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

Science.gov (United States)

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

1998-12-01

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

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

Science.gov (United States)

Fantola Lazzarini, Anna L.; Lazzarini, Ennio

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

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

International Nuclear Information System (INIS)

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

2006-01-01

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

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.)

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)

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.

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

International Nuclear Information System (INIS)

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

1982-01-01

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

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

International Nuclear Information System (INIS)

Genin, J.-M. R.

2004-01-01

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

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

OpenAIRE

Clemente Tejeda, David

2015-01-01

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

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

International Nuclear Information System (INIS)

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

2015-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-12-30

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

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

International Nuclear Information System (INIS)

Lengen, M.; Chaudhuri, P.

1994-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2012-12-01

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

Solid Phase Extraction of Trace Al(III), Fe(II), Co(II), Cu(II), Cd(II) and Pb(II) Ions in Beverages on Functionalized Polymer Microspheres Prior to Flame Atomic Absorption Spectrometric Determinations.

Science.gov (United States)

Berber, Hale; Alpdogan, Güzin

2017-01-01

In this study, poly(glycidyl methacrylate-methyl methacrylate-divinylbenzene) was synthesized in the form of microspheres, and then functionalized by 2-aminobenzothiazole ligand. The sorption properties of these functionalized microspheres were investigated for separation, preconcentration and determination of Al(III), Fe(II), Co(II), Cu(II), Cd(II) and Pb(II) ions using flame atomic absorption spectrometry. The optimum pH values for quantitative sorption were 2 - 4, 5 - 8, 6 - 8, 4 - 6, 2 - 6 and 2 - 3 for Al(III), Fe(II), Co(II), Cu(II), Cd(II) and Pb(II), respectively, and also the highest sorption capacity of the functionalized microspheres was found to be for Cu(II) with the value of 1.87 mmol g -1 . The detection limits (3σ; N = 6) obtained for the studied metals in the optimal conditions were observed in the range of 0.26 - 2.20 μg L -1 . The proposed method was successfully applied to different beverage samples for the determination of Al(III), Fe(II), Co(II), Cu(II), Cd(II) and Pb(II) ions, with the relative standard deviation of <3.7%.

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

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

Science.gov (United States)

Liu, Hongyan; Wang, Hongyu

2016-07-01

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

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

Science.gov (United States)

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

2006-06-01

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

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

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.

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

Directory of Open Access Journals (Sweden)

Lucia Helena Garófalo Chaves

2009-10-01

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

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.

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)].

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

Influence of organics and silica on Fe(II) oxidation rates and cell-mineral aggregate formation by the green-sulfur Fe(II)-oxidizing bacterium Chlorobium ferrooxidans KoFox - Implications for Fe(II) oxidation in ancient oceans

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Gauger, Tina; Byrne, James M.; Konhauser, Kurt O.; Obst, Martin; Crowe, Sean; Kappler, Andreas

2016-06-01

Most studies on microbial phototrophic Fe(II) oxidation (photoferrotrophy) have focused on purple bacteria, but recent evidence points to the importance of green-sulfur bacteria (GSB). Their recovery from modern ferruginous environments suggests that these photoferrotrophs can offer insights into how their ancient counterparts grew in Archean oceans at the time of banded iron formation (BIF) deposition. It is unknown, however, how Fe(II) oxidation rates, cell-mineral aggregate formation, and Fe-mineralogy vary under environmental conditions reminiscent of the geological past. To address this, we studied the Fe(II)-oxidizer Chlorobium ferrooxidans KoFox, a GSB living in co-culture with the heterotrophic Geospirillum strain KoFum. We investigated the mineralogy of Fe(III) metabolic products at low/high light intensity, and in the presence of dissolved silica and/or fumarate. Silica and fumarate influenced the crystallinity and particle size of the produced Fe(III) minerals. The presence of silica also enhanced Fe(II) oxidation rates, especially at high light intensities, potentially by lowering Fe(II)-toxicity to the cells. Electron microscopic imaging showed no encrustation of either KoFox or KoFum cells with Fe(III)-minerals, though weak associations were observed suggesting co-sedimentation of Fe(III) with at least some biomass via these aggregates, which could support diagenetic Fe(III)-reduction. Given that GSB are presumably one of the most ancient photosynthetic organisms, and pre-date cyanobacteria, our findings, on the one hand, strengthen arguments for photoferrotrophic activity as a likely mechanism for BIF deposition on a predominantly anoxic early Earth, but, on the other hand, also suggest that preservation of remnants of Fe(II)-oxidizing GSB as microfossils in the rock record is unlikely.

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

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

1999-01-01

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

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

Science.gov (United States)

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

1999-08-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2018-01-17

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2012-03-15

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

Simultaneous absorption of NO and SO{sub 2} into Fe-II-EDTA solution coupled with the Fe-II-EDTA regeneration catalyzed by activated carbon

Energy Technology Data Exchange (ETDEWEB)

Zhu, H.S.; Mao, Y.P.; Yang, X.J.; Chen, Y.; Long, X.L.; Yuan, W.K. [East China University of Science & Technology, Shanghai (China)

2010-07-30

The simultaneous removal of NO and SO{sub 2} from flue gases can be realized with Fe(II)-ethylenediamineteraacetate (EDTA) solution. Activated carbon is used to catalyze the reduction of Fe-III-EDTA to Fe-II-EDTA to maintain the capability of removing NO of the Fe-EDTA solution. The reductant is the sulfite/bisulfite ions produced by SO{sub 2} dissolving into the aqueous solution. Experiments have been performed to determine the effects of activated carbon of coconut shell, Fe-II-EDTA concentration, Fe/EDTA molar ratio, SO{sub 2} partial pressure, NO partial pressure and SO{sub 4}{sup 2-} concentration on the combined elimination of NO and SO{sub 2} with Fe-II-EDTA solution coupled with the Fe-II-EDTA regeneration catalyzed by activated carbon. According to the experimental results, activated carbon not only catalyzes the reduction of Fe-III-EDTA by sulfite/bisulfite greatly but also avoids the release of N{sub 2}O. The NO removal efficiency increases with the initial Fe-II-EDTA concentration and SO{sub 2} partial pressure. The ratio of Fe/EDTA and the SO{sub 4}{sup 2-} concentration has little effect on the catalytic reduction of Fe-III-EDTA. The optimal initial NO concentration range is from 600 ppm to 900 ppm. The experimental results manifest that the Fe-II-EDTA solution coupled with catalytic regeneration of Fe-II-EDTA can maintain high nitric oxide removal efficiency for a long period of time.

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

Energy Technology Data Exchange (ETDEWEB)

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

2002-07-01

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

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.

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

Science.gov (United States)

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

2017-11-01

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

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

Science.gov (United States)

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

2012-11-28

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

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.

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.

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

Science.gov (United States)

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

2002-04-01

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

Physiology, Fe(II oxidation, and Fe mineral formation by a marine planktonic cyanobacterium grown under ferruginous conditions

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Elizabeth D. Swanner

2015-10-01

Full Text Available Evidence for Fe(II oxidation and deposition of Fe(III-bearing minerals from anoxic or redox-stratified Precambrian oceans has received support from decades of sedimentological and geochemical investigation of Banded Iron Formations (BIF. While the exact mechanisms of Fe(II oxidation remains equivocal, reaction with O2 in the marine water column, produced by cyanobacteria or early oxygenic phototrophs, was likely. In order to understand the role of cyanobacteria in the deposition of Fe(III minerals to BIF, we must first know how planktonic marine cyanobacteria respond to ferruginous (anoxic and Fe(II-rich waters in terms of growth, Fe uptake and homeostasis, and Fe mineral formation. We therefore grew the common marine cyanobacterium Synechococcus PCC 7002 in closed bottles that began anoxic, and contained Fe(II concentrations that span the range of possible concentrations in Precambrian seawater. These results, along with cell suspension experiments, indicate that Fe(II is likely oxidized by this strain via chemical oxidation with oxygen produced during photosynthesis, and not via any direct enzymatic or photosynthetic pathway. Imaging of the cell-mineral aggregates with scanning electron microscopy (SEM and confocal laser scanning microscopy (CLSM are consistent with extracellular precipitation of Fe(III (oxyhydroxide minerals, but that >10% of Fe(III sorbs to cell surfaces rather than precipitating. Proteomic experiments support the role of reactive oxygen species (ROS in Fe(II toxicity to Synechococcus PCC 7002. The proteome expressed under low Fe conditions included multiple siderophore biosynthesis and siderophore and Fe transporter proteins, but most siderophores are not expressed during growth with Fe(II. These results provide a mechanistic and quantitative framework for evaluating the geochemical consequences of perhaps life’s greatest metabolic innovation, i.e. the evolution and activity of oxygenic photosynthesis, in ferruginous

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

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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.

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

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

2012-03-01

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

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

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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.

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

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Bassez, Marie-Paule

2017-12-01

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

Fe (III), Co(II), Ni(II), Cu(II) and Zn(II) complexes of schiff bases based-on glycine and phenylalanine: Synthesis, magnetic/thermal properties and antimicrobial activity

Science.gov (United States)

Sevgi, Fatih; Bagkesici, Ugur; Kursunlu, Ahmed Nuri; Guler, Ersin

2018-02-01

Zinc (II), copper (II), nickel (II), cobalt (II) and iron (III) complexes of Schiff bases (LG, LP) derived from 2-hydroxynaphthaldehyde with glycine and phenylalanine were reported and characterized by 1H NMR, 13C NMR, elemental analyses, melting point, FT-IR, magnetic susceptibility and thermal analyses (TGA). TGA data show that iron and cobalt include to the coordinated water and metal:ligand ratio is 1:2 while the complex stoichiometry for Ni (II), Cu (II) and Zn (II) complexes is 1:1. As expected, Ni (II) and Zn (II) complexes are diamagnetic; Cu (II), Co (II) and Fe (III) complexes are paramagnetic character due to a strong ligand of LG and LP. The LG, LP and their metal complexes were screened for their antimicrobial activities against five Gram-positive (Staphylococcus aureus, Methicillin resistant Staphylococcus aureus (MRSA), Bacillus cereus, Streptococcus mutans and Enterococcus faecalis) and three Gram-negative (Escherichia coli, Klebsiella pneumoniae and Pseudomonas aeruginosa) and one fungi (Candida albicans) by using broth microdilution techniques. The activity data show that ligands and their metal complexes exhibited moderate to good activity against Gram-positive bacteria and fungi.

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

Redox characterization of the Fe(II)-catalyzed transformation of ferrihydrite to goethite

Science.gov (United States)

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

2017-12-01

The reduction potential of Fe(II)-Fe(III) (oxyhydr)oxide systems provides an important control on the biogeochemical cycling of redox-sensitive elements such as carbon and nitrogen as well as trace metals and organic contaminants in natural systems. As such, an in-depth understanding of the factors controlling the reduction potential of such systems is critical to predicting the likely transformation, transport and fate of these species in natural and perturbed environments. In this study the mineralogy and reduction potential of ferrihydrite suspensions at pH 6.50 and pH 7.00 were determined over the course of their Fe(II)-catalyzed transformation to lepidocrocite and goethite using X-ray absorption spectroscopy and mediated electrochemical approaches. The measured reduction potentials were compared to those of analogous Fe(II)-Fe(III) (oxyhydr)oxide suspensions reacted for 5 min containing pure ferrihydrite (Fh), lepidocrocite (L) and goethite (Gt). The reduction potentials of the pure Fe(II)-Fe(III) (oxyhydr)oxide suspensions were, respectively, +47.5, -13.5 and -122.3 mV vs. SHE at pH 6.5, and -22.9, -84.1 and -189.7 mV vs. SHE at pH 7. These values are in good agreement with reduction potentials calculated using the Nernst equation and reported thermodynamic solubility products indicating that these suspensions had reached equilibrium within 5 min. The reduction potential of the pH 6.50 Fe(II)-ferrihydrite suspension decreased from +47.4 mV to -126.4 mV over a week, and from -20.1 mV to -188.4 mV (all vs. SHE) after 24 h at pH 7. The changes in reduction potential over time matched well to those calculated from the relative proportion of each pure Fe(III) (oxyhydr)oxide present suggesting that Fe3+ activity was influenced by the mix of iron oxides present rather than the most insoluble solid species. Finally, evidence is provided that adsorbed Fe(II) has the capacity to reduce a significantly larger fraction of a reducible species than the aqueous Fe(II

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

Science.gov (United States)

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

1999-01-01

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

Microbiological evidence for Fe(III) reduction on early Earth

Science.gov (United States)

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

1998-09-01

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

Correlation of reactivity with structural factors in a series of Fe(II) substituted cobalt ferrites

International Nuclear Information System (INIS)

Sileo, Elsa E.; Garcia Rodenas, Luis; Paiva-Santos, Carlos O.; Stephens, Peter W.; Morando, Pedro J.; Blesa, Miguel A.

2006-01-01

A series of powdered cobalt ferrites, Co x Fe 3- x O 4 with 0.66≤x II , were synthesized by a mild procedure, and their Fe and Co site occupancies and structural characteristics were explored using X-ray anomalous scattering and the Rietveld refinement method. The dissolution kinetics, measured in 0.1 M oxalic acid aqueous solution at 70 deg. C, indicate in all cases the operation of a contracting volume rate law. The specific rates increased with the Fe II content following approximately a second-order polynomial expression. This result suggests that the transfer of Fe III controls the dissolution rate, and that the leaching of a first layer of ions Co II and Fe II leaves exposed a surface enriched in slower dissolving octahedral Fe III ions. Within this model, inner vicinal lattice Fe II accelerates the rate of Fe III transfer via internal electron hopping. A chain mechanism, involving successive electron transfers, fits the data very well. - Graphical abstract: The electron exchange between octahedral Fe II and Fe III ions has important consequences on the specific dissolution rates. Display Omitted

Kinetics and Products of Chromium(VI) Reduction by Iron(II/III)-Bearing Clay Minerals.

Science.gov (United States)

Joe-Wong, Claresta; Brown, Gordon E; Maher, Kate

2017-09-05

Hexavalent chromium is a water-soluble pollutant, the mobility of which can be controlled by reduction of Cr(VI) to less soluble, environmentally benign Cr(III). Iron(II/III)-bearing clay minerals are widespread potential reductants of Cr(VI), but the kinetics and pathways of Cr(VI) reduction by such clay minerals are poorly understood. We reacted aqueous Cr(VI) with two abiotically reduced clay minerals: an Fe-poor montmorillonite and an Fe-rich nontronite. The effects of ionic strength, pH, total Fe content, and the fraction of reduced structural Fe(II) [Fe(II)/Fe(total)] were examined. The last variable had the largest effect on Cr(VI) reduction kinetics: for both clay minerals, the rate constant of Cr(VI) reduction varies by more than 3 orders of magnitude with Fe(II)/Fe(total) and is described by a linear free energy relationship. Under all conditions examined, Cr and Fe K-edge X-ray absorption near-edge structure spectra show that the main Cr-bearing product is a Cr(III)-hydroxide and that Fe remains in the clay structure after reacting with Cr(VI). This study helps to quantify our understanding of the kinetics of Cr(VI) reduction by Fe(II/III)-bearing clay minerals and may improve predictions of Cr(VI) behavior in subsurface environments.

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

DEFF Research Database (Denmark)

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

2010-01-01

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

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.

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

Energy Technology Data Exchange (ETDEWEB)

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

1965-10-15

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

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

Directory of Open Access Journals (Sweden)

Nezamaddin Daneshvar

2007-03-01

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

Studies of the yields of 57Fe(II)-species produced after the EC-decay and of 60Co(II)-species produced in the (n, γ) reaction in cobalt(III) coordination compounds

International Nuclear Information System (INIS)

Sano, Hirotoshi; Harada, Masayuki; Endo, Kazutoyo

1978-01-01

The yields of 57 Fe(II)-species produced after EC-decay were compared with those of 60 Co(II)-species produced in the 59 Co(n, γ) 60 Co reaction for twelve cobalt(III) coordination compounds. The results indicate that the radiochemical yield of 60 Co(II)-species correlates with the yield of 57 Fe(II)-species except in the case of [Co(NH 3 ) 6 ] 2 (CrO 4 ) 3 . The anomalously low yield of 57 Fe(II)-species in [Co(NH 3 ) 6 ] 2 (CrO 4 ) 3 is ascribed to the reaction of chromate anions with ammine ligands initiated by the nuclear transformation in a solid. (author)

Modeling Fe II Emission and Revised Fe II (UV) Empirical Templates for the Seyfert 1 Galaxy I Zw 1

Science.gov (United States)

Bruhweiler, F.; Verner, E.

