chromium(III), manganese(II), iron(III), cobalt(II), nickel(II), copper(II), cadmium(II) and dioxouranium(VI) complexes of 4(2-pyridyl)-1-(2,4-dihydroxybenzaldehyde)-3-thiosemicarbazone

International Nuclear Information System (INIS)

Abu El-Reash, G.M.; Ibrahim, M.M.; Kenawy; El-Ayaan, Usama; Khattab, M.A.

1994-01-01

A few complexes of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and dioxouranium(VI) with 4(2-pyridyl)-1-(2,4-dihydroxybenzaldehyde)-3-thiosemicarbazone have been synthesised and characterized on the basis of elemental analysis, IR, electronic NMR, and magnetic moment data. An octahedral structure is proposed for the Cr(III), Fe(III), Co(II) and Ni(H 3 PBT) 2 Cl 2 .2H 2 O complexes; a tetrahedral structure for the Mn(II) and Ni 2 (PBT)OAc.H 2 0 complexes and a square planar structure for the Cu(II) complexes. The antimicrobial and antifungal activities of H 3 PBT and of its metal(II) complexes are investigated. The results reveal that H 3 PBT exhibits greater antimicrobial activities than its complexes. (author). 34 refs., 4 figs., 2 tabs

Thermal properties of graphite oxide, thermally reduced graphene and chemically reduced graphene

Science.gov (United States)

Jankovský, Ondřej; Sedmidubský, David; Lojka, Michal; Sofer, Zdeněk

2017-07-01

We compared thermal behavior and other properties of graphite oxide, thermally reduced graphene and chemically reduced graphene. Graphite was oxidized according to the Hofmann method using potassium chlorate as oxidizing agent in strongly acidic environment. In the next step, the formed graphite oxide was chemically or thermally reduced yielding graphene. The mechanism of thermal reduction was studied using STA-MS. Graphite oxide and both thermally and chemically reduced graphenes were analysed by SEM, EDS, elemental combustion analysis, XPS, Raman spectroscopy, XRD and BET. These findings will help for the large scale production of graphene with appropriate chemical composition.

A Combination of Stable Isotope Probing, Illumina Sequencing, and Co-occurrence Network to Investigate Thermophilic Acetate- and Lactate-Utilizing Bacteria.

Science.gov (United States)

Sun, Weimin; Krumins, Valdis; Dong, Yiran; Gao, Pin; Ma, Chunyan; Hu, Min; Li, Baoqin; Xia, Bingqing; He, Zijun; Xiong, Shangling

2018-01-01

Anaerobic digestion is a complicated microbiological process that involves a wide diversity of microorganisms. Acetate is one of the most important intermediates, and interactions between acetate-oxidizing bacteria and archaea could play an important role in the formation of methane in anoxic environments. Anaerobic digestion at thermophilic temperatures is known to increase methane production, but the effects on the microbial community are largely unknown. In the current study, stable isotope probing was used to characterize acetate- and lactate-oxidizing bacteria in thermophilic anaerobic digestion. In microcosms fed 13 C-acetate, bacteria related to members of Clostridium, Hydrogenophaga, Fervidobacterium, Spirochaeta, Limnohabitans, and Rhodococcus demonstrated elevated abundances of 13 C-DNA fractions, suggesting their activities in acetate oxidation. In the treatments fed 13 C-lactate, Anaeromyxobacter, Desulfobulbus, Syntrophus, Cystobacterineae, and Azospira were found to be the potential thermophilic lactate utilizers. PICRUSt predicted that enzymes related to nitrate and nitrite reduction would be enriched in 13 C-DNA fractions, suggesting that the acetate and lactate oxidation may be coupled with nitrate and/or nitrite reduction. Co-occurrence network analysis indicated bacterial taxa not enriched in 13 C-DNA fractions that may also play a critical role in thermophilic anaerobic digestion.

Coulometric titration of niobium in 1F sulfuric acid

International Nuclear Information System (INIS)

Pannu, S.S.

1975-01-01

A coulometric titration at constant current has been devised for Nb in 1F sulfuric acid. The titration was based on the oxidation of Nb(III) to Nb(V) by Fe(III) electrogenerated at a graphite anode. Both potentiometric and amperometric end points were used. The Nb(V) was prior reduced at a mercury cathode by exhaustive electrolysis at a current density of 15 ma/mc 2 for at least 10 hr. Ta,V,Ti and a working platinum anode interfered, but the separation of the potentials of Nb(V)/Nb(III) and Ti(IV)/Ti(III) permitted the titration of first Nb and then Ti. The average error for the titration of 0.30 to 13.00 mg of niobium in 100 ml of 1F sulfuric acid was + 0.57%. (author)

Heterologous Production and Yield Improvement of Epothilones in Burkholderiales Strain DSM 7029.

Science.gov (United States)

Bian, Xiaoying; Tang, Biao; Yu, Yucong; Tu, Qiang; Gross, Frank; Wang, Hailong; Li, Aiying; Fu, Jun; Shen, Yuemao; Li, Yue-Zhong; Stewart, A Francis; Zhao, Guoping; Ding, Xiaoming; Müller, Rolf; Zhang, Youming

2017-07-21

The cloning of microbial natural product biosynthetic gene clusters and their heterologous expression in a suitable host have proven to be a feasible approach to improve the yield of valuable natural products and to begin mining cryptic natural products in microorganisms. Myxobacteria are a prolific source of novel bioactive natural products with only limited choices of heterologous hosts that have been exploited. Here, we describe the use of Burkholderiales strain DSM 7029 as a potential heterologous host for the functional expression of myxobacterial secondary metabolites. Using a newly established electroporation procedure, the 56 kb epothilone biosynthetic gene cluster from the myxobacterium Sorangium cellulosum was introduced into the chromosome of strain DSM 7029 by transposition. Production of epothilones A, B, C, and D was detected despite their yields being low. Optimization of the medium, introduction of the exogenous methylmalonyl-CoA biosynthetic pathway, and overexpression of rare tRNA genes resulted in an approximately 75-fold increase in the total yields of epothilones to 307 μg L -1 . These results show that strain DSM 7029 has the potential to produce epothilones with reasonable titers and might be a broadly applicable host for the heterologous expression of other myxobacterial polyketide synthases and nonribosomal peptide synthetases, expediting the process of genome mining.