2008-03-01

We use the narrow-lined broad-line region (BLR) of the Seyfert 1 galaxy, I Zw 1, as a laboratory for modeling the ultraviolet (UV) Fe II 2100-3050 Å emission complex. We calculate a grid of Fe II emission spectra representative of BLR clouds and compare them with the observed I Zw 1 spectrum. Our predicted spectrum for log [nH/(cm -3) ] = 11.0, log [ΦH/(cm -2 s-1) ] = 20.5, and ξ/(1 km s-1) = 20, using Cloudy and an 830 level model atom for Fe II with energies up to 14.06 eV, gives a better fit to the UV Fe II emission than models with fewer levels. Our analysis indicates (1) the observed UV Fe II emission must be corrected for an underlying Fe II pseudocontinuum; (2) Fe II emission peaks can be misidentified as that of other ions in active galactic nuclei (AGNs) with narrow-lined BLRs possibly affecting deduced physical parameters; (3) the shape of 4200-4700 Å Fe II emission in I Zw 1 and other AGNs is a relative indicator of narrow-line region (NLR) and BLR Fe II emission; (4) predicted ratios of Lyα, C III], and Fe II emission relative to Mg II λ2800 agree with extinction corrected observed I Zw 1 fluxes, except for C IV λ1549 (5) the sensitivity of Fe II emission strength to microturbulence ξ casts doubt on existing relative Fe/Mg abundances derived from Fe II (UV)/Mg II flux ratios. Our calculated Fe II emission spectra, suitable for BLRs in AGNs, are available at http://iacs.cua.edu/people/verner/FeII. Based on observations made with the NASA/ESA Hubble Space Telescope, obtained at the Space Telescope Science Institute, which is operated by the Association of Universities for Research in Astronomy, Inc., under NASA contract NAS 05-26555.

Removal of Fe(II) from tap water by electrocoagulation technique

International Nuclear Information System (INIS)

Ghosh, D.; Solanki, H.; Purkait, M.K.

2008-01-01

Electrocoagulation (EC) is a promising electrochemical technique for water treatment. In this work electrocoagulation (with aluminum as electrodes) was studied for iron Fe(II) removal from aqueous medium. Different concentration of Fe(II) solution in tap water was considered for the experiment. During EC process, various amorphous aluminum hydroxides complexes with high sorption capacity were formed. The removal of Fe(II) was consisted of two principal steps; (a) oxidation of Fe(II) to Fe(III) and (b) subsequent removal of Fe(III) by the freshly formed aluminum hydroxides complexes by adsorption/surface complexation followed by precipitation. Experiments were carried out with different current densities ranging from 0.01 to 0.04 A/m 2 . It was observed that the removal of Fe(II) increases with current densities. Inter electrode distance was varied from 0.005 to 0.02 m and was found that least inter electrode distance is suitable in order to achieve higher Fe(II) removal. Other parameters such as conductivity, pH and salt concentration were kept constant as per tap water quality. Satisfactory iron removal of around 99.2% was obtained at the end of 35 min of operation from the initial concentration of 25 mg/L Fe(II). Iron concentration in the solution was determined using Atomic absorption spectrophotometer. By products obtained from the electrocoagulation bath were analyzed by SEM image and corresponding elemental analysis (EDAX). Cost estimation for the electrocoagulation was adopted and explained well. Up to 15 mg/L of initial Fe(II) concentration, the optimum total cost was 6.05 US$/m 3 . The EC process for removing Fe(II) from tap water is expected to be adaptable for household use

Reductive dehalogenation by layered iron(II)-iron(III) hydroxides and related iron(II) containing solids

DEFF Research Database (Denmark)

Yin, Weizhao

In the present PhD project, novel synthesis and modifications of layered Fe(II)-Fe(III) hydroxides (green rusts, GRs) were investigated with focus on improved dehalogenation of carbon tetrachloride by using modified green rusts and/or altered reaction conditions. The Ph.D. project has comprised: 1...... sulphate green rust formation by aerial oxidation of FeII or co-precipitation by adding Fe(III) salt to Fe(II). In comparison with traditional green rust synthesis, pure GRs were synthesized in minutes. 2. Enhanced dehalogenation of CT by GR in presence of selected amino acids. In presence of glycine......, chloroform (CF) formation is effectively suppressed: less than 10% of CT is transformed to CF, and more than 90% of dehalogenation products are found to be formic acid and carbon monoxide in presence of 60 mM glycine; while a 80% of CF recovery was obtained without amino acids addition. 3. A “switch...

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

Science.gov (United States)

Dot, K

1978-02-01

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

Removal of Fe(II) from tap water by electrocoagulation technique

Energy Technology Data Exchange (ETDEWEB)

Ghosh, D.; Solanki, H. [Department of Chemical Engineering, Indian Institute of Technology, Guwahati 781039 (India); Purkait, M.K. [Department of Chemical Engineering, Indian Institute of Technology, Guwahati 781039 (India)], E-mail: mihir@iitg.ernet.in

2008-06-30

Electrocoagulation (EC) is a promising electrochemical technique for water treatment. In this work electrocoagulation (with aluminum as electrodes) was studied for iron Fe(II) removal from aqueous medium. Different concentration of Fe(II) solution in tap water was considered for the experiment. During EC process, various amorphous aluminum hydroxides complexes with high sorption capacity were formed. The removal of Fe(II) was consisted of two principal steps; (a) oxidation of Fe(II) to Fe(III) and (b) subsequent removal of Fe(III) by the freshly formed aluminum hydroxides complexes by adsorption/surface complexation followed by precipitation. Experiments were carried out with different current densities ranging from 0.01 to 0.04 A/m{sup 2}. It was observed that the removal of Fe(II) increases with current densities. Inter electrode distance was varied from 0.005 to 0.02 m and was found that least inter electrode distance is suitable in order to achieve higher Fe(II) removal. Other parameters such as conductivity, pH and salt concentration were kept constant as per tap water quality. Satisfactory iron removal of around 99.2% was obtained at the end of 35 min of operation from the initial concentration of 25 mg/L Fe(II). Iron concentration in the solution was determined using Atomic absorption spectrophotometer. By products obtained from the electrocoagulation bath were analyzed by SEM image and corresponding elemental analysis (EDAX). Cost estimation for the electrocoagulation was adopted and explained well. Up to 15 mg/L of initial Fe(II) concentration, the optimum total cost was 6.05 US$/m{sup 3}. The EC process for removing Fe(II) from tap water is expected to be adaptable for household use.

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.

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.

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...

Charge transport in micas: The kinetics of FeII/III electron transfer in the octahedral sheet

International Nuclear Information System (INIS)

Rosso, Kevin M.; Ilton, Eugene S.

2003-01-01

The two principal FeII/III electron exchange reactions underlying charge transport in the octahedral sheet of ideal end-member annite were modeled using a combination of ab initio calculations and Marcus electron transfer theory. A small polaron model was applied which yielded electron hopping activation energies that agree well with the limited available experimental data. A small ab initio cluster model successfully reproduced several important structural, energetic, and magnetic characteristics of the M1 and M2 Fe sites in the annite octahedral sheet. The cluster enabled calculation of the internal reorganization energy and electronic coupling matrix elements for the M2-M2 and M1-M2 electron transfer reactions. The M2-M2 electron transfer is symmetric with a predicted forward/reverse electron hopping rate of 106 s-1. The M1-M2 electron transfers are asymmetric due to the higher ionization potential by 0.46 eV of FeII in the M1 site. The electronic coupling matrix elements for these reactions are predicted to be small and of similar magnitude, suggesting the possibility that the coupling is essentially direction independent amongst hopping directions in the octahedral sheet. M1 Fe sites are predicted to be efficient electron traps and charge transport should occur by nearest-neighbor electron hops along the M2 Fe sublattice

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.

Abiotic and microbial interactions during anaerobic transformations of Fe(II and NOx-

Directory of Open Access Journals (Sweden)

Flynn ePicardal

2012-03-01

Full Text Available Microbial Fe(II oxidation using NO3- as the terminal electron acceptor (nitrate-dependent Fe(II oxidation; NDFO has been studied for over 15 years. Although there are reports of autotrophic isolates and stable enrichments, many of the bacteria capable of NDFO are known organotrophic NO3- -reducers that require the presence of an organic, primary substrate, e.g., acetate, for significant amounts of Fe(II oxidation. Although the thermodynamics of Fe(II oxidation are favorable when coupled to either NO3- or NO2- reduction, the kinetics of abiotic Fe(II oxidation by NO3- are relatively slow except under special conditions. NDFO is typically studied in batch cultures containing millimolar concentrations of Fe(II, NO3-, and the primary substrate. In such systems, NO2- is often observed to accumulate in culture media during Fe(II oxidation. Compared to NO3-, abiotic reactions of biogenic NO2- and Fe(II are relatively rapid. The kinetics and reaction pathways of Fe(II oxidation by NO2- are strongly affected by medium composition and pH, reactant concentration, and the presence of Fe(II-sorptive surfaces, e.g., Fe(III oxyhydroxides and cellular surfaces. In batch cultures, the combination of abiotic and microbial Fe(II oxidation can alter product distribution and, more importantly, results in the formation of intracellular precipitates and extracellular Fe(III oxyhydroxide encrustations that apparently limit further cell growth and Fe(II oxidation. Unless steps are taken to minimize or account for potential abiotic reactions, results of microbial NDFO studies can be obfuscated by artifacts of the chosen experimental conditions, the use of inappropriate analytical methods, and the resulting uncertainties about the relative importance of abiotic and microbial reactions.In this manuscript, abiotic reactions of NO3- and NO2- with aqueous Fe2+, chelated Fe(II, and solid-phase Fe(II are reviewed along with factors that can influence overall NDFO reac

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.

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)

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-01-15

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

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

Thermodynamic controls on the kinetics of microbial low-pH Fe(II) oxidation.

Science.gov (United States)

Larson, Lance N; Sánchez-España, Javier; Kaley, Bradley; Sheng, Yizhi; Bibby, Kyle; Burgos, William D

2014-08-19

Acid mine drainage (AMD) is a major worldwide environmental threat to surface and groundwater quality. Microbial low-pH Fe(II) oxidation could be exploited for cost-effective AMD treatment; however, its use is limited because of uncertainties associated with its rate and ability to remove Fe from solution. We developed a thermodynamic-based framework to evaluate the kinetics of low-pH Fe(II) oxidation. We measured the kinetics of low-pH Fe(II) oxidation at five sites in the Appalachian Coal Basin in the US and three sites in the Iberian Pyrite Belt in Spain and found that the fastest rates of Fe(II) oxidation occurred at the sites with the lowest pH values. Thermodynamic calculations showed that the Gibbs free energy of Fe(II) oxidation (ΔG(oxidation)) was also most negative at the sites with the lowest pH values. We then conducted two series of microbial Fe(II) oxidation experiments in laboratory-scale chemostatic bioreactors operated through a series of pH values (2.1-4.2) and found the same relationships between Fe(II) oxidation kinetics, ΔG(oxidation), and pH. Conditions that favored the fastest rates of Fe(II) oxidation coincided with higher Fe(III) solubility. The solubility of Fe(III) minerals, thus plays an important role on Fe(II) oxidation kinetics. Methods to incorporate microbial low-pH Fe(II) oxidation into active and passive AMD treatment systems are discussed in the context of these findings. This study presents a simplified model that describes the relationship between free energy and microbial kinetics and should be broadly applicable to many biogeochemical systems.

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 ...

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.

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...

Reactive Fe(II) layers in deep-sea sediments

Science.gov (United States)

König, Iris; Haeckel, Matthias; Drodt, Matthias; Suess, Erwin; Trautwein, Alfred X.

1999-05-01

The percentage of the structural Fe(II) in clay minerals that is readily oxidized to Fe(III) upon contact with atmospheric oxygen was determined across the downcore tan-green color change in Peru Basin sediments. This latent fraction of reactive Fe(II) was only found in the green strata, where it proved to be large enough to constitute a deep reaction layer with respect to the pore water O 2 and NO 3-. Large variations were detected in the proportion of the reactive Fe(II) concentration to the organic matter content along core profiles. Hence, the commonly observed tan-green color change in marine sediments marks the top of a reactive Fe(II) layer, which may represent the major barrier to the movement of oxidation fronts in pelagic subsurface sediments. This is also demonstrated by numerical model simulations. The findings imply that geochemical barriers to pore water oxidation fronts form diagenetically in the sea floor wherever the stage of iron reduction is reached, provided that the sediments contain a significant amount of structural iron in clay minerals.

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

Science.gov (United States)

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

2017-12-01

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

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....

Kinetics of FeII-polyaminocarboxylate oxidation by molecular oxygen

Science.gov (United States)

Wilson, Jessica M.; Farley, Kevin J.; Carbonaro, Richard F.

2018-03-01

Complexation of iron by naturally-occurring and synthetic organic ligands has a large effect on iron oxidation and reduction rates which in turn affect the aqueous geochemistry of many other chemical constituents. In this study, the kinetics of FeII oxidation in the presence of the polyaminocarboxylate synthetic chelating agents ethylene glycol tetraacetic acid (EGTA) and trimethylenediamine-N,N,N‧,N‧-tetraacetic acid (TMDTA) was investigated over the pH range 5.50-8.53. Batch oxidation experiments in the presence of molecular oxygen were conducted using a 2:1 M concentration ratio of polyaminocarboxylate (ligand, L) to FeII. The experimental data resembled first order kinetics for the oxidation of FeII-L to FeIII-L and observed rate constants at pH 6.0 were comparable to rate constants for the oxidation of inorganic FeII. Similar to other structurally-similar FeII-polyaminocarboxylate complexes, oxidation rates of FeII-EGTA and FeII-TMDTA decrease with increasing pH, which is the opposite trend for the oxidation of FeII complexed with inorganic ligands. However, the oxidation rates of FeII complexed with EGTA and TMDTA were considerably lower (4-5 orders of magnitude) than FeII complexed to ethylenediaminetetraacetic acid (EDTA). The distinguishing feature of the slower-reacting complexes is that they have a longer backbone between diamine functional groups. An analytical equilibrium model was developed to determine the contributions of the species FeIIL2- and FeII(H)L- to the overall oxidation rate of FeII-L. Application of this model indicated that the protonated FeII(H)L species are more than three orders of magnitude more reactive than FeIIL2-. These rate constants were used in a coupled kinetic equilibrium numerical model where the ligand to iron ratio (TOTL:TOTFe) and pH were varied to evaluate the effect on the FeII oxidation rate. Overall, increasing TOTL:TOTFe for EGTA and TMDTA enhances FeII oxidation rates at lower pH and inhibits FeII oxidation

Potentiometric and electrokinetic signatures of iron(II) interactions with (α,γ)-Fe2O3.

Science.gov (United States)

Toczydłowska, Diana; Kędra-Królik, Karolina; Nejbert, Krzysztof; Preočanin, Tajana; Rosso, Kevin M; Zarzycki, Piotr

2015-10-21

The electrochemical signatures of Fe(II) interactions with iron(III) oxides are poorly understood, despite their importance in controlling the amount of mobilized iron. Here, we report the potentiometric titration of α,γ-Fe2O3 oxides exposed to Fe(II) ions. We monitored in situ surface and ζ potentials, the ratio of mobilized ferric to ferrous, and the periodically analyzed nanoparticle crystal structure using X-ray diffraction. Electrokinetic potential reveals weak but still noticeable specific sorption of Fe(II) to the oxide surface under acidic conditions, and pronounced adsorption under alkaline conditions that results in a surface potential reversal. By monitoring the aqueous iron(II/III) fraction, we found that the addition of Fe(II) ions produces platinum electrode response consistent with the iron solubility-activity curve. Although, XRD analysis showed no evidence of γ-Fe2O3 transformations along the titration pathway despite iron cycling between aqueous and solid reservoirs, the magnetite formation cannot be ruled out.

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.

Interaction of Cr (III), Ni (II), Pb (II) with DTPA complexes of essential metal ions

International Nuclear Information System (INIS)

Gulzar, S.; Zahida; Maqsood, T.; Naqvi, R.R.

2002-01-01

With the increase of anthropogenic activities in the environment, heavy metal toxicity (Chromium, Nickel and Lead) is more common now. DTPA (diethylene triamine pentaacetic acid) a polyamino carboxylic acid is widely used to form hydrophilic and stable complexes with most of the metal ions. In this spectrophotometric study, concentration of Cr(III), Ni(II) and Pb(II) (toxic metal ions) exchanged with Fe(III), Zn(II) and Ca(II) from their DTPA complexes were estimated at pH 4,7 and 9. Concentration of added metal was varied from 1-4 times to that of complexed metal. (author)

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.

Mechanisms for Fe(III) oxide reduction in sedimentary environments

Science.gov (United States)

Nevin, Kelly P.; Lovely, Derek R.

2002-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2012-01-06

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

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

Science.gov (United States)

Guo, Li; Zhang, Yan; Li, Quanmin

2009-12-01

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

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.

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

Directory of Open Access Journals (Sweden)

Ion Bulhac

2016-06-01

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

Speciation of Fe(II) and Fe(III) in Contaminated Aquifer Sediments Using Chemical Extraction Techniques

DEFF Research Database (Denmark)

Heron, Gorm; Crouzet, Catherine.; Bourg, Alain C. M.

1994-01-01

The iron mineralogy of aquifer sediments was described by chemical extraction techniques. Single-step extractions including 1 M CaC12, NaAc, oxalate, dithionite, Ti(II1)- EDTA, 0.5 M HC1,5 M HC1, hot 6 M HC1, and a sequential extraction by HI and CrIIHC1 were tested on standard iron minerals...... species are distinguished as AVS (acid volatile sulfide, hot 6 M HC1 extraction) and pyrite (sequential HI and CrIIHC1 extraction). By including a cold 5 M HC1 extraction, the total distribution of the major reactive Fe(I1) and Fe(II1) fractions in aquifer sediments can be assessed....

Glycine buffered synthesis of layered iron(II)-iron(III) hydroxides (green rusts)

DEFF Research Database (Denmark)

Yin, Weizhao; Huang, Lizhi; Pedersen, Emil Bjerglund

2017-01-01

Layered Fe(II)-Fe(III) hydroxides (green rusts, GRs) are efficient reducing agents against oxidizing contaminants such as chromate, nitrate, selenite, and nitroaromatic compounds and chlorinated solvents. In this study, we adopted a buffered precipitation approach where glycine (GLY) was used...

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

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

Science.gov (United States)

Lovley, D R

1991-06-01

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

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.

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

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.

Interaction between gold (III) chloride and potassium hexacyanoferrate (II/III)-Does it lead to gold analogue of Prussian blue?

Energy Technology Data Exchange (ETDEWEB)

Harish, S. [Electrodics and Electrocatalysis Division, CSIR-Central Electrochemical Research Institute, Karaikudi 630006, Tamilnadu (India); Joseph, James, E-mail: jameskavlam@yahoo.com [Electrodics and Electrocatalysis Division, CSIR-Central Electrochemical Research Institute, Karaikudi 630006, Tamilnadu (India); Phani, K.L.N. [Electrodics and Electrocatalysis Division, CSIR-Central Electrochemical Research Institute, Karaikudi 630006, Tamilnadu (India)

2011-06-30

Highlights: > In group IB, Cu and Ag form Prussian blue analogues but similar formation of gold hexacyanoferrate was not found in the literature and non-existence of gold hexacyanoferrate remains a mystery. > Potential cycling of gold chloride and potassium ferro/ferri cyanide was resulted in the formation of Au-PB nano-composite. > Redox reaction between gold chloride and potassium ferrocyanide ion is spontaneous but no reaction occurs when gold chloride and potassium ferricyanide is mixed. > We are proposing the formation of a compound with general formula 'KFe{sub x}[Au(CN){sub 2}]{sub y}' and discussing the formation of gold hexacyanoferrate is not feasible by simple chemical or electrochemical reaction in contrast to other PB analogues. - Abstract: Prussian blue analogues are a class of compounds formed by the reaction between metal salt and potassium hexacyanoferrate (II/III). In our earlier report, the formation of Au-Prussian blue nano-composite was noticed on potential cycling the glassy carbon electrode in a medium containing gold (III) chloride and potassium hexacyanoferrate (III). Hence in this work, the formation of gold hexacyanoferrate was attempted by a simple chemical reaction. The reaction of gold (III) chloride with potassium hexacyanoferrate (II/III) was examined by UV-Vis spectroscopy and found that there is no redox reaction between gold (III) chloride and potassium hexacyanoferrate (III). However, the redox reaction occurs between gold (III) chloride and potassium hexacyanoferrate (II) leading to the formation of charge transfer band and the conversion of hexacyanoferrate (II) to hexacyanoferrate (III) was evidenced by the emergence of new absorption peaks in UV-Vis spectra. The oxidation state of gold in Au-Fe complex was found to be +1 from X-ray photoelectron spectroscopy. The stability of the Au-Fe complex was also studied by cyclic voltammetry. Cyclic voltammetric results indicated the presence of high spin iron in Au-Fe

Interaction between gold (III) chloride and potassium hexacyanoferrate (II/III)-Does it lead to gold analogue of Prussian blue?

International Nuclear Information System (INIS)

Harish, S.; Joseph, James; Phani, K.L.N.

2011-01-01

Highlights: → In group IB, Cu and Ag form Prussian blue analogues but similar formation of gold hexacyanoferrate was not found in the literature and non-existence of gold hexacyanoferrate remains a mystery. → Potential cycling of gold chloride and potassium ferro/ferri cyanide was resulted in the formation of Au-PB nano-composite. → Redox reaction between gold chloride and potassium ferrocyanide ion is spontaneous but no reaction occurs when gold chloride and potassium ferricyanide is mixed. → We are proposing the formation of a compound with general formula 'KFe x [Au(CN) 2 ] y ' and discussing the formation of gold hexacyanoferrate is not feasible by simple chemical or electrochemical reaction in contrast to other PB analogues. - Abstract: Prussian blue analogues are a class of compounds formed by the reaction between metal salt and potassium hexacyanoferrate (II/III). In our earlier report, the formation of Au-Prussian blue nano-composite was noticed on potential cycling the glassy carbon electrode in a medium containing gold (III) chloride and potassium hexacyanoferrate (III). Hence in this work, the formation of gold hexacyanoferrate was attempted by a simple chemical reaction. The reaction of gold (III) chloride with potassium hexacyanoferrate (II/III) was examined by UV-Vis spectroscopy and found that there is no redox reaction between gold (III) chloride and potassium hexacyanoferrate (III). However, the redox reaction occurs between gold (III) chloride and potassium hexacyanoferrate (II) leading to the formation of charge transfer band and the conversion of hexacyanoferrate (II) to hexacyanoferrate (III) was evidenced by the emergence of new absorption peaks in UV-Vis spectra. The oxidation state of gold in Au-Fe complex was found to be +1 from X-ray photoelectron spectroscopy. The stability of the Au-Fe complex was also studied by cyclic voltammetry. Cyclic voltammetric results indicated the presence of high spin iron in Au-Fe complex. Hence 'as

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

Science.gov (United States)

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

2017-12-01

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

Multisensor system for determination of iron(II), iron(III) and uranium(VI) in complex solutions

International Nuclear Information System (INIS)

Legin, A.V.; Seleznev, B.L.; Rudnitskaya, A.M.; Vlasov, Yu.G.

1998-01-01

The aim of the present paper is the development and analytical evaluation of a multisensor system for determination of low content of iron(II), iron(III) and uranium(VI) in complex aqueous media. Sensor array included sensors on the basis of chalcogenide vitreous materials with redox and ionic cross-sensitivities, crystalline silver sulphide electrode, noble metal electrodes Pt, Au, Ag and redox sensor on the basis of oxide glass. Potentiometric measurements have been taken in a conventional electrochemical cell vs. a standard Ag/AgCl reference electrode. All measurements have been taken at room temperature. Calibration solutions contained UO 2 (NO 3 ) 2 in concentration range 10 -6 -1,610 -5 mol/L, K 3 Fe(CN) 6 and K 4 Fe(CN) 6 or FeSO 4 (NH 4 ) 2 SO 4 and FeCl 3 , with the ratio of Fe(II)/Fe(III) concentration from 100:1 to 1:100, the total concentration of Fe was 10 -4 and 10 -5 mol/L. All solutions have been made on the background electrolyte of calcium and magnesium chlorides and sulphates with the fixed content of 5-27 mmol/L of each component which is a typical one for groundwater or mining water. Sensor potentials have been processed by a back-propagation artificial neural net. Average error of determination of Fe(II) and Fe(III) is about 20 %, of uranium(VI) - 40 %. It was found that sensitivity of the sensor array to iron and uranium is irrespective of the chemical form of these species

Potential Role of Nitrite for Abiotic Fe(II) Oxidation and Cell Encrustation during Nitrate Reduction by Denitrifying Bacteria

Science.gov (United States)

Klueglein, Nicole; Zeitvogel, Fabian; Stierhof, York-Dieter; Floetenmeyer, Matthias; Konhauser, Kurt O.; Obst, Martin

2014-01-01

Microorganisms have been observed to oxidize Fe(II) at neutral pH under anoxic and microoxic conditions. While most of the mixotrophic nitrate-reducing Fe(II)-oxidizing bacteria become encrusted with Fe(III)-rich minerals, photoautotrophic and microaerophilic Fe(II) oxidizers avoid cell encrustation. The Fe(II) oxidation mechanisms and the reasons for encrustation remain largely unresolved. Here we used cultivation-based methods and electron microscopy to compare two previously described nitrate-reducing Fe(II) oxidizers ( Acidovorax sp. strain BoFeN1 and Pseudogulbenkiania sp. strain 2002) and two heterotrophic nitrate reducers (Paracoccus denitrificans ATCC 19367 and P. denitrificans Pd 1222). All four strains oxidized ∼8 mM Fe(II) within 5 days in the presence of 5 mM acetate and accumulated nitrite (maximum concentrations of 0.8 to 1.0 mM) in the culture media. Iron(III) minerals, mainly goethite, formed and precipitated extracellularly in close proximity to the cell surface. Interestingly, mineral formation was also observed within the periplasm and cytoplasm; intracellular mineralization is expected to be physiologically disadvantageous, yet acetate consumption continued to be observed even at an advanced stage of Fe(II) oxidation. Extracellular polymeric substances (EPS) were detected by lectin staining with fluorescence microscopy, particularly in the presence of Fe(II), suggesting that EPS production is a response to Fe(II) toxicity or a strategy to decrease encrustation. Based on the data presented here, we propose a nitrite-driven, indirect mechanism of cell encrustation whereby nitrite forms during heterotrophic denitrification and abiotically oxidizes Fe(II). This work adds to the known assemblage of Fe(II)-oxidizing bacteria in nature and complicates our ability to delineate microbial Fe(II) oxidation in ancient microbes preserved as fossils in the geological record. PMID:24271182

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.

Structure of short-range-ordered iron(III)-precipitates formed by iron(II) oxidation in water containing phosphate, silicate, and calcium

Science.gov (United States)

Voegelin, A.; Frommer, J.; Vantelon, D.; Kaegi, R.; Hug, S. J.

2009-04-01

The oxidation of Fe(II) in water leads to the formation of Fe(III)-precipitates that strongly affect the fate of nutrients and contaminants in natural and engineered systems. Examples include the cycling of As in rice fields irrigated with As-rich groundwater or the treatment of drinking water for As removal. Knowledge of the types of Fe(III)-precipitates forming in such systems is essential for the quantitative modeling of nutrient and contaminant dynamics and for the optimization of water purification techniques on the basis of a mechanistic understanding of the relevant biogeochemical processes. In this study, we investigated the local coordination of Fe, P, and Ca in Fe(III)-precipitates formed by aeration of synthetic Fe(II)-containing groundwater with variable composition (pH 7, 2-30 mg/L Fe(II), 2-20 mg/L phosphate-P, 2-20 mg/L silicate-Si, 8 mM Na-bicarbonate or 2.5 mM Ca-&1.5 mM Mg-bicarbonate). After 4 hours of oxidation, Fe(III)-precipitates were collected on 0.2 µm nylon filters and dried. The precipitates were analyzed by Fe K-edge EXAFS (XAS beamline, ANKA, Germany) and by P and Ca K-edge XANES spectroscopy (LUCIA beamline, SLS, Switzerland). The Fe K-edge EXAFS spectra indicated that local Fe coordination in the precipitates systematically shifted with water composition. As long as water contained P, mainly short-range-ordered Fe(III)-phosphate formed (with molar P/Fe ~0.5). In the absence of P, Fe(III) precipitated as hydrous ferric oxide at high Si/Fe>0.5, as ferrihydrite at intermediate Si/Fe, and mainly as lepidocrocite at Si/Fe<0.2. Analysis of the EXAFS by shell-fitting indicated that Fe(III)-phosphates mainly contained mono- or oligomeric (edge- or corner-sharing) Fe and that the linkage between neighboring Fe(III)-octahedra changed from predominantly edge-sharing in Si-rich hydrous ferric oxide to edge- and corner-sharing in ferrihydrite. Electron microscopic data showed that changes in local precipitate structure were systematically

A comparative study of nitrite reduction by synthetic and biogenic Fe(II-III) hydroxysalts green rusts: Evidence for hydroxyl-nitrite green rust formation as an intermediate reaction product.

Science.gov (United States)

Ona-Nguema, G.; Guerbois, D.; Morin, G.; Zhang, Y.; Noel, V.; Brest, J.

2013-12-01

The occurrence of high nitrite concentrations as a result of anthropogenic activities is an important water quality concern as it is highly toxic to human and fauna, and it is used as a nitrogen source for the assimilation process. The toxicity of nitrite is related to its transformation into carcinogenic N-nitroso compounds, which are suspected to be responsible for some gastric cancers, and to its ability to convert the hemoglobin to methaemoglobin what is then unable to fix oxygen and to transport it to the tissues, involving hypoxia and the blue-baby syndrome [1]. To reduce the adverse effect of nitrite on human health and on macroalgal blooms, any process enhancing the transformation of nitrite ions to nitrogen gas is of interest for the remediation of natural environments. To achieve this purpose the use of processes involving Fe(II)-containing minerals could be considered as one of the best options. Green-rusts are mixed Fe(II-III) layered double hydroxides commonly found in anoxic zones of natural environments such as sediments and hydromorphic soils. In such anoxic environments, green rust minerals play an important role in the biogeochemical redox cycling of iron and nitrogen, and can affect the speciation and mobility of many organic and inorganic contaminants. The present study investigates the reduction of nitrite by two synthetic and two biogenic green rusts. On the one hand, Fe(II-III) hydroxychloride and Fe(II-III) hydroxycarbonate green rusts were used as synthetic interlayer forms of GR, which are referred to as ';syn-GR(CO3)' and ';syn-GR(Cl)', respectively. On the other hand, the study was performed with biogenic Fe(II-III) hydroxycarbonate green rusts obtained from the bioreduction of two ferric precursors, either Fe(III)-oxyhydroxycarbonate or lepidocrocite; these biogenic green rusts are referred to as ';bio-GR(CO3)F' and ';bio-GR(CO3)L', respectively. For synthetic green rusts, results showed that the oxidation of both syn-GR(CO3) and syn

Fe(II)–Al(III) layered double hydroxides prepared by ultrasound-assisted co-precipitation method for the reduction of bromate

International Nuclear Information System (INIS)

Zhong, Yu; Yang, Qi; Luo, Kun; Wu, Xiuqiong; Li, Xiaoming; Liu, Yang; Tang, Wangwang; Zeng, Guangming; Peng, Bo

2013-01-01

Highlights: ► Fe(II)–Al(III) LDHs were synthesized by ultrasound-assisted co-precipitation method. ► The Fe–Al (30 min) exhibited highly reduction reactivity on bromate. ► Pseudo-first-order model described the experimental data well. ► The mechanisms of bromate removal were proposed. -- Abstract: Bromate is recognized as an oxyhalide disinfection byproduct in drinking water. In this paper, Fe(II)–Al(III) layered double hydroxides (Fe–Al LDHs) prepared by the ultrasound-assisted co-precipitation method were used for the reduction of bromate in solution. The Fe–Al LDHs particles were characterized by X-ray diffractometer, scanning electron microscopy and thermogravimetry–differential scanning calorimetry. It was found that ultrasound irradiation assistance promoted the formation of the hydrotalcite-like phase and then improved the removal efficiency of bromate. In addition, the effects of solid-to-solution ratio, contact time, initial bromate concentration, initial pH, coexisting anions on the bromate removal were investigated. The results showed the bromate with an initial concentration of 1.56 μmol/L could be completely removed from solution by Fe–Al LDHs within 120 min. When the initial bromate concentration was 7.81 μmol/L, the Fe–Al LDHs with irradiation time of 30 min exhibited the optimum removal efficiency and the bromate removal capacity (q e ) was 6.80 μmol/g. In addition, the appearance of sulfate and production of bromide were observed simultaneously in this process, which suggested that ion-exchange between sulfate and bromate, and the reduction of bromate to bromide by Fe 2+ were the main mechanisms responsible for the bromate removal by Fe–Al LDHs

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

International Nuclear Information System (INIS)

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

2014-01-01

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

Thioether-ligated iron(ii) and iron(iii)-hydroperoxo/alkylperoxo complexes with an H-bond donor in the second coordination sphere†

OpenAIRE

Widger, Leland R.; Jiang, Yunbo; McQuilken, Alison C.; Yang, Tzuhsiung; Siegler, Maxime A.; Matsumura, Hirotoshi; Moënne-Loccoz, Pierre; Kumar, Devesh; de Visser, Sam P.; Goldberg, David P.

2014-01-01

The non-heme iron complexes, [FeII(N3PySR)(CH3CN)](BF4)2 (1) and [FeII(N3PyamideSR)](BF4)2 (2), afford rare examples of metastable Fe(iii)-OOH and Fe(iii)-OOtBu complexes containing equatorial thioether ligands and a single H-bond donor in the second coordination sphere. These peroxo complexes were characterized by a range of spectroscopic methods and density functional theory studies. The influence of a thioether ligand and of one H-bond donor on the stability and spectroscopic properties of...

Mechanisms of electron transfer from structrual Fe(II) in reduced nontronite to oxygen for production of hydroxyl radicals

Science.gov (United States)

Yuan, Songhu; Liu, Xixiang; Liao, Wenjuan; Zhang, Peng; Wang, Xiaoming; Tong, Man

2018-02-01

, dioctahedral Al-Fe(II), Fe(II)-Fe(II) and Fe(II)-Fe(III) entities were slowly oxidized, and the interior electrons were transported through Fe(II)-O-Fe(III) linkages to edges and then ejected to O2. In the slow stage of oxidation, electrons from interior Fe(II) accumulated towards the near surface layers and fueled the regeneration of edge Fe(II) for radOH production. In both stages, one-electron transfer mechanism with the involvement of O2rad - and H2O2 applies for radOH production from the oxidation of structural Fe(II) by O2. The mechanisms unraveled in this study advance the understanding of reactive oxygen species (ROS) production and structural Fe variation when Fe(II)-bearing clay minerals are oxygenated in redox-dynamic systems.