Reduced abrasion drilling fluid

NARCIS (Netherlands)

2010-01-01

A reduced abrasion drilling fluid system and method of drilling a borehole by circulating the reduced abrasion drilling fluid through the borehole is disclosed. The reduced abrasion drilling fluid comprises a drilling fluid, a first additive and a weighting agent, wherein the weighting agent has a

Reduced abrasion drilling fluid

NARCIS (Netherlands)

2012-01-01

A reduced abrasion drilling fluid system and method of drilling a borehole by circulating the reduced abrasion drilling fluid through the borehole is disclosed. The reduced abrasion drilling fluid comprises a drilling fluid, a first additive and a weighting agent, wherein the weighting agent has a

Energy sources for chemolithotrophs in an arsenic- and iron-rich shallow-sea hydrothermal system.

Science.gov (United States)

Akerman, N H; Price, R E; Pichler, T; Amend, J P

2011-09-01

The hydrothermally influenced sediments of Tutum Bay, Ambitle Island, Papua New Guinea, are ideal for investigating the chemolithotrophic activities of micro-organisms involved in arsenic cycling because hydrothermal vents there expel fluids with arsenite (As(III)) concentrations as high as 950 μg L(-1) . These hot (99 °C), slightly acidic (pH ~6), chemically reduced, shallow-sea vent fluids mix with colder, oxidized seawater to create steep gradients in temperature, pH, and concentrations of As, N, Fe, and S redox species. Near the vents, iron oxyhydroxides precipitate with up to 6.2 wt% arsenate (As(V)). Here, chemical analyses of sediment porewaters from 10 sites along a 300-m transect were combined with standard Gibbs energies to evaluate the energy yields (-ΔG(r)) from 19 potential chemolithotrophic metabolisms, including As(V) reduction, As(III) oxidation, Fe(III) reduction, and Fe(II) oxidation reactions. The 19 reactions yielded 2-94 kJ mol(-1) e(-) , with aerobic oxidation of sulphide and arsenite the two most exergonic reactions. Although anaerobic As(V) reduction and Fe(III) reduction were among the least exergonic reactions investigated, they are still potential net metabolisms. Gibbs energies of the arsenic redox reactions generally correlate linearly with pH, increasing with increasing pH for As(III) oxidation and decreasing with increasing pH for As(V) reduction. The calculated exergonic energy yields suggest that micro-organisms could exploit diverse energy sources in Tutum Bay, and examples of micro-organisms known to use these chemolithotrophic metabolic strategies are discussed. Energy modeling of redox reactions can help target sampling sites for future microbial collection and cultivation studies. © 2011 Blackwell Publishing Ltd.

Geochemistry of aquifer sediments and arsenic-rich groundwaters from Kandal Province, Cambodia

International Nuclear Information System (INIS)

Rowland, Helen A.L.; Gault, Andrew G.; Lythgoe, Paul; Polya, David A.

2008-01-01

Elevated As is well known to be present in aquifers utilised for drinking water and irrigation in West Bengal and Bangladesh. This problem has also more recently been discovered in other parts of Asia, including Vietnam, Cambodia, Inner Mongolia and the Middle Ganges Plain. Analysis of groundwaters in Kandal Province of Cambodia found waters with comparable geochemistry to the As-rich groundwaters of the West Bengali Delta. Similarities included high but heterogeneous As distributions, predominantly in the form As(III), high Fe, moderate to high HCO 3 - , circumneutral pH, low SO 4 2- and geochemical components indicative of reducing conditions. Good positive correlations between As, Fe, HCO 3 - and NH 4 + , and dissolved organic C is consistent with As release predominantly via microbially mediated reductive dissolution of As bearing Fe(III) oxides. Further evidence for such a process is found from correlations between As, Fe and organic matter from analysis of aquifer sediments, by the presence of goethite in the finer fractions and from the association of As with amorphous, poorly crystalline and well crystallised hydrous Fe oxides. The presence of several high As, but low Fe, wells implies that microbes could have a more direct role in mediating As release via the direct utilisation of Fe(III) or As(V) as electron acceptors. The presence of elevated As in waters with short aquifer residence times (as indicated by their geochemical signature) highlights the possible vulnerability of these aquifers to the influx of surface derived waters, providing an additional source of labile organic C that could exacerbate As release by stimulating microbial activity

New Trend for Acceleration Solid Phase Extraction Process Based on Using Magnetic Nano-adsorbents along with Surface Functionalization through Microwave Assisted Solvent-free Technique.