Fate of nickel ion in (II-III hydroxysulphate green rust synthesized by precipitation and coprecipitation Adsorção de íon níquel em (II-III green rust hidroxisulfato sintetizado por precipitação e co-precipitação

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Lucia Helena Garófalo Chaves

2007-08-01

Full Text Available In order to investigate the efficiency of sulfate green rust (GR2 to remove Ni from solution, GR2 samples were synthesized under controlled laboratory conditions. Some GR2 samples were synthesized from Fe(II and Fe(III sulfate salts by precipitation. Other samples were prepared by coprecipitation, of Ni(II, Fe(II and Fe(III sulfate salts, i.e., in the presence of Ni. In another sample, Ni(II sulfate salt was added to pre-formed GR2. After an initial X-ray diffraction (XRD characterization all samples were exposed to ambient air in order to understand the role of Ni in the transformation of the GR2 samples. XRD was repeated after 45 days. The results showed that Nious GR2 prepared by coprecipitation is isomorphous to Ni-free GR2, i.e. Ni is incorporated into the crystalline structure. Fe(II was not replaced by Ni(II in the crystalline structure of GR2 formed prior to exposure to solution-phase Ni. This suggests Ni was adsorbed to the GR2 surface. Sulfate green rust is more efficient in removing Ni from the environment by coprecipitation.Com objetivo de investigar a eficiência do "sulfate green rust" (GR2 na remoção de Ni da solução, amostras de GR2 foram sintetizadas em laboratório sob condições controladas. Algumas amostras de GR2 foram sintetizadas pela precipitação de sais de Fe(II e de Fe(III; outras amostras, pela co-precipitação de sais de Ni(II, Fe(II e de Fe(III; e em outras amostras, o sulfato de Ni(II foi adicionado às amostras GR2 pré-formadas. Após caracterização inicial, por difração de raios X, todas as amostras ficaram expostas ao ar atmosférico durante 45 dias, a fim de se avaliar o papel do Ni na transformação delas. Após esse período, a difração de raios X das amostras foi repetida. Os resultados mostraram que Ni-GR2 preparado por co-precipitação é isomórfico do GR2, estando o íon Ni na estrutura cristalina deste. Fe(II não foi substituído por Ni(II na estrutura cristalina de GR2 formado a priori

Stochastic Simulation of Isotopic Exchange Mechanisms for Fe(II)-Catalyzed Recrystallization of Goethite

Energy Technology Data Exchange (ETDEWEB)

Zarzycki, Piotr [Energy; Institute; Rosso, Kevin M. [Pacific Northwest

2017-06-15

Understanding Fe(II)-catalyzed transformations of Fe(III)- (oxyhydr)oxides is critical for correctly interpreting stable isotopic distributions and for predicting the fate of metal ions in the environment. Recent Fe isotopic tracer experiments have shown that goethite undergoes rapid recrystallization without phase change when exposed to aqueous Fe(II). The proposed explanation is oxidation of sorbed Fe(II) and reductive Fe(II) release coupled 1:1 by electron conduction through crystallites. Given the availability of two tracer exchange data sets that explore pH and particle size effects (e.g., Handler et al. Environ. Sci. Technol. 2014, 48, 11302-11311; Joshi and Gorski Environ. Sci. Technol. 2016, 50, 7315-7324), we developed a stochastic simulation that exactly mimics these experiments, while imposing the 1:1 constraint. We find that all data can be represented by this model, and unifying mechanistic information emerges. At pH 7.5 a rapid initial exchange is followed by slower exchange, consistent with mixed surface- and diffusion-limited kinetics arising from prominent particle aggregation. At pH 5.0 where aggregation and net Fe(II) sorption are minimal, that exchange is quantitatively proportional to available particle surface area and the density of sorbed Fe(II) is more readily evident. Our analysis reveals a fundamental atom exchange rate of ~10-5 Fe nm-2 s-1, commensurate with some of the reported reductive dissolution rates of goethite, suggesting Fe(II) release is the rate-limiting step in the conduction mechanism during recrystallization.

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-03-01

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

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

International Nuclear Information System (INIS)

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

2014-01-01

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

Phototrophic Fe(II-oxidation in the chemocline of a ferruginous meromictic lake

Directory of Open Access Journals (Sweden)

Xavier Alexis eWalter

2014-12-01

Full Text Available Precambrian Banded Iron Formation (BIF deposition was conventionally attributed to the precipitation of iron-oxides resulting from the abiotic reaction of ferrous iron (Fe(II with photosynthetically-produced oxygen. Earliest traces of oxygen date from 2.7 Ga, thus raising questions as to what may have caused BIF precipitation before oxygenic photosynthesis evolved. The discovery of anoxygenic phototrophic bacteria thriving through the oxidation of Fe(II has provided support for a biological origin for some BIFs, but despite reports suggesting that anoxygenic phototrophs may oxidize Fe(II in the environment, a model ecosystem of an ancient ocean where they are demonstrably active was lacking. Here we show that anoxygenic phototrophic bacteria contribute to Fe(II oxidation in the water column of the ferruginous sulfate-poor, meromictic lake La Cruz (Spain. We observed in-situ photoferrotrophic activity through stimulation of phototrophic carbon uptake in the presence of Fe(II, and determined light-dependent Fe(II-oxidation by the natural chemocline microbiota. Moreover, a photoferrotrophic bacterium most closely related to Chlorobium ferrooxidans was enriched from the ferruginous water column. Our study for the first time demonstrates a direct link between anoxygenic photoferrotrophy and the anoxic precipitation of Fe(III-oxides in a ferruginous water column, providing a plausible mechanism for the bacterial origin of BIF’s before the advent of free oxygen.

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-01-15

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

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)

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)

Sol-gel based optical sensor for determination of Fe (II): a novel probe for iron speciation.

Science.gov (United States)

Samadi-Maybodi, Abdolraouf; Rezaei, Vida; Rastegarzadeh, Saadat

2015-02-05

A highly selective optical sensor for Fe (II) ions was developed based on entrapment of a sensitive reagent, 2,4,6-tri(2-pyridyl)-s-triazine (TPTZ), in a silica sol-gel thin film coated on a glass substrate. The thin films fabricated based on tetraethoxysilane (TEOS) as precursor, sol-gel pH∼3, water:alkoxyde ratio of 4:1 and TPTZ concentration of 0.112 mol L(-1). The influence of sol-gel parameters on sensing behavior of the fabricated sensor was also investigated. The fabricated sensor can be used for determination of Fe (II) ion with an outstanding high selectivity over a dynamic range of 5-115 ng mL(-1) and a detection limit of 1.68 ng mL(-1). It also showed reproducible results with relative standard deviation of 3.5% and 1.27% for 10 and 90 ng mL(-1) of Fe (II), respectively, along with a fast response time of ∼120 s. Total iron also was determined after reduction of Fe (III) to Fe (II) using ascorbic acid as reducing agent. Then, the concentration of Fe (III) was calculated by subtracting the concentration of Fe (II) from the total iron concentration. Interference studies showed a good selectivity for Fe (II) with trapping TPTZ into sol-gel matrix and appropriately adjusting the structure of doped sol-gel. The sensor was compared with other sensors and was applied to determine iron in different water samples with good results. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis and biological activity of acetates of copper (II and iron (III for the control of Aedes aegypti (Diptera: Culicidae

Directory of Open Access Journals (Sweden)

Jéssica V. Nardeli

2012-06-01

Full Text Available This work aimed to the synthesis of basic acetates of Cu (II and Fe(III against larvae of Aedes aegypti and Gram negative and Gram positive. The transition metal ions Cu (II and Fe (III have bactericidal activity and are toxic to Aedes aegypti larvae in the eggs and larval stages of initial, precludes the eggs hatch and slow reproductive cycle of the insect. The theme investigates the importance of carboxyl groups in complex formation, transport and cellular internalization of the toxic ions. It is known that the bactericide or insecticide activity is due to metal ions and Cu (IIor Fe (III.

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

International Nuclear Information System (INIS)

Liu, Hongyan; Wang, Guangce

2015-01-01

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

Feasibility of closed Fe(II)/Fe(III) system for product-reflux in Nitrox process

International Nuclear Information System (INIS)

Adachi, M.; Ishida, T.

1981-01-01

A concept of closed reflux system for stable isotope fractionation by chemical exchange method has been introduced. In a closed system a chemical agent used to convert one chemical species of an isotopic exchange reaction into the other at the product end is regenerated on site by means of an electrochemical or thermal process. It offers a convenience of eliminating the needs for transporting chemicals to and from the site and an advantage of allowing leniency in the degree of completeness of the reflux reaction. Feasibility of use of Fe(II) salt solutions in a closed reflux system for the Nitrox process for 15 N fractionation has been studied. Two of such systems, FeSO 4 in H 2 SO 4 and Fe(ClO 4 ) 2 in HClO 4 , are adopted for packed column operation. For both systems, the rate of reduction of nitric acid increases with increasing acid concentration, the solubility of the salts decreases with the increasing acid concentration, and the reflux reaction can be made to go to completion. Evaluation of such a closed reflux system will have to include that of performance of regenerative process

Rate law of Fe(II) oxidation under low O2 conditions

Science.gov (United States)

Kanzaki, Yoshiki; Murakami, Takashi

2013-12-01

Despite intensive studies on Fe(II) oxidation kinetics, the oxidation rate law has not been established under low O2 conditions. The importance of Fe(II) oxidation under low O2 conditions has been recently recognized; for instance, the Fe(II)/Fe(III) compositions of paleosols, ancient soils formed by weathering, can produce a quantitative pattern of the atmospheric oxygen increase during the Paleoproterozoic. The effects of partial pressure of atmospheric oxygen (PO2) on the Fe(II) oxidation rate were investigated to establish the Fe(II) oxidation rate - PO2 relationships under low O2 conditions. All oxidation experiments were carried out in a glove box by introducing Ar gas at ∼10-5-∼10-4 atm of PO2, pH 7.57-8.09 and 22 °C. Luminol chemiluminescence was adopted to measure low Fe(II) concentrations (down to ∼2 nM). Combining previous data under higher PO2 conditions (10-3-0.2 atm) with the present data, the rate law for Fe(II) oxidation over a wide range of PO2 (10-5-0.2 atm) was found to be written as: d[Fe(II)]/dt=-k[Fe(II)][[]2 where the exponent of [O2], x, and the rate constant, k, change from x = 0.98 (±0.04) and log k = 15.46 (±0.06) at ∼6 × 10-3-0.2 atm of PO2 to x = 0.58 (±0.02) and log k = 13.41 (±0.03) at 10-5-∼6 × 10-3 atm of PO2. The most plausible mechanism that explains the change in x under low O2 conditions is that, instead of O2, oxygen-derived oxidants, H2O2 and to some extent, O2rad -, dominate the oxidation reactions at PO2. The rate law found in the present study requires us to reconsider distributions of Fe redox species at low PO2 in natural environments, especially in paleoweathering profiles, and may provide a deeper understanding of the evolution of atmospheric oxygen in the Precambrian.

Uranium Immobilization through Fe(II) bio-oxidation: A Column study

Energy Technology Data Exchange (ETDEWEB)

Coates, John D.

2009-09-14

Current research on the bioremediation of heavy metals and radionuclides is focused on the ability of reducing organisms to use these metals as alternative electron acceptors in the absence of oxygen and thus precipitate them out of solution. However, many aspects of this proposed scheme need to be resolved, not the least of which is the time frame of the treatment process. Once treatment is complete and the electron donor addition is halted, the system will ultimately revert back to an oxic state and potentially result in the abiotic reoxidation and remobilization of the immobilized metals. In addition, the possibility exists that the presence of more electropositive electron acceptors such as nitrate or oxygen will also stimulate the biological oxidation and remobilization of these contaminants. The selective nitrate-dependent biooxidation of added Fe(II) may offer an effective means of “capping off” and completing the attenuation of these contaminants in a reducing environment making the contaminants less accessible to abiotic and biotic reactions and allowing the system to naturally revert to an oxic state. Our previous DOE-NABIR funded studies demonstrated that radionuclides such as uranium and cobalt are rapidly removed from solution during the biogenic formation of Fe(III)-oxides. In the case of uranium, X-ray spectroscopy analysis indicated that the uranium was in the hexavalent form (normally soluble) and was bound to the precipitated Fe(III)-oxides thus demonstrating the bioremediative potential of this process. We also demonstrated that nitrate-dependent Fe(II)- oxidizing bacteria are prevalent in the sediment and groundwater samples collected from sites 1 and 2 and the background site of the NABIR FRC in Oakridge, TN. However, all of these studies were performed in batch experiments in the laboratory with pure cultures and although a significant amount was learned about the microbiology of nitrate-dependent bio-oxidation of Fe(II), the effects of

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.

Moessbauer spectroscopic study on valence-detrapping and trapping of mixed-valence trinuclear iron (III, III, II) fluorine-substitute benzoate complexes

International Nuclear Information System (INIS)

Sakai, Y.; Onaka, S.; Ogiso, R.; Takayama, T.; Takahashi, M.; Nakamoto, T.

2012-01-01

Four mixed-valence trinuclear iron(III, III, II) fluorine-substituted benzoate complexes were synthesized; Fe 3 O(C 6 F 5 COO) 6 (C 5 H 5 N) 3 ·CH 2 Cl 2 (1), Fe 3 O(C 6 F 5 COO) 6 (C 5 H 5 N) 3 (2), Fe 3 O(2H-C 6 F 4 COO) 6 (C 5 H 5 N) 3 (3), and Fe 3 O(4H-C 6 F 4 COO) 6 (C 5 H 5 N) 3 (4). By means of 57 Fe-Moessbauer spectroscopy, valence-detrapping and trapping phenomena have been investigated for the four mixed-valence complexes. The valence state of three iron ions is trapped at lower temperatures while it is fully detrapped at higher temperatures for 1. Valence detrapping is not observed for 2, 3, and 4 even at room temperature, although Moessbauer spectra for 3 and 4 show a complicated temperature dependence. (author)

Particle Aggregation During Fe(III) Bioreduction in Nontronite

Science.gov (United States)

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

2005-12-01

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

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

International Nuclear Information System (INIS)

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

2003-01-01

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

Carbonate-mediated Fe(II) oxidation in the air-cathode fuel cell: a kinetic model in terms of Fe(II) speciation.

Science.gov (United States)

Song, Wei; Zhai, Lin-Feng; Cui, Yu-Zhi; Sun, Min; Jiang, Yuan

2013-06-06

Due to the high redox activity of Fe(II) and its abundance in natural waters, the electro-oxidation of Fe(II) can be found in many air-cathode fuel cell systems, such as acid mine drainage fuel cells and sediment microbial fuel cells. To deeply understand these iron-related systems, it is essential to elucidate the kinetics and mechanisms involved in the electro-oxidation of Fe(II). This work aims to develop a kinetic model that adequately describes the electro-oxidation process of Fe(II) in air-cathode fuel cells. The speciation of Fe(II) is incorporated into the model, and contributions of individual Fe(II) species to the overall Fe(II) oxidation rate are quantitatively evaluated. The results show that the kinetic model can accurately predict the electro-oxidation rate of Fe(II) in air-cathode fuel cells. FeCO3, Fe(OH)2, and Fe(CO3)2(2-) are the most important species determining the electro-oxidation kinetics of Fe(II). The Fe(II) oxidation rate is primarily controlled by the oxidation of FeCO3 species at low pH, whereas at high pH Fe(OH)2 and Fe(CO3)2(2-) are the dominant species. Solution pH, carbonate concentration, and solution salinity are able to influence the electro-oxidation kinetics of Fe(II) through changing both distribution and kinetic activity of Fe(II) species.

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.

Precise Wavelengths and Energy Levels for the Spectra of Cr I, Mn I, and Mn III, and Branching Fractions for the Spectra of Fe II and Cr II

Science.gov (United States)

Nave, Gillian

I propose to measure wavelengths and energy levels for the spectra of Cr I, Mn I, and Mn III covering the wavelength range 80 nm to 5500 nm, and oscillator strengths for Fe II and Cr II in the region 120 nm to 2500 nm. I shall also produce intensity calibrated atlases and linelists of the iron-neon and chromium-neon hollow cathode lamps that can be compared with astrophysical spectra. The spectra will be obtained from archival data from spectrometers at NIST and Kitt Peak National Observatory and additional experimental observations as necessary from Fourier transform (FT) and grating spectrometers at NIST. The wavelength uncertainty of the strong lines will be better than 1 part in 10^7. The radiometric calibration of the spectra will be improved in order to reduce the uncertainty of measured oscillator strengths in the near UV region and extend the wavelength range of these measurements down to 120 nm. These will complement and support the measurements of lifetimes and branching fractions by J. E. Lawler in the near UV region. An intensive effort by NIST and Imperial College London that was partly funded by previous NASA awards has resulted in comprehensive analyses of the spectra of Fe II, Cr II and Cu II, with similar analyses of Mn II, Ni II, and Sc II underway. The species included in this proposal will complete the analysis of the first two ionization stages of the elements titanium through nickel using the same techniques, and add the spectrum of Mn III - one of the most important doubly-ionized elements. The elements Cr I and Mn I give large numbers of spectral lines in spectra of cool stars and important absorption lines in the interstellar medium. The spectrum of Mn III is important in chemically peculiar stars and can often only be studied in the UV region. Analyses of many stellar spectra depend on comprehensive analyses of iron-group elements and are hampered by incomplete spectroscopic data. As a result of many decades of work by the group at the

Sorption and reduction of selenite on chlorite surfaces in the presence of Fe(II) ions.

Science.gov (United States)

Baik, Min Hoon; Lee, Seung Yeop; Jeong, Jongtae

2013-12-01

The sorption and reduction of selenite on chlorite surfaces in the presence of Fe(II) ions were investigated as a function of pH, Se(IV) concentration, and Fe(II) concentration under an anoxic condition. The sorption of Se(IV) onto chlorite surfaces followed the Langmuir isotherm regardless of the presence of Fe(II) ions in the solution. The Se(IV) sorption was observed to be very low at all pH values when the solution was Fe(II)-free or the concentration of Fe(II) ions was as low as 0.5 mg/L. However, the Se(IV) sorption was enhanced at a pH > 6.5 when the Fe(II) concentration was higher than 5 mg/L because of the increased sorption of Fe(II) onto the chlorite surfaces. XANES (X-ray absorption near edge structure) spectra of the Se K-edge showed that most of the sorbed Se(IV) was reduced to Se(0) by Fe(II) sorbed onto the chlorite surfaces, especially at pH > 9. The combined results of field-emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD) also showed that elemental selenium and goethite were formed and precipitated on the chlorite surfaces during the sorption of selenite. Consequently it can be concluded that Se(IV) can be reduced to Se(0) in the presence of Fe(II) ions by the surface catalytic oxidation of Fe(II) into Fe(III) and the formation of goethite at neutral and particularly alkaline conditions. Thus the mobility of selenite in groundwater is expected to be reduced by the presence of a relatively higher concentration of Fe(II) in subsurface environments. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

Oxidation of Fe(II) in rainwater.

Science.gov (United States)

Willey, J D; Whitehead, R F; Kieber, R J; Hardison, D R

2005-04-15

Photochemically produced Fe(II) is oxidized within hours under environmentally realistic conditions in rainwater. The diurnal variation between photochemical production and reoxidation of Fe(II) observed in our laboratory accurately mimics the behavior of ferrous iron observed in field studies where the highest concentrations of dissolved Fe(ll) occur in afternoon rain during the period of maximum sunlight intensity followed by gradually decreasing concentrations eventually returning to early morning pre-light values. The experimental work presented here, along with the results of kinetics studies done by others, suggests thatthe primary process responsible for the decline in photochemically produced Fe(II) concentrations is oxidation by hydrogen peroxide. This reaction is first order with respect to both the concentrations of Fe(II) and H2O2. The second-order rate constant determined for six different authentic rain samples varied over an order of magnitude and was always less than or equal to the rate constant determined for this reaction in simple acidic solutions. Oxidation of photochemically produced ferrous iron by other oxidants including molecular oxygen, ozone, hydroxyl radical, hydroperoxyl/superoxide radical, and hexavalent chromium were found to be insignificant under the conditions present in rainwater. This study shows that Fe(II) occurs as at least two different chemical species in rain; photochemically produced Fe(II) that is oxidized over time periods of hours, and a background Fe(II) that is protected against oxidation, perhaps by organic complexation, and is stable against oxidation for days. Because the rate of oxidation of photochemically produced Fe(II) does not increase with increasing rainwater pH, the speciation of this more labile form of Fe(II) is also not controlled by simple hydrolysis reactions.

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

Directory of Open Access Journals (Sweden)

Shaofeng Zhou

2016-06-01

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

Competing retention pathways of uranium upon reaction with Fe(II)

Science.gov (United States)

Massey, Michael S.; Lezama-Pacheco, Juan S.; Jones, Morris E.; Ilton, Eugene S.; Cerrato, José M.; Bargar, John R.; Fendorf, Scott

2014-10-01

Biogeochemical retention processes, including adsorption, reductive precipitation, and incorporation into host minerals, are important in contaminant transport, remediation, and geologic deposition of uranium. Recent work has shown that U can become incorporated into iron (hydr)oxide minerals, with a key pathway arising from Fe(II)-induced transformation of ferrihydrite, (Fe(OH)3·nH2O) to goethite (α-FeO(OH)); this is a possible U retention mechanism in soils and sediments. Several key questions, however, remain unanswered regarding U incorporation into iron (hydr)oxides and this pathway's contribution to U retention, including: (i) the competitiveness of U incorporation versus reduction to U(IV) and subsequent precipitation of UO2; (ii) the oxidation state of incorporated U; (iii) the effects of uranyl aqueous speciation on U incorporation; and, (iv) the mechanism of U incorporation. Here we use a series of batch reactions conducted at pH ∼7, [U(VI)] from 1 to 170 μM, [Fe(II)] from 0 to 3 mM, and [Ca] at 0 or 4 mM coupled with spectroscopic examination of reaction products of Fe(II)-induced ferrihydrite transformation to address these outstanding questions. Uranium retention pathways were identified and quantified using extended X-ray absorption fine structure (EXAFS) spectroscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. Analysis of EXAFS spectra showed that 14-89% of total U was incorporated into goethite, upon reaction with Fe(II) and ferrihydrite. Uranium incorporation was a particularly dominant retention pathway at U concentrations ⩽50 μM when either uranyl-carbonato or calcium-uranyl-carbonato complexes were dominant, accounting for 64-89% of total U. With increasing U(VI) and Fe(II) concentrations, U(VI) reduction to U(IV) became more prevalent, but U incorporation remained a functioning retention pathway. These findings highlight the potential importance of U(V) incorporation within iron

DFT predictions, synthesis, stoichiometric structures and anti-diabetic activity of Cu (II) and Fe (III) complexes of quercetin, morin, and primuletin

Science.gov (United States)

Jabeen, Erum; Janjua, Naveed Kausar; Ahmed, Safeer; Murtaza, Iram; Ali, Tahir; Masood, Nosheen; Rizvi, Aysha Sarfraz; Murtaza, Gulam

2017-12-01

The current study is aimed at the synthesis of Cu (II) and Fe (III) complexes of three flavonoids {morin (mor), quercetin (quer) and primuletin (prim)} and characterization through UV-Vis spectroscopy, cyclic voltammetry, FTIR, and thermal analysis. Structure prediction through DFT calculation was supported by experimental data. Benesi-Hildebrand equation was modified to function for 1:2 Cu-flavonoid and 1:3 Fe-flavonoid complexes. DFT predictions revealed that out of poly chelation sites present in morin and quercetin, 3-OH site was utilized as preferable chelation site while primuletin chelated through 5-OH position. In-vivo trials revealed the complexes to have better anti-diabetic potential than respective flavonoid. Fls/M-Fls proved as antagonistic to Alloxan induced diabetes and also retained anti-diabetic activity even in the presence of (2-hydroxypropyl)-β-cyclodextrin (HPβCD).

As(III) oxidation by MnO2 during groundwater treatment.

Science.gov (United States)

Gude, J C J; Rietveld, L C; van Halem, D

2017-03-15

The top layer of natural rapid sand filtration was found to effectively oxidise arsenite (As(III)) in groundwater treatment. However, the oxidation pathway has not yet been identified. The aim of this study was to investigate whether naturally formed manganese oxide (MnO 2 ), present on filter grains, could abiotically be responsible for As(III) oxidation in the top of a rapid sand filter. For this purpose As(III) oxidation with two MnO 2 containing powders was investigated in aerobic water containing manganese(II) (Mn(II)), iron(II) (Fe(II)) and/or iron(III) (Fe(III)). The first MnO 2 powder was a very pure - commercially available - natural MnO 2 powder. The second originated from a filter sand coating, produced over 22 years in a rapid filter during aeration and filtration. Jar test experiments showed that both powders oxidised As(III). However, when applying the MnO 2 in aerated, raw groundwater, As(III) removal was not enhanced compared to aeration alone. It was found that the presence of Fe(II)) and Mn(II) inhibited As(III) oxidation, as Fe(II) and Mn(II) adsorption and oxidation were preferred over As(III) on the MnO 2 surface (at pH 7). Therefore it is concluded that just because MnO 2 is present in a filter bed, it does not necessarily mean that MnO 2 will be available to oxidise As(III). However, unlike Fe(II), the addition of Fe(III) did not hinder As(III) oxidation on the MnO 2 surface; resulting in subsequent effective As(V) removal by the flocculating hydrous ferric oxides. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of pH and Fe/U ratio on the U(VI) removal rate by the synergistic effect of Fe(II) and O2

Science.gov (United States)

Fu, Yukui; Luo, Yingfeng; Fang, Qi; Xie, Yanpei; Wang, Zhihong; Zhu, Xiangyu

2018-02-01

As for the decommissioned uranium deposits of acid in-situ leaching, both of the concentrations of U(VI) and Fe(II) are relatively high in groundwater. In the presence of O2, the oxidation of Fe(II) into Fe(III) that forms Fe-hydroxides could effectively remove U(VI) in the forms of sorption or co-precipitation. In this process, pH condition and Fe content will have a significant effect on the U(VI) removal rate by the synergistic effect of Fe(II) and O2. In the present work, a series of batch experiments were carried out to investigate the effect of pH values and Fe/U mass ratio on the U(VI) removal rate by the synergistic effect of Fe(II) and O2. Experiment results show that the removal rate of U(VI) is mainly controlled by pH and secondly by Fe/U mass ratio. In the neutral conditions with pH at 7 and 8, the removal rate of U(VI) reaches up to 90% for all solutions with different initial Fe(II) concentrations. The optimal pH for the removal rate of U(VI) is above 7. In the acidic conditions with pH below 6, the effect of Fe/U mass ratio on the removal rate of U(VI) becomes more obvious and the optimal Fe/U mass ratio for U(VI) removal is 1:2.

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

Science.gov (United States)

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

2014-01-06

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

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

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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

Abiotic Deposition of Fe Complexes onto Leptothrix Sheaths

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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

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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.

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

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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.

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

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

2011-01-01

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

Preparation and Eh-pH diagrams of Fe(II)-Fe(III) green rust compounds; hyperfine interaction characteristics and stoichiometry of hydroxy-chloride, -sulphate and -carbonate

International Nuclear Information System (INIS)

Genin, J.-M.R.; Refait, Ph.; Simon, L.; Drissi, S.H.

1998-01-01

Fe(II)-Fe(III) hydroxy-chloride, -sulphate and -carbonate were prepared by oxidation of a ferrous hydroxide precipitate in anion-containing aqueous solutions. The compounds are characterized by monitoring the redox potential E h and the pH of stochiometric suspension vs time with the appropriate concentration ratios. X-ray diffraction allows us to characterize the crystal structure by distinguishing 'green rust one' (GR1) from 'green rust two' (GR2). Since green rusts (GRs) are of a pyroaurite-sjoegrenite-like structure, i.e., consisting of intercalated foreign anions and water molecules in the interlayers between the brucite-like layers of Fe(OH) 2 , their chemical formulae can be determined from the Moessbauer spectra. Three quadrupole doublets are observed: D 1 and D 2 correspond to a ferrous state with isomershift IS of about 1.27 mm s -1 and quadrupole splittings QS of about 2.85 and 2.60 mm s -1 , respectively, whereas D 3 corresponds to a ferric state with IS and QS of about 0.4 mm s -1 . The hyperfine parameters of these doublets are similar from one green rust to another but their intensity ratios vary considerably. Finally, E h and pH equilibrium diagrams of the Fe species in the presence of chloride, sulphate and carbonate anions contained within the water solution are drawn and the thermodynamic conditions of existence and degrees of oxidation of green rusts are discussed

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

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

2006-07-19

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

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

Science.gov (United States)

Ishida, Akihiko; Yamada, Yasuko; Kamidate, Tamio

2008-11-01

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

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

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

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

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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).

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

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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

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

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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

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

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)

Effect of Organic Matter on Cr(VI Removal from Groundwaters by Fe(II Reductive Precipitation for Groundwater Treatment

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Anna Gröhlich

2017-06-01

Full Text Available Due to its toxicity, Cr(VI is undesirable in groundwater. Its chemical reduction to Cr(III species, followed by precipitation is the most widely practiced treatment technique for the removal of Cr(VI from polluted waters. The resulting Cr(III species present low solubility, is much less toxic, and can be subsequently removed either by precipitation, or by adsorption onto iron oxy-hydroxides and co-precipitation. The effects of several parameters, such as the pH value of water to be treated, the applied Fe(II dose, and the presence of appropriate mineral surfaces, are well investigated and understood. However, the impact of the presence of humic acids (HAs in this process has only been considered by rather few studies. The main aim of this study was to determine the effect of humic substances on Fe(II reductive precipitation of Cr(VI within a pH range relevant for drinking water treatment. Jar test experiments were performed, using artificial groundwater of defined composition and initial Cr(VI concentration 100 μg/L, ferrous sulphate dosages 0.25–2 mg Fe(II/L, and pH values 6.5–8. It was found that Cr(VI and total chromium (Cr(total can be reliably removed in the absence of HAs in the tested pH range with the addition of Fe(II dosage of 1 mg Fe(II/L. Further on, the results indicated that the reduction of Cr(VI is only slightly affected by the presence of HAs. However, increased residual total Cr concentrations were found at lower Fe(II dosages and/or higher pH values. Additionally, the removal of the Cr(III species formed during Cr(VI reduction was strongly inhibited by the presence of HAs under the examined experimental conditions, since residual concentrations higher than 60 μg/L were determined. The results of this study will have implications to the ongoing discussion of a new, stricter, European Union regulation limit, regarding the presence of total chromium in drinking water.

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

International Nuclear Information System (INIS)

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

2009-01-01

The heating effect on films of polyacrylonitrile and doping of the ions Fe(II) and Fe (III) may reveal important aspects of the use of this polymer in the search for new materials. This paper was done the doping of the films of PAN with ions Fe(II) and Fe (III), with thermo heating is range of 60 a 90 deg C e de 90 a 170 deg C through the alkaline and acid hydrolysis of the CN groups used spectroscopy of FTIR and Moessbauer techniques to evaluate the structural changes results of doping process this polymer. The results showed that the FTIR spectral have a strong interaction of the ions Fe(II) and Fe (III) with PAN and confirmed by Moessbauer data. (author)

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

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

2017-07-01

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

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

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

2018-02-16

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

Syntheses of polystyrene supported chelating resin containing the Schiff base derived from salicylaldehyde and triethylene tetramine and its copper(II), nickel(II), cobalt(II), iron(III), zinc(II), cadmium(II), molybdenum(VI), zirconium(IV) and uranium(VI) complexes

International Nuclear Information System (INIS)

Syamal, A.; Singh, M.M.

1998-01-01

A new polymer-anchored chelating ligand has been synthesized by the reaction of chloromethylated polystyrene (containing 0.94 mmol of Cl per gram of resin and 1% cross-linked with divinylbenzene) and the Schiff base derived from salicylaldehyde and triethylenetetramine. A new series of polystyrene supported, Cu(II), Ni(II), Co(II), Fe(III), Zn(II), Cd(II), Zr(IV), dioxomolybdenum (VI) and dioxouranium (VI) complexes of the formulae PS-LCu, PS-LNi, PS-LCo, PS-LFeCl.DMF, PS-LZn, PS-LCd, PS-LZr(OH) 2 . DMF, PS L MoO 2 and PS-LUO 2 (where PS-LH 2 = polymer-anchored Schiff base and DMF dimethyl-formamide) have been synthesized and characterised by elemental analysis, infrared, electronic spectra and magnetic susceptibility measurements. The complexes PS-LCu, PS-LNi and PS-LCo have square planar structure, PS-LFeCl.DMF, PS-LMoO 2 and PS-LUO 2 have octahedral structure, PS L Zn and PS-LCd are tetrahedral and PS-LZr(OH) 2 .DMF is pentagonal bipyramidal. The polymer-anchored Cu(II), Co(II) and Fe(III) complexes are paramagnetic while Ni(II), Zn(II), Cd(II), Zr(IV), dioxomolybdenum(VI) and dioxouranium(VI) complexes are diamagnetic. The negative shift of the v (C=N) (azomethine) and the positive shift of v (C--O)(phenolic) are indicative of ONNO donor behaviour of the polymer-anchored Schiff base. (author)

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.

Effects of 3d-4f magnetic exchange interactions on the dynamics of the magnetization of Dy(III)-M(II)-Dy(III) trinuclear clusters.

Science.gov (United States)

Pointillart, Fabrice; Bernot, Kevin; Sessoli, Roberta; Gatteschi, Dante

2007-01-01

[{Dy(hfac)(3)}(2){Fe(bpca)(2)}] x CHCl(3) ([Dy(2)Fe]) and [{Dy(hfac)(3)}(2){Ni(bpca)(2)}]CHCl(3) ([Dy(2)Ni]) (in which hfac(-)=1,1,1,5,5,5-hexafluoroacetylacetonate and bpca(-)=bis(2-pyridylcarbonyl)amine anion) were synthesized and characterized. Single-crystal X-ray diffraction shows that [Dy(2)Fe] and [Dy(2)Ni] are linear trinuclear complexes. Static magnetic susceptibility measurements reveal a weak ferromagnetic exchange interaction between Ni(II) and Dy(III) ions in [Dy(2)Ni], whereas the use of the diamagnetic Fe(II) ion leads to the absence of magnetic exchange interaction in [Dy(2)Fe]. Dynamic susceptibility measurements show a thermally activated behavior with the energy barrier of 9.7 and 4.9 K for the [Dy(2)Fe] and [Dy(2)Ni] complexes, respectively. A surprising negative effect of the ferromagnetic exchange interaction has been found and has been attributed to the structural conformation of these trinuclear complexes.

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.

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.