Science.gov (United States)

Ahmed, Salwa A; Soliman, Ezzat M

2015-01-01

The use of a microwave assisted solvent-free technique for silica coating of iron magnetic nanoparticles (Fe3O4-MNPs) and their functionalization with three aliphatic diamines: 1,2-ethylenediamine (1,2EDA), 1,5-pentanediamine (1,5PDA) and 1.8-octanediamine (1,8-ODA), were successfully achieved in a very short time. Only 60 min were needed for the nano-adsorbent modification as compared with more than 1000 min using conventional methods under reflux conditions. Their surface characteristics (observed by TEM, XRD and FT-IR), in addition to Cu(II) adsorption capacities (1.805, 1.928 and 2.116 mmol g(-1)) and time of equilibration (5 s) were almost the same. Thus, the time required to accomplish the solid phase extraction process is greatly reduced. On the other hand, the phenomenon of the fast equilibration kinetics was successfully extended on using the functionalized aliphatic diamines magnetic nano-adsorbents as precursors for further microwave treatment. Three selective magnetic nano-adsorbents (Fe3O4-MNPs-SiO2-1,2EDA-3FSA, Fe3O4-MNPs-SiO2-1,5PDA-3FSA and Fe3O4-MNPs-SiO2-1,8ODA-3FSA) were obtained via the reaction with 3-formayl salicylic acid (3FSA) as a selective reagent for Fe(III). At 5 s contact time, they exhibited maximum Fe(III) uptake equal to 4.512, 4.987 and 5.367 mmol g(-1), respectively. Furthermore, modeling of values of metal uptake capacity obtained at different shaking time intervals supports pseudo-second order kinetics.

Role of H2O2 in the photo-transformation of phenol in artificial and natural seawater

International Nuclear Information System (INIS)

Calza, Paola; Campra, Laura; Pelizzetti, Ezio; Minero, Claudio

2012-01-01

In previous works, it was observed that phenol photo-induced transformation in natural seawater (NSW) mediated by natural photosensitizers occurs and leads to the formation of numerous hydroxylated, condensed, halogenated and nitroderivatives. Irradiation of NSW added with phenol and iron species had provided the enhanced formation of several halophenols, suggesting a central role played by iron species on the phenol halogenation in marine water. In this paper, we focus on hydrogen peroxide, another key photosensitizer, and its interaction with iron species. The ability of Fe(II)/Fe(III) and H 2 O 2 species to act as photo-sensitizers towards the transformation of organic compounds in seawater was investigated under simulated solar radiation. Light activation is necessary to induce the transformation of phenol, as no degradation occurs in the dark when either H 2 O 2 or iron/H 2 O 2 are initially added to artificial seawater (ASW). Fe(II) is easily transformed into Fe(III), assessing that a Fenton reaction (dark, Fe(II)/H 2 O 2 ) does not take place in marine environment, in favour of a photo-activated reaction involving Fe(III) and H 2 O 2 . When NSW is spiked with H 2 O 2 and Fe(III), halophenols' and nitrophenols' concentration decreases and completely disappears at high hydrogen peroxide concentration. Since Fe(II) and Fe(III) in spiked seawater induce an enhanced formation of haloderivatives, an excess of hydrogen peroxide act as scavenger towards the photo-produced chloro/bromo radicals, so hindering halogenation process in seawater. Hence, even if hydrogen peroxide efficiently induces the ·OH radical formation, and could then promote the phenol phototransformation, nevertheless it is negligibly involved in the production of the intermediates formed during phenol photolysis in seawater, whose formation is necessarily linked to other photosensitizer species. - Highlights: ► Hydrogen peroxide-mediated solar-driven transformations of pollutant in seawater are

Effects of exogenous pyoverdines on Fe availability and their impacts on Mn(II) oxidation by Pseudomonas putida GB-1

Science.gov (United States)

Lee, Sung-Woo; Parker, Dorothy L.; Geszvain, Kati; Tebo, Bradley M.

2014-01-01

Pseudomonas putida GB-1 is a Mn(II)-oxidizing bacterium that produces pyoverdine-type siderophores (PVDs), which facilitate the uptake of Fe(III) but also influence MnO2 formation. Recently, a non-ribosomal peptide synthetase mutant that does not synthesize PVD was described. Here we identified a gene encoding the PVDGB-1 (PVD produced by strain GB-1) uptake receptor (PputGB1_4082) of strain GB-1 and confirmed its function by in-frame mutagenesis. Growth and other physiological responses of these two mutants and of wild type were compared during cultivation in the presence of three chemically distinct sets of PVDs (siderotypes n°1, n°2, and n°4) derived from various pseudomonads. Under iron-limiting conditions, Fe(III) complexes of various siderotype n°1 PVDs (including PVDGB-1) allowed growth of wild type and the synthetase mutant, but not the receptor mutant, confirming that iron uptake with any tested siderotype n°1 PVD depended on PputGB1_4082. Fe(III) complexes of a siderotype n°2 PVD were not utilized by any strain and strongly induced PVD synthesis. In contrast, Fe(III) complexes of siderotype n°4 PVDs promoted the growth of all three strains and did not induce PVD synthesis by the wild type, implying these complexes were utilized for iron uptake independent of PputGB1_4082. These differing properties of the three PVD types provided a way to differentiate between effects on MnO2 formation that resulted from iron limitation and others that required participation of the PVDGB-1 receptor. Specifically, MnO2 production was inhibited by siderotype n°1 but not n°4 PVDs indicating PVD synthesis or PputGB1_4082 involvement rather than iron-limitation caused the inhibition. In contrast, iron limitation was sufficient to explain the inhibition of Mn(II) oxidation by siderotype n°2 PVDs. Collectively, our results provide insight into how competition for iron via siderophores influences growth, iron nutrition and MnO2 formation in more complex environmental

Effect of Eu(III) on the degradation of malic acid by Pseudomonas fluorescens

International Nuclear Information System (INIS)

Nankawa, T.; Ozaki, T.; Ohnuki, T.; Suzuki, Y.; Francis, A.J.

2005-01-01

Full text of publication follows: The transuranic elements, such as Am(III) and Cm(III), are highly toxic because they emit high-energy α particles and have long half-lives. To estimate their long-term environmental behavior, we need to elucidate degradation of actinide-organic complexes by microorganisms. We studied the biodegradation of Eu(III)-malic acid complexes by Pseudomonas fluorescens. Malic acid is ubiquitous in the environment and is one of the microbial metabolites that is part of the tri-carboxylic acid (TCA) cycle. Europium(III) is a good analogue for Am(III) and Cm(III). To investigate the effect of Eu(III) on the degradation of malic acid by P. fluorescens, we compared the degradation behavior of Eu(III)-malic acid complexes to that of Fe(III) and Al(III)-malic acid complexes. In the medium containing 1 mM malic acid and 0-0.5 mM Fe(III), malic acid was degraded completely. In the medium containing 1 mM malic acid and 0.05-0.5 mM Al(III), malic acid was degraded until the concentration of malic acid became equal to that of Al(III), indicating that Al(III)-malic acid complex with 1: 1 molar ratio was recalcitrant to biodegradation. In the medium containing 1 mM malic acid and 0.05-0.5 mM Eu(III), degradation of malic acid was not observed. The effect of metals on degradation of malic acid was in the order of Fe(III) < Al(III) < Eu(III). The stability constants of 1:1 Fe(III)-, Al(III)-, and Eu(III)-malic acid complexes are 7.1, 4.6, and 4.9, respectively. These results indicate that degradability of malic acid does not depend on the stability constants of metal-malic acid complexes. We found that 10 mM malic acid was degraded in the presence of 0.05 and 0.1 mM Eu(III) but 1 mM malic acid was not degraded in the presence of 0.05 and 0.1 mM Eu(III). The degradation rate of malic acid increased with a decreasing ratio of Eu(III) to malic acid. (authors)

Isolation and Distribution of a Novel Iron-Oxidizing Crenarchaeon from Acidic Geothermal Springs in Yellowstone National Park▿ †

Science.gov (United States)

Kozubal, M.; Macur, R. E.; Korf, S.; Taylor, W. P.; Ackerman, G. G.; Nagy, A.; Inskeep, W. P.

2008-01-01

Novel thermophilic crenarchaea have been observed in Fe(III) oxide microbial mats of Yellowstone National Park (YNP); however, no definitive work has identified specific microorganisms responsible for the oxidation of Fe(II). The objectives of the current study were to isolate and characterize an Fe(II)-oxidizing member of the Sulfolobales observed in previous 16S rRNA gene surveys and to determine the abundance and distribution of close relatives of this organism in acidic geothermal springs containing high concentrations of dissolved Fe(II). Here we report the isolation and characterization of the novel, Fe(II)-oxidizing, thermophilic, acidophilic organism Metallosphaera sp. strain MK1 obtained from a well-characterized acid-sulfate-chloride geothermal spring in Norris Geyser Basin, YNP. Full-length 16S rRNA gene sequence analysis revealed that strain MK1 exhibits only 94.9 to 96.1% sequence similarity to other known Metallosphaera spp. and less than 89.1% similarity to known Sulfolobus spp. Strain MK1 is a facultative chemolithoautotroph with an optimum pH range of 2.0 to 3.0 and an optimum temperature range of 65 to 75°C. Strain MK1 grows optimally on pyrite or Fe(II) sorbed onto ferrihydrite, exhibiting doubling times between 10 and 11 h under aerobic conditions (65°C). The distribution and relative abundance of MK1-like 16S rRNA gene sequences in 14 acidic geothermal springs containing Fe(III) oxide microbial mats were evaluated. Highly related MK1-like 16S rRNA gene sequences (>99% sequence similarity) were consistently observed in Fe(III) oxide mats at temperatures ranging from 55 to 80°C. Quantitative PCR using Metallosphaera-specific primers confirmed that organisms highly similar to strain MK1 comprised up to 40% of the total archaeal community at selected sites. The broad distribution of highly related MK1-like 16S rRNA gene sequences in acidic Fe(III) oxide microbial mats is consistent with the observed characteristics and growth optima of

SYNTHESES, SPECTROSCOPIC AND MAGNETIC PROPERTIES ...

African Journals Online (AJOL)

Preferred Customer

suspension of II reacts with Mn(II), Ni(II), Cd(II), Fe(III) and UO2(VI) ions and ... There has been considerable interest in the synthesis and use of ... chelating abilities in recent years due to their practical convenience, operational flexibility and.

nceiju-iy

Indian Academy of Sciences (India)

students and engaging their minds needs innovative teaching methods. Any novel approach in classroom teaching, even if its impact is marginal, is ... may work them out. For any ... The fact that Fe(III) is more stable than Fe(II) and the concept.

Mitigation of algal organic matter released from Chaetoceros affinis and Hymenomonas by in situ generated ferrate

KAUST Repository

Deka, Bhaskar Jyoti; Jeong, Sanghyun; AlizadehTabatabai, S.Assiyeh; An, Alicia Kyoungjin

2018-01-01

This study demonstrates the application of in situ ferrate (Fe(VI)) for the efficient removal of dissolved algal organic matter (AOM) from seawater. Sodium hypochlorite (NaOCl) and ferric (Fe(III)) were used to produce in situ Fe(VI) by wet chemical

Direct oxide reducing method

International Nuclear Information System (INIS)

Tokiwai, Moriyasu.