Synthesis of linear alkylbenzene sulphonate intercalated iron(II) iron(III) hydroxide sulphate (green rust) and adsorption of carbon tetrachloride

DEFF Research Database (Denmark)

Ayala Luis, Karina Barbara; Kaldor, D.K.; Bender Koch, Christian

2007-01-01

) into the interlayer space of synthetic sulphate green rust, GR . Mössbauer analysis of GRLAS indicates that the structure of the organo-GR is very similar to SO4 that of the initial GR with regard to the FeII/FeIII ratio and local coordination of Fe atoms. X-ray SO4 diffraction demonstrates that the GRLAS formed...

Accumulation of Fe oxyhydroxides in the Peruvian oxygen deficient zone implies non-oxygen dependent Fe oxidation

Science.gov (United States)

Heller, Maija I.; Lam, Phoebe J.; Moffett, James W.; Till, Claire P.; Lee, Jong-Mi; Toner, Brandy M.; Marcus, Matthew A.

2017-08-01

Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here we have measured the redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). We present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen.

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.

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.

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.

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

International Nuclear Information System (INIS)

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

2010-01-01

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

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.

Evaluation of Fe(II) oxidation at an acid mine drainage site using laboratory-scale reactors

Science.gov (United States)

Brown, Juliana; Burgos, William

2010-05-01

Acid mine drainage (AMD) is a severe environmental threat to the Appalachian region of the Eastern United States. The Susquehanna and Potomac River basins of Pennsylvania drain to the Chesapeake Bay, which is heavily polluted by acidity and metals from AMD. This study attempted to unravel the complex relationships between AMD geochemistry, microbial communities, hydrodynamic conditions, and the mineral precipitates for low-pH Fe mounds formed downstream of deep mine discharges, such as Lower Red Eyes in Somerset County, PA, USA. This site is contaminated with high concentrations of Fe (550 mg/L), Mn (115 mg/L), and other trace metals. At the site 95% of dissolved Fe(II) and 56% of total dissolved Fe is removed without treatment, across the mound, but there is no change in the concentration of trace metals. Fe(III) oxides were collected across the Red Eyes Fe mound and precipitates were analyzed by X-ray diffraction, electron microscopy and elemental analysis. Schwertmannite was the dominant mineral phase with traces of goethite. The precipitates also contained minor amounts of Al2O3, MgO,and P2O5. Laboratory flow-through reactors were constructed to quantify Fe(II) oxidation and Fe removal over time at terrace and pool depositional facies. Conditions such as residence time, number of reactors in sequence and water column height were varied to determine optimal conditions for Fe removal. Reactors with sediments collected from an upstream terrace oxidized more than 50% of dissolved Fe(II) at a ten hour residence time, while upstream pool sediments only oxidized 40% of dissolved Fe(II). Downstream terrace and pool sediments were only capable of oxidizing 25% and 20% of Fe(II), respectively. Fe(II) oxidation rates measured in the reactors were determined to be between 3.99 x 10-8and 1.94 x 10-7mol L-1s-1. The sediments were not as efficient for total dissolved Fe removal and only 25% was removed under optimal conditions. The removal efficiency for all sediments

Mössbauer spectroscopy of reduced forms of a Fe-tetraphenylporphyrine complex

Directory of Open Access Journals (Sweden)

Kaczmarzyk Tomasz

2015-03-01

Full Text Available Molecular and electronic structure changes during successive reduction of a Fe-tetraphenylporphyrin chloride [Fe(III(TPP:Cl] complex are reported on the basis of Mössbauer spectroscopy and DFT calculations. It is established that the attachment of additional electrons to a neutral Fe(III(TPP:Cl molecule leads to significant shortening of Fe-N distances at the first stage of the reduction Fe(III(TPP:Cl → Fe(II(TPP and lengthening of these bonds at the second stage Fe(II(TPP → Fe(I(TPP. Changes of other bond lengths of the porphyrin ring also appear but in less degree. Interaction of Fe(II and Fe(I(TPP with tetrahydrofuran (THF solvent is considered. Electron configuration of Fe(II(TPP corresponds to intermediate-spin (S = 1 state and in the case of Fe(I(TPP low-spin state (S = ½ is observed. Electron density distribution in Fe(II- and Fe(I(TPP complexes, in association with Mössbauer data, is analyzed. Good correlation between experimental and theoretical results was obtained.

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

Science.gov (United States)

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

2011-01-01

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

Immobilization of aqueous Hg(II) by mackinawite (FeS)

International Nuclear Information System (INIS)

Liu Jianrong; Valsaraj, Kalliat T.; Devai, Istvan; DeLaune, R.D.

2008-01-01

As one of the major constituents of acid volatile sulfide (AVS) in anoxic sediments, mackinawite (FeS) is known for its ability to scavenge trace metals. The interaction between aqueous Hg(II) (added as HgCl 2 ) and synthetic FeS was studied via batch sorption experiments conducted under anaerobic conditions. Due to the release of H + during formation of hydrolyzed Hg(II) species which is more reactive than Hg 2+ in surface adsorption, the equilibrium pH decreased with the increase in Hg(II)/FeS molar ratio. Counteracting the loss of FeS solids at lower pH, the maximum capacity for FeS to remove aqueous Hg(II) was approximately 0.75 mol Hg(II) (mol FeS) -1 . The comparison of X-ray power diffraction (XRPD) patterns of synthetic FeS sorbent before and after sorption showed that the major products formed from the interaction between FeS and the aqueous Hg(II) were metacinnabar, cinnabar, and mercury iron sulfides. With the addition of FeS at 0.4 g L -1 to a 1 mM Hg(II) solution with an initial pH of 5.6, Fe 2+ release was approximately 0.77 mol Fe 2+ per mol Hg(II) removed, suggesting that 77% of Hg(II) was removed via precipitation reaction under these conditions, with 23% of Hg(II) removed by adsorption. Aeration does not cause significant release of Hg(II) into the water phase

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.

Moderate KMnO4-Fe(II) pre-oxidation for alleviating ultrafiltration membrane fouling by algae during drinking water treatment.

Science.gov (United States)

Ma, Baiwen; Qi, Jing; Wang, Xing; Ma, Min; Miao, Shiyu; Li, Wenjiang; Liu, Ruiping; Liu, Huijuan; Qu, Jiuhui

2018-05-21

Although ultrafiltration (UF) membranes are highly beneficial for removing algae, the removal process causes serious UF membrane fouling. To avoid the unfavorable effects of algal cells that have been damaged by oxidants, our previous study reported a novel, moderate pre-oxidation method (KMnO 4 -Fe(II) process) that aimed to achieve a balance between the release of intracellular organic matter and enhanced algae removal. This study further investigated the performance of a UF membrane with KMnO 4 -Fe(II) pretreatment in the presence of algae-laden reservoir water after a long running time. We found that algae could be completely removed, membrane fouling was significantly alleviated, and the overall performance was much better than that of Fe(III) coagulation alone. The transmembrane pressure (TMP) during Fe(III) coagulation increased to 42.8 kPa, however, that of the KMnO 4 -Fe(II) process only increased to 25.1 kPa for after running for 90 d. The slower transmembrane pressure was attributed to the larger floc size, higher surface activity, and inactivation of algae. Although there was little effect on microorganism development, lower microorganism abundance (20.7%) was observed during the KMnO 4 -Fe(II) process than during coagulation alone (44.9%) due to the release of extracellular polymeric substances. We also found that the floc cake layer was easily removed by washing, and many of the original membrane pores were clearly observed. Further analysis demonstrated that the effluent quality was excellent, especially its turbidity, chromaticity, and Mn and Fe concentrations. Based on the outstanding UF membrane performance, it may be concluded that the KMnO 4 -Fe(II) process exhibits considerable potential for application in the treatment of algae-laden water. Copyright © 2018. Published by Elsevier Ltd.

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

The role of order-disorder transitions in the quest for molecular multiferroics: structural and magnetic neutron studies of a mixed valence iron(II)-iron(III) formate framework.

Science.gov (United States)

Cañadillas-Delgado, Laura; Fabelo, Oscar; Rodríguez-Velamazán, J Alberto; Lemée-Cailleau, Marie-Hélène; Mason, Sax A; Pardo, Emilio; Lloret, Francesc; Zhao, Jiong-Peng; Bu, Xian-He; Simonet, Virginie; Colin, Claire V; Rodríguez-Carvajal, Juan

2012-12-05

Neutron diffraction studies have been carried out to shed light on the unprecedented order-disorder phase transition (ca. 155 K) observed in the mixed-valence iron(II)-iron(III) formate framework compound [NH(2)(CH(3))(2)](n)[Fe(III)Fe(II)(HCOO)(6)](n). The crystal structure at 220 K was first determined from Laue diffraction data, then a second refinement at 175 K and the crystal structure determination in the low temperature phase at 45 K were done with data from the monochromatic high resolution single crystal diffractometer D19. The 45 K nuclear structure reveals that the phase transition is associated with the order-disorder of the dimethylammonium counterion that is weakly anchored in the cavities of the [Fe(III)Fe(II)(HCOO)(6)](n) framework. In the low-temperature phase, a change in space group from P31c to R3c occurs, involving a tripling of the c-axis due to the ordering of the dimethylammonium counterion. The occurrence of this nuclear phase transition is associated with an electric transition, from paraelectric to antiferroelectric. A combination of powder and single crystal neutron diffraction measurements below the magnetic order transition (ca. 37 K) has been used to determine unequivocally the magnetic structure of this Néel N-Type ferrimagnet, proving that the ferrimagnetic behavior is due to a noncompensation of the different Fe(II) and Fe(III) magnetic moments.

Constraining the role of anoxygenic phototrophic Fe(II)-oxidizing bacteria in deposition of BIFs

Science.gov (United States)

Kappler, A.; Posth, N. R.; Hegler, F.; Wartha, E.; Huelin, S.

2007-12-01

Banded Iron Formations (BIFs) are Precambrian sedimentary deposits of alternating iron oxide and silica mineral layers. Their presence in the rock record ca.3.8-2.2 Ga makes them particularly intriguing formations for the debate over when oxygen became dominant on Earth. The mechanism(s) of BIF deposition is still unclear; suggestions including both abiotic and biotic processes. We are interested in constraining one of these proposed mechanisms; the direct biological oxidation of Fe(II) via anoxygenic Fe(II)-oxidizing autophototrophs. In order to find the limitations of photoferrotrophic BIF deposition, we take a holistic approach, investigating the oxidation of Fe(II) by modern Fe(II)-oxidizing phototrophs, the precipitation of Fe(III) (hydr)oxides, and the fate of the cell-mineral aggregates in the water column and at the basin floor. Specifically, physiology experiments with Fe(II)-oxidizing phototrophs under various conditions of light intensity, pH, Fe(II) concentration and temperature allow us to determine the environmental limits of such organisms. We carry out precipitation experiments to characterize the sedimentation rates, aggregate size and composition in order to resolve the effect of reactions in the water column. Finally, we simulate the diagenetic fate of these aggregates on the basin floor by placing them in gold capsules under T and P conditions relevant for the Transvaal Supergroup BIFs of South Africa. Recently, we have developed a tank simulating the Archean ocean in which the strains grow in continuous culture and collect the aggregates formed under various geochemical conditions. We aim to model the extent of and limitations to photoferrotrophs in BIF deposition. This information will help constrain whether biotic processes were dominant in the Archean ocean and will offer insight to the evolution of the early biogeosphere.

Moessbauer study of Fe(III)-reducing sugar complexes

International Nuclear Information System (INIS)

Wolowiec, S.; Drabent, K.

1985-01-01

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

Fe++/Fe+++ concentration relationship and mechanical properties of phosphate glasses useful for wastes immobilization

International Nuclear Information System (INIS)

Garcia, D.A.; Prado, Miguel O.

2007-01-01

Under different melting conditions, glasses with different Fe(II)/Fe(III) concentration relationship were prepared within each type of glass 43Fe 2 O 3 -57P 2 O 5 and 33,33Fe 2 O 3 - 66,67P 2 O 5 . Using Moessbauer spectroscopy Fe(II)/Fe(III) concentration values were determined. Vickers and Knoop indentations were used for determining their hardness, toughness, Young modulus and brittleness. The same measurements were carried on some silicate and aluminosilicate glasses. Also Weibull statistics was done to determine the characteristics (Weibull modulus and and fracture probability) of glass fracture. We found that silicate glasses (SG) are harder than phosphate glasses (PG). Toughness values for PG, are in the same range than for SG, although for the same density exhibit larger values or smaller brittleness than silicate glasses. For one of the glasses it was found that the mechanical load P 0 needed for a fracture probability of 63% increases with the Fe(II) content. (author)

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

International Nuclear Information System (INIS)

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

2005-01-01

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

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...

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

Science.gov (United States)

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

2009-04-06

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

A serials of sandwich-like trinuclear and one-dimensional chain cyanide-bridged iron(III)-copper(II) complexes: Syntheses, crystal structures and magnetic properties

Science.gov (United States)

Shi, Jingwen; Lan, Wenlong; Ren, Yanjie; Liu, Qingyun; Liu, Hui; Dong, Yunhui; Zhang, Daopeng

2018-04-01

Four pyridinecarboxamide trans-dicyanideiron(III) building blocks and one macrocyclic copper(II) compound have been employed to assemble cyanide-bridged heterometallic complexes, resulting in a serials of cyanide-bridged FeIII-CuII complexes with different structure types. The series of complexes can be formulated as: {[Cu(Cyclam)][Fe(bpb)(CN)2]2}·4H2O (1), {{[Cu(Cyclam)][Fe(bpb)(CN)2]}ClO4}n·nH2O (2), and {[Cu(Cyclam)][Fe(bpmb)(CN)2]2}·4H2O (3), {[Cu(Cyclam)][Fe(bpClb)(CN)2]2}·4H2O (4) and {{[Cu(Cyclam)][Fe(bpdmb)(CN)2]}ClO4}n·2nCH3OH (5) (bpb2- = 1,2-bis(pyridine-2-carboxamido)benzenate, bpmb2- = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate, bpClb2- = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate, bpdmb2- = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate, Cyclam = 1,4,8,11-tetraazacyclotetradecane). All the complexes have been characterized by elemental analysis, IR spectra and structural determination. Single X-ray diffraction analysis shows the similar neutral sandwich-like structures for complexes 1, 3 and 4, in which the two cyano precursors acting as monodentate ligand through one of their two cyanide groups were coordinated face to face to central Cu(II) ion. The complexes 2 and 5 can be structurally characterized as one-dimensional cationic single chain consisting of alternating units of [Cu(Cyclam)]2+ and [Fe(bpb/bpdmb)(CN)2]- with free ClO4- as balanced anion. Investigation over magnetic properties of the whole serials of complexes reveals the antiferromagnetic magnetic coupling between the neighboring cyanide-bridged Fe(III) and Cu(II) ions in complexes 3 and 4 and the ferromagnetic interaction in complexes 1, 2 and 5, respectively.

Factors to Enable Crystallization of Environmentally Stable Bioscorodite from Dilute As(III-Contaminated Waters

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Masahito Tanaka

2018-01-01

Full Text Available Applicability of the bioscorodite method (use of the thermo-acidophilic Fe(II-oxidizing archaeon Acidianus brierleyi for arsenic (As oxidation and immobilization at 70 °C was tested for synthetic copper refinery wastewaters of a wide range of dilute initial As(III concentrations ([As(III]ini = 3.3–20 mM with varying initial [Fe(II]/[As(III] molar ratios ([Fe(II]ini/[As(III]ini = 0.8–6.0. Crystallization of scorodite (FeAsO4·2H2O tends to become increasingly challenging at more dilute As(III solutions. Optimization of conditions such as initial pH, seed feeding and initial [Fe(II]/[As(III] molar ratio was found critical in improving final As removal and product stability: Whilst setting the initial pH at 1.2 resulted in an immediate single-stage precipitation of crystalline bioscorodite, the initial pH 1.5 led to a two-stage As precipitation (generation of brown amorphous precursors followed by whitish crystalline bioscorodite particles with a greater final As removal. The formation process of bioscorodite precipitates differed significantly depending on the type of seed crystals fed (bio- versus chemical- scorodite seeds. Feeding the former was found effective not only in accelerating the reaction, but also in forming more recalcitrant bioscorodite products (0.59 mg/L; Toxicity Characteristic Leaching Procedure (TCLP test. Under such favorable conditions, 94–99% of As was successfully removed as crystalline bioscorodite at all dilute As(III concentrations tested by setting [Fe(II]ini/[As(III]ini at 1.4–2.0. Providing an excess Fe(II (closer to [Fe(II]ini/[As(III]ini = 2.0 was found beneficial to improve the final As removal (up to 98–99% especially from more dilute As(III solutions.