1995-01-01

Calcium oxides and magnetic oxides as wastes generated upon direct reduction are subjected to molten salt electrolysis, and reduced metallic calcium and magnesium are separated and recovered. Then calcium and magnesium are used recyclically as the reducing agent upon conducting direct oxide reduction. Even calcium oxides and magnesium oxides, which have high melting points and difficult to be melted usually, can be melted in molten salts of mixed fluorides or chlorides by molten-salt electrolysis. Oxides are decomposed by electrolysis, and oxygen is removed in the form of carbon monoxide, while the reduced metallic calcium and magnesium rise above the molten salts on the side of a cathode, and then separated. Since only carbon monoxide is generated as radioactive wastes upon molten salt electrolysis, the amount of radioactive wastes can be greatly reduced, and the amount of the reducing agent used can also be decreased remarkably. (N.H.)

The long term tsunami impact: Evolution of iron speciation and major elements concentration in tsunami deposits from Thailand.

Science.gov (United States)

Kozak, Lidia; Niedzielski, Przemyslaw

2017-08-01

The article describes the unique studies of the chemical composition changes of new geological object (tsunami deposits in south Thailand - Andaman Sea Coast) during four years (2005-2008) from the beginning of formation of it (deposition of tsunami transported material, 26 December 2004). The chemical composition of the acid leachable fraction of the tsunami deposits has been studied in the scope of concentration macrocompounds - concentration of calcium, magnesium, iron, manganese and iron speciation - the occurrence of Fe(II), Fe(III) and non-ionic iron species described as complexed iron (Fe complex). The changes of chemical composition and iron speciation in the acid leachable fraction of tsunami deposits have been observed with not clear tendencies of changes direction. For iron speciation changes the transformation of the Fe complex to Fe(III) has been recorded with no significant changes of the level of Fe(II). Copyright © 2017 Elsevier Ltd. All rights reserved.

Magnetic interactions and magnetic anisotropy in exchange coupled 4f-3d systems: a case study of a heterodinuclear Ce3+-Fe3+ cyanide-bridged complex.

Science.gov (United States)

Sorace, Lorenzo; Sangregorio, Claudio; Figuerola, Albert; Benelli, Cristiano; Gatteschi, Dante

2009-01-01

We report here a detailed single-crystal EPR and magnetic study of a homologous series of complexes of the type Ln-M (Ln = La(III), Ce(III); M = Fe(III), Co(III)). We were able to obtain a detailed picture of the low-lying levels of Ce(III) and Fe(III) centres through the combined use of single-crystal EPR and magnetic susceptibility data. We show that classical ligand field theory can be of great help in rationalising the energies of the low-lying levels of both the transition-metal and rare-earth ions. The combined analysis of single-crystal EPR and magnetic data of the coupled system Ce-Fe confirmed the great complexity of the interactions involving rare-earth elements. With little uncertainty, it turned out clearly that the description of the interaction involving the lowest lying spin levels requires the introduction of the isotropic, anisotropic and antisymmetric terms.

Specific sequestering agents for iron and the actinides

Energy Technology Data Exchange (ETDEWEB)

Raymond, K.N.

1983-06-01

The transuranium actinide ions represent one unique environmental hazard associated with the waste of the nuclear power industry. A major component associated with that waste and a potential hazard is plutonium. The synthesis of metal-ion-specific complexing agents for ions such as Pu(IV) potentially represents a powerful new approach to many of the problems posed by waste treatment. This document is a progress report of a rational approach to the synthesis of such chelating agents based on the similarities of Pu(IV) and Fe(III), the structures of naturally-occurring complexing agents which are highly specific for Fe(III), and the incorporation of the same kinds of ligating groups present in the iron complexes to make octadentate complexes highly specific for plutonium. Both thermodynamic and animal test results indicate that a relatively high degree of success has already been achieved in this aim.

Determination of uranium (IV) by flow voltammetry

International Nuclear Information System (INIS)

Ding Anqing

1987-01-01

According to the quantitative reaction of U(IV) and Fe(III) in H 2 SO 4 as well as the relation between current and concentration of substance detected, U(IV) has been determined indirectly by measurement of the electrolysis current of residual Fe(III). The columniform electrode used is made of glass carbon particles. At the range of U(IV) from a few micrograms to 40 μg, the linear relation is excellent. The relative standard deviation is within ±4%. The interference of Fe(II), Ti(IV) and U(VI) is negligible but of Ti(III) is serious. This method has been successfully applied in the determination of actual samples (both out line and on line). Main advantages of this procedure are rapid, simple, small amount of sample (only at microgram level) and easy to realize automation, able to use for on line or process analysis

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

DEFF Research Database (Denmark)

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

1995-01-01

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

Pyridinium bis(pyridine-κNtetrakis(thiocyanato-κNferrate(III

Directory of Open Access Journals (Sweden)

Sergii I. Shylin

2013-06-01

Full Text Available In the title compound, (C5H6N[Fe(NCS4(C5H5N2], the FeIII ion is coordinated by four thiocyanate N atoms and two pyridine N atoms in a trans arrangement, forming an FeN6 polyhedron with a slightly distorted octahedral geometry. Charge balance is achieved by one pyridinium cation bound to the complex anion via N—H...S hydrogen bonding. The asymmetric unit consists of one FeIII cation, four thiocyanate anions, two coordinated pyridine molecules and one pyridinium cation. The structure exhibits π–π interactions between pyridine rings [centroid–centroid distances = 3.7267 (2, 3.7811 (2 and 3.8924 (2 Å]. The N atom and a neighboring C atom of the pyridinium cation are statistically disordered with an occupancy ratio of 0.58 (2:0.42 (2.

Using proteomic data to assess a genome-scale "in silico" model of metal reducing bacteria in the simulation of field-scale uranium bioremediation

Science.gov (United States)

Yabusaki, S.; Fang, Y.; Wilkins, M. J.; Long, P.; Rifle IFRC Science Team

2011-12-01

A series of field experiments in a shallow alluvial aquifer at a former uranium mill tailings site have demonstrated that indigenous bacteria can be stimulated with acetate to catalyze the conversion of hexavalent uranium in a groundwater plume to immobile solid-associated uranium in the +4 oxidation state. While this bioreduction of uranium has been shown to lower groundwater concentrations below actionable standards, a viable remediation methodology will need a mechanistic, predictive and quantitative understanding of the microbially-mediated reactions that catalyze the reduction of uranium in the context of site-specific processes, properties, and conditions. At the Rifle IFRC site, we are investigating the impacts on uranium behavior of pulsed acetate amendment, acetate-oxidizing iron and sulfate reducing bacteria, seasonal water table variation, spatially-variable physical (hydraulic conductivity, porosity) and geochemical (reactive surface area) material properties. The simulation of three-dimensional, variably saturated flow and biogeochemical reactive transport during a uranium bioremediation field experiment includes a genome-scale in silico model of Geobacter sp. to represent the Fe(III) terminal electron accepting process (TEAP). The Geobacter in silico model of cell-scale physiological metabolic pathways is comprised of hundreds of intra-cellular and environmental exchange reactions. One advantage of this approach is that the TEAP reaction stoichiometry and rate are now functions of the metabolic status of the microorganism. The linkage of in silico model reactions to specific Geobacter proteins has enabled the use of groundwater proteomic analyses to assess the accuracy of the model under evolving hydrologic and biogeochemical conditions. In this case, the largest predicted fluxes through in silico model reactions generally correspond to high abundances of proteins linked to those reactions (e.g. the condensation reaction catalyzed by the protein

Effect of metal cation ratio on chemical properties of ZnFe2O4/AC composite and adsorption of organic contaminant

Science.gov (United States)

Meilia, Demara; Misbah Khunur, Mochamad; Setianingsih, Tutik

2018-01-01

Porous woody char is biochar prepared through pyrolisis. The biochar can be used as adsorbent. In this research, ZnFe2O4/AC composite was synthesized through imregnation of the woody biochar with ZnFe2O4 to study effect of mol ratio of Fe(III) and Zn(II) toward their physicochemistry and adsorption of drug wastewater. Paracetamol was used as adsorbate model. This research was conducted in several steps, including activation of the woody biochar using KOH activator at temperatur 500 °C for 15 min to produce the activated carbon, fungsionalization of the carbon using H2SO4 oxidator (6M) at temperature of 80 °C for 3 h, impregnation of the oxidized activated carbon with Zn-Fe-LDH (Layered Double Hydroxide) at various mol ratio of Fe(III) and Zn(III), including 1:2, 1:3 and 1:4 using NaOH solution (5M) for coprecipitation, and calcination of Zn-Fe-LDH/AC at 950 °C for 5 min to produce ZnFe2O4/AC. FTIR diffraction characterization indicated existence of M-O (M = Zn(II), Fe(III)) and OH functional groups. FTIR spectra showed increasing of bands connected to -OH by increasing of the ratio till the ratio was achieved at 1:4, then decreased again. The ratio mol showed effect on the adsorption of paracetamol. Profile of adsorption value was fit with changing of functional groups. The highest adsorption was achieved at the ratio of 1:4. After calcination it gave the adsorption value of 17,66 mg/g.

Genomic insights into the iron uptake mechanisms of the biomining microorganism Acidithiobacillus ferrooxidans.

Science.gov (United States)

Quatrini, Raquel; Jedlicki, Eugenia; Holmes, David S

2005-12-01

Commercial bioleaching of copper and the biooxidation of gold is a cost-effective and environmentally friendly process for metal recovery. A partial genome sequence of the acidophilic, bioleaching bacterium Acidithiobacillus ferrooxidans is available from two public sources. This information has been used to build preliminary models that describe how this microorganism confronts unusually high iron loads in the extremely acidic conditions (pH 2) found in natural environments and in bioleaching operations. A. ferrooxidans contains candidate genes for iron uptake, sensing, storage, and regulation of iron homeostasis. Predicted proteins exhibit significant amino acid similarity with known proteins from neutrophilic organisms, including conservation of functional motifs, permitting their identification by bioinformatics tools and allowing the recognition of common themes in iron transport across distantly related species. However, significant differences in amino acid sequence were detected in pertinent domains that suggest ways in which the periplasmic and outer membrane proteins of A. ferrooxidans maintain structural integrity and relevant protein-protein contacts at low pH. Unexpectedly, the microorganism also contains candidate genes, organized in operon-like structures that potentially encode at least 11 siderophore systems for the uptake of Fe(III), although it does not exhibit genes that could encode the biosynthesis of the siderophores themselves. The presence of multiple Fe(III) uptake systems suggests that A. ferrooxidans can inhabit aerobic environments where iron is scarce and where siderophore producers are present. It may also help to explain why it cannot tolerate high Fe(III) concentrations in bioleaching operations where it is out-competed by Leptospirillum species.

Spectrophotometric determination of metal complexes of 1-nitroso-2-naphthol in micellar medium

International Nuclear Information System (INIS)

Shar, G.A.; Bhanger, M.I.