Moessbauer study of FePO4 cathode for lithium- and sodium-ion batteries

International Nuclear Information System (INIS)

Tetsuaki Nishida; Masahiro Tokunaga; Toshiharu Nishizumi; Takafumi Yamamoto; Tomoyuki Shiratsuchi; Shigeto Okada; Jun-ichi Yamaki

2005-01-01

LiFePO 4 of olivine type has attracted much interest as a rare-metal free cathode for lithium-ion battery. The present authors' group has found a low-cost preparation method for new cathode material FePO 4 (P 321 ) from an aqueous solution of metallic iron and P 2 O 5 . A cathode pellet was prepared by mixing FePO 4 , acetylene black (AB) and polytetrafluoroethylene (PTFE) binder at a mass ratio of 70:25:5. Electrochemical cathode performance was investigated under a constant current density of 0.1 mA/cm 2 with a coin-type cell with an anode of metallic Li and Na for Li- and Na-ion batteries, respectively. Moessbauer spectra were measured by a constant accele- ration method with a Moessbauer source of 57 Co(Pd) and an α-Fe foil as a reference of the isomer shift. Moessbauer spectra of the original cathode pellet top left and right) composed of amorphous FePO 4 indicate that all the Fe III atoms have a tetrahedral symmetry. After discharging the Li-(second left) and Na-batteries (second right), all the Fe III were reduced to octahedral Fe II . The reduction of Fe III to Fe II indicates penetration of Li + and Na + into the FePO 4 cathode which accompanies an electron capture; Li + (or Na + ) + Fe III PO 4 + e - = LiFe II PO 4 (or NaFe II PO 4 ) After charging the Li-cell (bottom left), all the Fen atoms were oxidized to tetrahedral Fe III , while 69 % of Fe II was oxidized to Fe III in the Na-ion cell (bottom right) due to a lower cell voltage: 4.0 V. Oxidation of Fe II to Fe III reflects a release of Li + or Na + ions from the FePO 4 cathode to the electrolyte, i.e., an inverse reaction of eq.

Articulación de fones en individuos clase esqueletal I,II y III Speech patterns in skeletal class I, II and III subjects

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Pía Villanueva

2009-09-01

Full Text Available OBJETIVO: determinar los patrones de articulación de fones consonánticos en sujetos de habla española chilena clases I, II y III esqueletal; comparar las diferencias fonéticas que existan entre clases esqueletales. MÉTODOS: se seleccionaron 54 individuos que cumplían con los criterios de inclusión determinados mediante un examen clínico intraoral y a través del análisis de Ricketts, y se conformaron los grupos de estudio de pacientes clases esqueletales I, II y III. Se les realizó un examen fonoarticulatorio estandarizado para determinar los fones modificados y el patrón articulatorio compensatorio realizado. RESULTADOS: se observaron cambios en el punto de articulación de fones consonánticos en las tres clases esqueletales, con diferencias significativas en los grupos de fones anteriores y medios entre pacientes clases I y II, sólo en el grupo de los fones anteriores entre pacientes I y III. Entre pacientes clases II y III no se observaron diferencias significativas. Se reportan modificaciones y compensaciones cualitativamente distintas entre las clases esqueletales. CONCLUSIONES: en relación a pacientes clase I, los pacientes clase II o III, presentan distinto grado de modificación en el punto de articulación de fones consonánticos. Las diferencias observadas se relacionan con los patrones esqueletales propios de cada clase.PURPOSE: to determine the consonant phonemes articulation patterns in Chilean skeletal class I, II and III Spanish speakers and compare their phonetic differences. METHODS: fifty-four skeletal class I, II and III subjects were selected, based on intraoral clinical examination and Ricketts cephalometric analysis, constituting the study groups. A standardized phonoarticulatory test was applied to each patient to determine the modified phonemes and their compensatory patterns. RESULTS: the findings indicate changes in articulation in all three groups. Significant differences were found in anterior and medium

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.

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

Science.gov (United States)

Snyder, Shelly R.; White, Henry S.

1991-11-01

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

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.

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

Science.gov (United States)

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

2006-06-21

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

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.

Effect of Organic Fe-Ligands, Released by Emiliania huxleyi, on Fe(II Oxidation Rate in Seawater Under Simulated Ocean Acidification Conditions: A Modeling Approach

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Guillermo Samperio-Ramos

2018-06-01

Full Text Available The potential effect of ocean acidification on the exudation of organic matter by phytoplankton and, consequently, on the iron redox chemistry is largely unknown. In this study, the coccolithophorid Emiliania huxleyi was exposed to different pCO2 conditions (225–900 μatm, in order to determine the role of natural organic ligands on the Fe(II oxidation rate. Oxidation kinetics of Fe(II were studied as a function of pH (7.75–8.25 and dissolved organic carbon levels produced (0–141.11 μmol C L−1 during the different growth stages. The Fe(II oxidation rate always decreased in the presence of exudates as compared to that in the exudates-free seawater. The organic ligands present in the coccolithophorid exudates were responsible for this decrease. The oxidation of Fe(II in artificial seawater was also investigated at nanomolar levels over a range of pH (7.75–8.25 at 25°C in the presence of different glucuronic acid concentrations. Dissolved uronic acids (DUA slightly increased the experimental rate compared to control artificial seawater (ASW which can be ascribed to the stabilization of the oxidized form by chelation. This behavior was a function of the Fe(II:DUA ratio and was a pH dependent process. A kinetic model in ASW, with a single organic ligand, was applied for computing the equilibrium constant (log KFeCHO+ = 3.68 ± 0.81 M−1 and the oxidation rate (log kFeCHO+ = 3.28 ± 0.41 M−1 min−1 for the Fe(II-DUA complex (FeCHO+, providing an excellent description of data obtained over a wide range of DUA concentrations and pH conditions. Considering the Marcus theory the Fe(III complexing constant with DUA was limited to between 1013 and 1016. For the seawater enriched with exudates of E. huxleyi a second kinetic modeling approach was carried out for fitting the Fe(II speciation, and the contribution of each Fe(II species to the overall oxidation rate as a function of the pH/pCO2 conditions. The influence of organic ligands in the

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

Science.gov (United States)

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

2010-01-01

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

Spectroscopic, Elemental and Thermal Analysis, and Positron Annihilation Studies on Ca(II), Sr(II), Ba(II), Pb(II), and Fe(III) Penicillin G Potassium Complexes

Science.gov (United States)

Refat, M. S.; Sharshara, T.

2015-11-01

The [Pb(Pin)2] · 3H2O, [M(Pin)(H2O)2(Cl)] · nH2O (M = SrII, CaII or BaII; n = 0-1), and [Fe(Pin)2(Cl)(H2O)] · H2O penicillin G potassium (Pin) complexes were synthesized and characterized using elemental analyses, molar conductivity, thermal analysis and electronic spectroscopy techniques. The positron annihilation lifetime (PAL) and Doppler broadening (DB) techniques have been employed to probe the defects and structural changes of Pin ligand and its complexes. The PAL and DB line-shape parameters were discussed in terms of the structure, molecular weight, ligand-metal molar ratio, and other properties of the Pin complexes.

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

International Nuclear Information System (INIS)

Purohit, K.; Desai, K.K.

2006-01-01

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

Highly sensitive amperometric sensor for micromolar detection of trichloroacetic acid based on multiwalled carbon nanotubes and Fe(II)–phtalocyanine modified glassy carbon electrode

International Nuclear Information System (INIS)

Kurd, Masoumeh; Salimi, Abdollah; Hallaj, Rahman

2013-01-01

A highly sensitive electrochemical sensor for the detection of trichloroacetic acid (TCA) is developed by subsequent immobilization of phthalocyanine (Pc) and Fe(II) onto multiwalled carbon nanotubes (MWCNTs) modified glassy carbon (GC) electrode. The GC/MWCNTs/Pc/Fe(II) electrode showed a pair of well-defined and nearly reversible redox couple correspondent to (Fe(III)Pc/Fe(II)Pc) with surface-confined characteristics. The surface coverage (Γ) and heterogeneous electron transfer rate constant (k s ) of immobilized Fe(II)–Pc were calculated as 1.26 × 10 −10 mol cm −2 and 28.13 s −1 , respectively. Excellent electrocatalytic activity of the proposed GC/MWCNTs/Pc/Fe(II) system toward TCA reduction has been indicated and the three consequent irreversible peaks for electroreduction of CCl 3 COOH to CH 3 COOH have been clearly seen. The observed chronoamperometric currents are linearly increased with the concentration of TCA at concentration range up to 20 mM. Detection limit and sensitivity of the modified electrode were 2.0 μM and 0.10 μA μM −1 cm −2 , respectively. The applicability of the sensor for TCA detection in real samples was tested. The obtained results suggest that the proposed system can serve as a promising electrochemical platform for TCA detection. Highlights: ► Phthalocyanine (PC) and Fe(II) immobilized onto MWCNTs modified GC electrode. ► A pair of well-defined redox couple correspondent to (Fe(III)Pc/Fe(II)Pc) observed. ► Modified electrode shows excellent catalytic activity to electroreduction of CCl 3 COOH. ► Amperometry and cyclic voltammetry techniques were used for detection of CCl 3 COOH. ► Detection limit and sensitivity were 2.0 μM and 0.10 μA μM −1 cm −2 , respectively

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.

A role of copper(II) ions in the enhancement of visible and near-infrared lanthanide(III) luminescence

International Nuclear Information System (INIS)

Eliseeva, Svetlana V.; Golovach, Iurii P.; Liasotskyi, Valerii S.; Antonovich, Valery P.; Petoud, Stéphane; Meshkova, Svetlana B.

2016-01-01

Most of the existing optical methods for Cu II detection rely on a “turn-off” approach using visible lanthanide(III) luminescence. In this work we present an innovative molecular systems where the podands bis(2-hydrazinocarbonylphenyl) ethers of ethylene glycol (L1) and diethylene glycol (L2) have been designed, synthesised and tested with an ultimate goal to create a "turn-on" lanthanide(III)-based molecular probe for the specific detection of Cu II ions based on both visible (Tb III , Eu III ) and near-infrared (Nd III , Yb III ) emission. Quantum yields of the characteristic Ln III emission signals increases by at least two-orders of magnitude upon addition of Cu II into water/acetonitrile (9/1) solutions of LnL (L=L1, L2) complexes. A detailed investigation of ligand-centred photophysical properties of water/acetonitrile (9/1) solutions of CuL, GdL and GdCuL complexes revealed that the presence of Cu II ions does not significantly affect the energy positions of the singlet (32,260 cm −1 ) and triplet (25,640–25,970 cm −1 ) states, but partially or fully eliminates the singlet state quenching through an electron transfer mechanism. This effect increases the probability of intersystem crossing leading to enhanced triplet-to-singlet emission ratio and to longer triplet state lifetimes. The redox activity of hydrazine moieties and their ability to reduce Cu II to Cu I has been indicated by a qualitative assay with neocuproine. Finally, the probe demonstrates a good selectivity towards Cu II over other transition metal ions: the addition of divalent Zn II , Cd II , Pd II , Ni II , Co II or trivalent Fe III , Ga III , In III ion salts into solutions of TbL either does not affect emission intensity or increases it to a maximum of 2–3 times, while, under similar experimental conditions, the presence of Cu II results in a 20- to 30-times lanthanide luminescence enhancement. This new strategy results in a versatile and selective optical platform for the

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

Science.gov (United States)

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

2015-11-01

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

Sequestration of chelated copper by structural Fe(II): Reductive decomplexation and transformation of Cu{sup II}-EDTA

Energy Technology Data Exchange (ETDEWEB)

He, Hongping [State Key Laboratory of Pollution Control and Resources Reuse, School of Environmental Science & Engineering, Tongji University, Shanghai 200092 (China); Wu, Deli, E-mail: wudeli@tongji.edu.cn [State Key Laboratory of Pollution Control and Resources Reuse, School of Environmental Science & Engineering, Tongji University, Shanghai 200092 (China); Zhao, Linghui [State Key Laboratory of Pollution Control and Resources Reuse, School of Environmental Science & Engineering, Tongji University, Shanghai 200092 (China); Luo, Cong [School of Civil and Environmental Engineering, Georgia Institute of Technology, GA 30332 (United States); Dai, Chaomeng; Zhang, Yalei [State Key Laboratory of Pollution Control and Resources Reuse, School of Environmental Science & Engineering, Tongji University, Shanghai 200092 (China)

2016-05-15

Highlights: • Structural Fe(II) was found to reveal high sequestration potential in various chelated copper. • Chelated copper was reduced to Cu(0) and Cu{sub 2}O by =Fe(II), whcih was oxidized to Fe{sub 2}O{sub 3}·H{sub 2}O. • Both electron transfer and surface =Fe(II) were found to be crucial during chelated copper reduction. • The indispensible role of reductive decomplexation was identified in chelated copper sequestration. - Abstract: Chelated coppers, such as Cu{sup II}-EDTA, are characteristically refractory and difficult to break down because of their high stability and solubility. Cu{sup II}–EDTA sequestration by structural Fe(II) (=Fe(II)) was investigated intensively in this study. Up to 101.21 mgCu(II)/gFe(II) was obtained by =Fe(II) in chelated copper sequestration under near neutral pH condition (pH 7.70). The mechanism of Cu{sup II}-EDTA sequestration by =Fe(II) was concluded as follows: 3Cu{sup II}–EDTA + 7=Fe(II) + 9H{sub 2}O → Cu(0) ↓ + Cu{sub 2}O ↓ (the major product) + 2Fe{sub 2}O{sub 3}·H{sub 2}O ↓ + 3Fe{sup II}–EDTA +14H{sup +} Novel results strongly indicate that Cu{sup II} reductive transformation induced by surface =Fe(II) was mainly responsible for chelated copper sequestration. Cu(0) generation was initially facilitated, and subsequent reduction of Cu(II) into Cu(I) was closely combined with the gradual increase of ORP (Oxidation-Reduction Potential). Cu-containing products were inherently stable, but Cu{sub 2}O would be reoxidized to Cu(II) with extra-aeration, resulting in the release of copper, which was beneficial to Cu reclamation. Concentration diminution of Cu{sup II}–EDTA within the electric double layer and competitive adsorption were responsible for the negative effects of Ca{sup 2+}, Mg{sup 2+}. By generating vivianite, PO{sub 4}{sup 3−} was found to decrease surface =Fe(II) content. This study is among the first ones to identify the indispensible role of reductive decomplexation in chelated copper

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)

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

International Nuclear Information System (INIS)

Maurice, P.

2004-01-01

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

Size, density and composition of cell-mineral aggregates formed during anoxygenic phototrophic Fe(II) oxidation: Impact on modern and ancient environments

DEFF Research Database (Denmark)

Posth, Nicole R.; Huelin, Sonia; Konhauser, Kurt O.

2010-01-01

Cell-Fe(III) mineral aggregates produced by anoxygenic Fe(II)-oxidizing photoautotrophic microorganisms (photoferrotrophs) may be influential in the modern Fe cycle and were likely an integral part of ancient biogeochemical cycles on early Earth. While studies have focused on the environmental...... conditions under which modern photoferrotrophs grow and the kinetics, physiology and mechanism of Fe(II) oxidation, no systematic analyses of the physico-chemical characteristics of those aggregates, such as shape, size, density and chemical composition, have as yet been conducted. Herein, experimental...... results show most aggregates are bulbous or ragged in shape, with an average particle size of 10-40??m, and densities that typically range between 2.0 and 2.4g/cm 3; the cell fraction of the aggregates increased and their density decreased with initial Fe(II) concentration. The mineralogy of the ferric...

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

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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

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

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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.

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.

Mechanisms of Fe biofortification and mitigation of Cd accumulation in rice (Oryza sativa L.) grown hydroponically with Fe chelate fertilization.

Science.gov (United States)

Chen, Zhe; Tang, Ye-Tao; Zhou, Can; Xie, Shu-Ting; Xiao, Shi; Baker, Alan J M; Qiu, Rong-Liang

2017-05-01

Cadmium contaminated rice from China has become a global food safety issue. Some research has suggested that chelate addition to substrates can affect metal speciation and plant metal content. We investigated the mitigation of Cd accumulation in hydroponically-grown rice supplied with EDTANa 2 Fe(II) or EDDHAFe(III). A japonica rice variety (Nipponbare) was grown in modified Kimura B solution containing three concentrations (0, 10, 100 μΜ) of the iron chelates EDTANa 2 Fe(II) or EDDHAFe(III) and 1 μΜ Cd. Metal speciation in solution was simulated by Geochem-EZ; growth and photosynthetic efficiency of rice were evaluated, and accumulation of Cd and Fe in plant parts was determined. Net Cd fluxes in the meristematic zone, growth zone, and maturation zone of roots were monitored by a non-invasive micro-test technology. Expression of Fe- and Cd-related genes in Fe-sufficient or Fe-deficient roots and leaves were studied by QRT-PCR. Compared to Fe deficiency, a sufficient or excess supply of Fe chelates significantly enhanced rice growth by elevating photosynthetic efficiency. Both Fe chelates increased the Fe content and decreased the Cd content of rice organs, except for the Cd content of roots treated with excess EDDHAFe(III). Compared to EDDHAFe(III), EDTANa 2 Fe(II) exhibited better mitigation of Cd accumulation in rice by generating the EDTANa 2 Cd complex in solution, decreasing net Cd influx and increasing net Cd efflux in root micro-zones. Application of EDTANa 2 Fe(II) and EDDHAFe(III) also reduced Cd accumulation in rice by inhibiting expression of genes involved in transport of Fe and Cd in the xylem and phloem. The 'win-win' situation of Fe biofortification and Cd mitigation in rice was achieved by application of Fe chelates. Root-to-stem xylem transport of Cd and redistribution of Cd in leaves by phloem transport can be regulated in rice through the use of Fe chelates that influence Fe availability and Fe-related gene expression. Fe fertilization

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

Science.gov (United States)

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

2006-07-10

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

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.

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

International Nuclear Information System (INIS)

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

2012-01-01

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

The effects of iron(II) on the kinetics of arsenic oxidation and sorption on manganese oxides.