2002-01-01

Spectrophotometric determination of iron(III), nickel(II) and cobalt(II) is carried out with 1-nitroso-2-naphthol as complexing reagent in aqueous phase using non-ionic surfactant Tween 40. This replaces a tedious and time consuming solvent extraction method, because these solvents are costly and also toxic. Beer's law was obeyed, for Fe(III), Ni(II) and Co(II) over the range 0.5 - 4.0, 0.5 - 4.0 and 0.12 - 3.0 micro g ml/sup -1/ with detection limit (2 sigma ) of 3.3, 5.8 and 3.1 ng ml/sup -1/ respectively. The lambda /sub max/ molar absorption, molar absorptivity and Sandell's sensitivity of Fe(III), Ni(II) and Co(II) were (lambda /sub max/ 446 nm), (lambda/sub max/ 483.5 nm) and (lambda/sub max/ 444.5 nm); sigma/sub max/ x 10/sp 4/ mol/sp -1/ cm/sup -1/) is 1.69, 1.0 and 1.86, 3.3, 5.8 and 3.1 ng cm/sup -2/, respectively. The pH at which the complex is formed for Fe(III), Ni(II) and Co(II) is 1, 8 and 5 respectively. The critical micelle concentration (cmc) of 1-nitroso-2-naphthol is 5% solution. The present method is compared with that of atomic absorption spectroscopy and no significant difference is noted between the two methods at 95% confidence level. The method has been applied to the determination of iron(III), nickel(II) and cobalt(II) in pharmaceutical and industrial wastewater samples. (author)

Iron-Mediated Oxidation of Methoxyhydroquinone under Dark Conditions: Kinetic and Mechanistic Insights.

Science.gov (United States)

Yuan, Xiu; Davis, James A; Nico, Peter S

2016-02-16

Despite the biogeochemical significance of the interactions between natural organic matter (NOM) and iron species, considerable uncertainty still remains as to the exact processes contributing to the rates and extents of complexation and redox reactions between these important and complex environmental components. Investigations on the reactivity of low-molecular-weight quinones, which are believed to be key redox active compounds within NOM, toward iron species, could provide considerable insight into the kinetics and mechanisms of reactions involving NOM and iron. In this study, the oxidation of 2-methoxyhydroquinone (MH2Q) by ferric iron (Fe(III)) under dark conditions in the absence and presence of oxygen was investigated within a pH range of 4-6. Although Fe(III) was capable of stoichiometrically oxidizing MH2Q under anaerobic conditions, catalytic oxidation of MH2Q was observed in the presence of O2 due to further cycling between oxygen, semiquinone radicals, and iron species. A detailed kinetic model was developed to describe the predominant mechanisms, which indicated that both the undissociated and monodissociated anions of MH2Q were kinetically active species toward Fe(III) reduction, with the monodissociated anion being the key species accounting for the pH dependence of the oxidation. The generated radical intermediates, namely semiquinone and superoxide, are of great importance in reaction-chain propagation. The kinetic model may provide critical insight into the underlying mechanisms of the thermodynamic and kinetic characteristics of metal-organic interactions and assist in understanding and predicting the factors controlling iron and organic matter transformation and bioavailability in aquatic systems.

Fluorometric determination of aluminium (III) and cadmium (II) by solvent extraction of the ternary complex composed of metal ion, 8-hydroxy-5-quinolinesulfonic acid, and methyltrioctylammonium ion

International Nuclear Information System (INIS)

Kondoh, Yukihiro; Kataoka, Masamitsu; Kambara, Tomihito

1982-01-01

A fluorometric micro determination of aluminium (III) and cadmium (II) using the formation of metal-8-hydroxy-5-quinolinesulfonic acid-capriquat (methyltrioctylammonium) ternary complex is described. These complexes are easily extracted into chloroform phase and the extract emits a strong fluorescence. Spectra of aluminium (III) and cadmium (II) ternary complexes have the excitation maximum at 396 nm and 400 nm, and emission maximum at 501 nm and 524 nm, respectively. Fluorescence intensity of the aluminium (III) and cadmium (II) ternary complexes extracted into chloroform showed the constant and maximum values in the pH range of aqueous phase from 5.3 to 8.5 and 8.1 to 8.5, respectively. The calibration curves for aluminium (III) and cadmium (II) show good proportionality int the concentration range from 0.5 to 5.0 and 1.0 to 50.0 μg, respectively. The relative standard deviation observed with four measurements was found to be 1.8% for 0.5 μg of aluminium (III) and 1.1% for 10.0 μg of cadmium (II). The effect of diverse ions is studied and a 25-fold amount of Cu(II), Ni(II), Fe(II), Fe(III) in weight gave errors, however, the interferences were easily eliminated by the addition of appropriate masking agent. In the determination of cadmium (II), an equal amount of Co(II), Ni(II), Mn(II), Fe(III) and twice amount of Al(III) gave negative errors, however, the interference of Fe(III) and Al(III) were also eliminated as above. (author)

Bulletin of Materials Science | Indian Academy of Sciences

Indian Academy of Sciences (India)

Photoelectrochemical studies on colloidal copper (I) oxide/modified with some organic semiconductors: Incentive for use of nanoparticle systems ... The research is now focused on the use of microwave processing for industrial applications. ... for Fe(III) determination in rock sample, pharmaceutical sample and water sample.

Evidence for Microbial Iron Reduction in a Landfill Leachate-Polluted Aquifer (Vejen, Denmark)

DEFF Research Database (Denmark)

Albrechtsen, Hans-Jørgen; Christensen, Thomas Højlund

1994-01-01

Aquifer sediment samples obtained from the anaerobic part of a landfill leachate plume in Vejen, Denmark, were suspended in groundwater or in an artificial medium and incubated. The strictly anaerobic suspensions were tested for reduction of ferric iron (Fe(III)) oxides, which was measured...

Au/iron oxide catalysts: temperature programmed reduction and X-ray diffraction characterization

International Nuclear Information System (INIS)

Neri, G.; Visco, A.M.; Galvagno, S.; Donato, A.; Panzalorto, M.

1999-01-01

Gold on iron oxides catalysts have been characterized by temperature programmed reduction (TPR) and X-ray diffraction spectroscopy (XRD). The influence of preparation method, gold loading and pretreatment conditions on the reducibility of iron oxides have been investigated. On the impregnated Au/iron oxide catalysts as well as on the support alone the partial reduction of Fe(III) oxy(hydroxides) to Fe 3 O 4 starts in the 550 and 700 K temperature range. On the coprecipitated samples, the temperature of formation of Fe 3 O 4 is strongly dependent on the presence of gold. The reduction temperature is lowered as the gold loading is increased. The reduction of Fe 3 O 4 to FeO occurs at about 900 K and is not dependent on the presence of gold and the preparation method. It is suggested that the effect of gold on the reducibility of the iron oxides is related to an increase of the structural defects and/or of the surface hydroxyl groups. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

Radiolysis of Aqueous Toluene Solutions

International Nuclear Information System (INIS)

Christensen, H.C.; Gustafson, R.

1971-04-01

Aqueous toluene solutions have been irradiated with Co γ-rays. In unbuffered solutions the various cresol isomers are formed in a total yield of 0.45, 0.87 and 0.94 molecules/100 eV absorbed energy in argon-, N 2 O- and air - saturated solutions, respectively. The yields are reduced in acid (pH 3) solutions (G 0.14, 0.14 and 0.52, respectively) but the reduction is compensated by the formation of 1,2-di-phenylethane in yields of 0.49 and 1.60 in argon- and N 2 O-saturated solutions, respectively. Benzyl radicals are formed through an acid catalysed water elimination reaction from the initially formed hydroxymethylcyclohexadienyl radical. Phenyltolylmethanes, dimethylbiphenyls and partly reduced dimers are also formed during the radiolysis. Hydrogen is formed in the same yield as the molecular yield, g(H 2 ). Xylene isomers and benzene are formed in trace quantities. The most remarkable effects of the addition of Fe(III) ions to deaerated acid toluene solutions are the formation of benzyl alcohol and benzaldehyde and an increase in the yield of 1,2-diphenylethane

Interruption with the Migration of Iodide by GR(CT)

International Nuclear Information System (INIS)

Min, J. H.; Lee, J. K.; Jeong, J. T.

2012-01-01

The purpose of this study is to understand the influence of green rust on the migration of iodide. GR(CT) would be major corrosion product of iron near the seawater or saline layer in underground. The GR(CT) may play an important role in the retardation of the iodide migration in a deep geological environment due to it's anionic exchange reaction. In underground radioactive waste repository, the corrosion of iron canisters would be proceed as follows; Fe(II) and/or Fe(III) dissolved from iron containers → Fe(II)(OH) 2 and/or Fe(III)(OH) 3 → Green rust → Lepidocrocite or Magnetite → Goetite etc. Generally, the green rust has known to exist in environments close to the Fe(Π)/Fe(ΠΙ) transition zone or between the oxidized layer and reduced layer in the underground. As anion exchanger and strong reducer, the green rusts can affect the migration of anions, reactions involving green rusts were poorly studied in relation to the safety assessment of radioactive waste repository

Oxygen-reducing catalyst layer

Science.gov (United States)

O'Brien, Dennis P [Maplewood, MN; Schmoeckel, Alison K [Stillwater, MN; Vernstrom, George D [Cottage Grove, MN; Atanasoski, Radoslav [Edina, MN; Wood, Thomas E [Stillwater, MN; Yang, Ruizhi [Halifax, CA; Easton, E Bradley [Halifax, CA; Dahn, Jeffrey R [Hubley, CA; O'Neill, David G [Lake Elmo, MN

2011-03-22

An oxygen-reducing catalyst layer, and a method of making the oxygen-reducing catalyst layer, where the oxygen-reducing catalyst layer includes a catalytic material film disposed on a substrate with the use of physical vapor deposition and thermal treatment. The catalytic material film includes a transition metal that is substantially free of platinum. At least one of the physical vapor deposition and the thermal treatment is performed in a processing environment comprising a nitrogen-containing gas.

Hydroxylamine Nitrate Decomposition under Non-radiological Conditions

Energy Technology Data Exchange (ETDEWEB)

McFarlane, Joanna [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Delmau, Laetitia Helene [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); DePaoli, David W. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Mattus, Catherine H. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Phelps, Clarice E. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Roach, Benjamin D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2015-07-01

Hydroxylamine nitrate (HAN) is used to reduce Pu(IV) to Pu(III) in the separation of plutonium from uranium. HAN becomes unstable under certain conditions and has been known to explode, causing injury to humans including death. Hence, it is necessary to deactivate HAN once the reduction of plutonium is finished. This report reviews what is known about the chemistry of HAN and various methods to achieve a safe decomposition. However, there are areas where more information is needed to make a decision about the handling of HAN in reprocessing of nuclear fuel. Experiments have demonstrated a number of non-radiolytic ways to safely decompose HAN, including heating in HNO3, photolytic oxidation in the presence of H2O2, and the addition of a metal such as Fe(III) that will oxidize the HAN.