Science.gov (United States)

Wu, Yun; Li, Wei; Sparks, Donald L

2015-11-01

In this study, As(III) oxidation kinetics by a poorly-crystalline phyllomanganate (δ-MnO2) in the presence and absence of dissolved Fe(II) was investigated using stirred-flow and batch experiments. Chemically synthetic δ-MnO2 was reacted with four influent solutions, containing the same As(III) concentration but different Fe(II) concentrations, at pH 6. The results show an initial rapid As(III) oxidation by δ-MnO2, which is followed by an appreciably slow reaction after 8h. In the presence of Fe(II), As(III) oxidation is inhibited due to the competitive oxidation of Fe(II) as well as the formation of Fe(III)-(hydr)oxides on the δ-MnO2 surface. However, the sorption of As(III), As(V) and Mn(II) are increased, for the newly formed Fe(III)-(hydr)oxides provide additional sorption sites. This study suggests that the competitive oxidation of Fe(II) and consequently the precipitation of Fe(III) compounds on the δ-MnO2 surface play an important role in As(III) oxidation and As sequestration. Understanding these processes would be helpful in developing in situ strategies for remediation of As-contaminated waters and soils. Copyright © 2015 Elsevier Inc. All rights reserved.

[FeII] as a tracer supernova rate

International Nuclear Information System (INIS)

Rosenberg, M J F; Van der Werf, P P; Israel, F P

2012-01-01

Supernovae play an integral role in the feedback of processed material into the ISM of galaxies and are responsible for most of the chemical enrichment of the universe. The rate of supernovae can also reveal the star formation histories. Supernova rate is usually measured through the non-thermal radio continuum luminosity, but in this paper we establish a quantitative relationship between the [FeII] 1.26 luminosity and supernova rate in a sample of 11 near-by starburst galaxies. SINFONI data cubes are used to perform a pixel pixel analysis of this correlation. Using Bry equivalent width and luminosity as the only observational inputs into Starburst 99, the supernova rate is derived at each pixel and a map of supernova rate is created. This is then compared morphologically and quantitatively to [FeII] 1.26 luminosity map. We find a strong linear and morphological correlation between supernova rate and [FeII] 1.26 on a pixel-pixel basis. The Starburst 99 derived supernova rates are also in good agreement with the radio derived supernova rates, which further demonstrates the strength of [FeII] as a tracer of supernova rate. With the strong correlation found in this sample of galaxies, we now qualitatively use [FeII] 1.26 to derive supernova rate on either a pixel-pixel or integrated galactic basis.

The Physiological Functions and Structural Determinants of Catalytic Bias in the [FeFe]-Hydrogenases CpI and CpII of Clostridium pasteurianum Strain W5

Directory of Open Access Journals (Sweden)

Jesse B. Therien

2017-07-01

Full Text Available The first generation of biochemical studies of complex, iron-sulfur-cluster-containing [FeFe]-hydrogenases and Mo-nitrogenase were carried out on enzymes purified from Clostridium pasteurianum (strain W5. Previous studies suggested that two distinct [FeFe]-hydrogenases are expressed differentially under nitrogen-fixing and non-nitrogen-fixing conditions. As a result, the first characterized [FeFe]-hydrogenase (CpI is presumed to have a primary role in central metabolism, recycling reduced electron carriers that accumulate during fermentation via proton reduction. A role for capturing reducing equivalents released as hydrogen during nitrogen fixation has been proposed for the second hydrogenase, CpII. Biochemical characterization of CpI and CpII indicated CpI has extremely high hydrogen production activity in comparison to CpII, while CpII has elevated hydrogen oxidation activity in comparison to CpI when assayed under the same conditions. This suggests that these enzymes have evolved a catalytic bias to support their respective physiological functions. Using the published genome of C. pasteurianum (strain W5 hydrogenase sequences were identified, including the already known [NiFe]-hydrogenase, CpI, and CpII sequences, and a third hydrogenase, CpIII was identified in the genome as well. Quantitative real-time PCR experiments were performed in order to analyze transcript abundance of the hydrogenases under diazotrophic and non-diazotrophic growth conditions. There is a markedly reduced level of CpI gene expression together with concomitant increases in CpII gene expression under nitrogen-fixing conditions. Structure-based analyses of the CpI and CpII sequences reveal variations in their catalytic sites that may contribute to their alternative physiological roles. This work demonstrates that the physiological roles of CpI and CpII are to evolve and to consume hydrogen, respectively, in concurrence with their catalytic activities in vitro, with CpII

The Physiological Functions and Structural Determinants of Catalytic Bias in the [FeFe]-Hydrogenases CpI and CpII of Clostridium pasteurianum Strain W5

Science.gov (United States)

Therien, Jesse B.; Artz, Jacob H.; Poudel, Saroj; Hamilton, Trinity L.; Liu, Zhenfeng; Noone, Seth M.; Adams, Michael W. W.; King, Paul W.; Bryant, Donald A.; Boyd, Eric S.; Peters, John W.

2017-01-01

The first generation of biochemical studies of complex, iron-sulfur-cluster-containing [FeFe]-hydrogenases and Mo-nitrogenase were carried out on enzymes purified from Clostridium pasteurianum (strain W5). Previous studies suggested that two distinct [FeFe]-hydrogenases are expressed differentially under nitrogen-fixing and non-nitrogen-fixing conditions. As a result, the first characterized [FeFe]-hydrogenase (CpI) is presumed to have a primary role in central metabolism, recycling reduced electron carriers that accumulate during fermentation via proton reduction. A role for capturing reducing equivalents released as hydrogen during nitrogen fixation has been proposed for the second hydrogenase, CpII. Biochemical characterization of CpI and CpII indicated CpI has extremely high hydrogen production activity in comparison to CpII, while CpII has elevated hydrogen oxidation activity in comparison to CpI when assayed under the same conditions. This suggests that these enzymes have evolved a catalytic bias to support their respective physiological functions. Using the published genome of C. pasteurianum (strain W5) hydrogenase sequences were identified, including the already known [NiFe]-hydrogenase, CpI, and CpII sequences, and a third hydrogenase, CpIII was identified in the genome as well. Quantitative real-time PCR experiments were performed in order to analyze transcript abundance of the hydrogenases under diazotrophic and non-diazotrophic growth conditions. There is a markedly reduced level of CpI gene expression together with concomitant increases in CpII gene expression under nitrogen-fixing conditions. Structure-based analyses of the CpI and CpII sequences reveal variations in their catalytic sites that may contribute to their alternative physiological roles. This work demonstrates that the physiological roles of CpI and CpII are to evolve and to consume hydrogen, respectively, in concurrence with their catalytic activities in vitro, with CpII capturing excess

A role of copper(II) ions in the enhancement of visible and near-infrared lanthanide(III) luminescence

Energy Technology Data Exchange (ETDEWEB)

Eliseeva, Svetlana V., E-mail: svetlana.eliseeva@cnrs-orleans.fr [Centre de Biophysique Moléculaire CNRS UPR 4301, Rue Charles Sadron, 45071 Orléans Cedex 2 (France); Le Studium, Loire Valley Institute for Advanced Studies, 1 Rue Dupanloup, 45000 Orléans (France); Golovach, Iurii P.; Liasotskyi, Valerii S. [I.I.Mechnikov Odessa National University, 2 Dvoryanska street, 65082 Odessa (Ukraine); Antonovich, Valery P. [A.V. Bogatsky Physico-Chemical Institute of the National Academy of Sciences of Ukraine, 86 Lustdorfskaya doroga, 65080 Odessa (Ukraine); Petoud, Stéphane, E-mail: stephane.petoud@inserm.fr [Centre de Biophysique Moléculaire CNRS UPR 4301, Rue Charles Sadron, 45071 Orléans Cedex 2 (France); Meshkova, Svetlana B., E-mail: s_meshkova@ukr.net [A.V. Bogatsky Physico-Chemical Institute of the National Academy of Sciences of Ukraine, 86 Lustdorfskaya doroga, 65080 Odessa (Ukraine)

2016-03-15

Most of the existing optical methods for Cu{sup II} detection rely on a “turn-off” approach using visible lanthanide(III) luminescence. In this work we present an innovative molecular systems where the podands bis(2-hydrazinocarbonylphenyl) ethers of ethylene glycol (L1) and diethylene glycol (L2) have been designed, synthesised and tested with an ultimate goal to create a 'turn-on' lanthanide(III)-based molecular probe for the specific detection of Cu{sup II} ions based on both visible (Tb{sup III}, Eu{sup III}) and near-infrared (Nd{sup III}, Yb{sup III}) emission. Quantum yields of the characteristic Ln{sup III} emission signals increases by at least two-orders of magnitude upon addition of Cu{sup II} into water/acetonitrile (9/1) solutions of LnL (L=L1, L2) complexes. A detailed investigation of ligand-centred photophysical properties of water/acetonitrile (9/1) solutions of CuL, GdL and GdCuL complexes revealed that the presence of Cu{sup II} ions does not significantly affect the energy positions of the singlet (32,260 cm{sup −1}) and triplet (25,640–25,970 cm{sup −1}) states, but partially or fully eliminates the singlet state quenching through an electron transfer mechanism. This effect increases the probability of intersystem crossing leading to enhanced triplet-to-singlet emission ratio and to longer triplet state lifetimes. The redox activity of hydrazine moieties and their ability to reduce Cu{sup II} to Cu{sup I} has been indicated by a qualitative assay with neocuproine. Finally, the probe demonstrates a good selectivity towards Cu{sup II} over other transition metal ions: the addition of divalent Zn{sup II}, Cd{sup II}, Pd{sup II}, Ni{sup II}, Co{sup II} or trivalent Fe{sup III}, Ga{sup III}, In{sup III} ion salts into solutions of TbL either does not affect emission intensity or increases it to a maximum of 2–3 times, while, under similar experimental conditions, the presence of Cu{sup II} results in a 20- to 30-times

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

Science.gov (United States)

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

2017-09-01

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

Stable Fe isotope fractionation during anaerobic microbial dissimilatory iron reduction at low pH

Science.gov (United States)

Chanda, P.; Amenabar, M. J.; Boyd, E. S.; Beard, B. L.; Johnson, C.

2017-12-01

In low-temperature anaerobic environments microbial dissimilatory iron reduction (DIR) plays an important role in Fe cycling. At neutral pH, sorption of aqueous Fe(II) (Fe(II)aq, produced by DIR) catalyzes isotopic exchange between Fe(II) and solid Fe(III), producing 56Fe/54Fe fractionations on the order of 3‰ during DIR[1,2,3]. At low pH, however, the absence of sorbed Fe(II) produces only limited abiologic isotopic exchange[4]. Here we investigated the scope of isotopic exchange between Fe(II)aq and ferric (hydr)oxides (ferrihydrite and goethite) and the associated stable Fe isotope fractionation during DIR by Acidianus strain DS80 at pH 3.0 and 80°C[5]. Over 19 days, 13% reduction of both minerals via microbial DIR was observed. The δ56Fe values of the fluid varied from -2.31 to -1.63‰ (ferrihydrite) and -0.45 to 0.02‰ (goethite). Partial leaching of bulk solid from each reactor with dilute HCl showed no sorption of Fe(II), and the surface layers of the solids were composed of Fe(III) with high δ56Fe values (ferrihydrite: 0.20 to 0.48‰ and goethite: 1.20 to 1.30‰). These results contrast with the lack of Fe isotope exchange in abiologic low-pH systems and indicate a key role for biology in catalyzing Fe isotope exchange between Fe(II)aq and Fe(III) solids, despite the absence of sorbed Fe(II). The estimated fractionation factor (ΔFeFe(III) -Fe(II)aq 2.6‰) from leaching of ferrihydrite is similar to the abiologic equilibrium fractionation factor ( 3.0‰)[3]. The fractionation factor (ΔFeFe(III) -Fe(II)aq 2.0‰) for goethite is higher than the abiologic fractionation factor ( 1.05‰)[2], but is consistent with the previously proposed "distorted surface layer" of goethite produced during the exchange with Fe(II)aq at neutral pH[1]. This study indicates that significant variations in Fe isotope compositions may be produced in low-pH environments where biological cycling of Fe occurs, in contrast to the expected lack of isotopic fractionation in

Study of the interference of uranium, vanadium, aluminium and molebdenum in the determination of FeII, FeIII in Syrian phosphoric acid by spectrophotometry

International Nuclear Information System (INIS)

Zaizafoun, Ghadir; Elian, Nazha

1991-04-01

The spectrophotometric determination of the ratio of iron I I to iron I II in crude phosphoric acid is of great importance because of its influence on the redox potential in the different stages which lead to the extraction of uranium from crude phosphoric acid. The suitability of a number of reagents for this determination was examined and only 1,10-phenanthroline, 5-sulfosalicylic acid and 2,2'-bipyridine were selected for further experimentation. 1-10-phenanthroline can give a deep red complex with Fe I I, in phosphoric acid medium at PH 4-6, absorbs at λ = 510 nm. The total iron was determined by reducing Fe I II to Fe I I using hydroxylamine hydrochloride. The second reagent was found capable of forming a yellow complex absorbs light at λ = 430 nm in amonia medium at PH 8.5 - 11 with Fe I II. The adopted procedure was to determine total iron first by oxidation with nitric acid. Then iron I I was determined in a second test at PH 1.5 and at λ = 500 nm. The third reagent i.e. 2-2' bipyridine is capable of forming a red complex with iron I I absorbs at λ = 522 nm. The interference of U, V, Al, and Mo was investigated. These elements were selected because of their presence in considerable amounts in Syrian commercial phosphoric acid. The work was designed so that the effect of the presence of each element as well as the presence of all possible combinations of these elements can be estimated. The investigation revealed that the interference is very high in the case of 2-2' bipyridine in addition to the instability of the complex. In the case of 1,10-phenanthroline the interference was also found high. Thus these two reagents were disregarded. The 5-sulfosalicylic reagent was found satisfactory when determining iron I II, However when Fe I I is considered the error resulting from interference ranges between 17.5 - 50%. This error was found very dependent on the PH of the medium and further work is in progress in order to lower the value of interferences

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

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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.

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

Directory of Open Access Journals (Sweden)

Elena Sorokina

2013-01-01

Full Text Available The effect of iron ions Fe2+ and Fe3+ on the bioluminescent recombinant strain of Escherichia coli in a single-component and binary system. Found that for the bacteria E. coli Fe3+ ions are more toxic than Fe2+. Under the combined effect of iron toxicity increases, the percentage of luminescence quenching increases, but the value is much less than the sum of the indicator for the Fe2+ and Fe3+. The biological effect of insertion of iron is not proportional to their content in the mixture.

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

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)

Highly sensitive amperometric sensor for micromolar detection of trichloroacetic acid based on multiwalled carbon nanotubes and Fe(II)–phtalocyanine modified glassy carbon electrode

Energy Technology Data Exchange (ETDEWEB)

Kurd, Masoumeh [Department of Chemistry, University of Kurdistan, P. O. Box 416, Sanandaj (Iran, Islamic Republic of); Salimi, Abdollah, E-mail: absalimi@uok.ac.ir [Department of Chemistry, University of Kurdistan, P. O. Box 416, Sanandaj (Iran, Islamic Republic of); Research Center for Nanotechnology, University of Kurdistan, P. O. Box 416, Sanandaj (Iran, Islamic Republic of); Hallaj, Rahman [Department of Chemistry, University of Kurdistan, P. O. Box 416, Sanandaj (Iran, Islamic Republic of)

2013-04-01

A highly sensitive electrochemical sensor for the detection of trichloroacetic acid (TCA) is developed by subsequent immobilization of phthalocyanine (Pc) and Fe(II) onto multiwalled carbon nanotubes (MWCNTs) modified glassy carbon (GC) electrode. The GC/MWCNTs/Pc/Fe(II) electrode showed a pair of well-defined and nearly reversible redox couple correspondent to (Fe(III)Pc/Fe(II)Pc) with surface-confined characteristics. The surface coverage (Γ) and heterogeneous electron transfer rate constant (k{sub s}) of immobilized Fe(II)–Pc were calculated as 1.26 × 10{sup −10} mol cm{sup −2} and 28.13 s{sup −1}, respectively. Excellent electrocatalytic activity of the proposed GC/MWCNTs/Pc/Fe(II) system toward TCA reduction has been indicated and the three consequent irreversible peaks for electroreduction of CCl{sub 3}COOH to CH{sub 3}COOH have been clearly seen. The observed chronoamperometric currents are linearly increased with the concentration of TCA at concentration range up to 20 mM. Detection limit and sensitivity of the modified electrode were 2.0 μM and 0.10 μA μM{sup −1} cm{sup −2}, respectively. The applicability of the sensor for TCA detection in real samples was tested. The obtained results suggest that the proposed system can serve as a promising electrochemical platform for TCA detection. Highlights: ► Phthalocyanine (PC) and Fe(II) immobilized onto MWCNTs modified GC electrode. ► A pair of well-defined redox couple correspondent to (Fe(III)Pc/Fe(II)Pc) observed. ► Modified electrode shows excellent catalytic activity to electroreduction of CCl{sub 3}COOH. ► Amperometry and cyclic voltammetry techniques were used for detection of CCl{sub 3}COOH. ► Detection limit and sensitivity were 2.0 μM and 0.10 μA μM{sup −1} cm{sup −2}, respectively.

An extreme Fe II emitter the narrow line quasar PHL 1092

CERN Document Server

Bergeron, J

1980-01-01

A search for Fe II emission in a sample of radio-quiet quasars has revealed the outstanding properties of PHL 1092. Intense Fe II lines dominate the entire spectrum, and the Fe II UV multiplets are nearly as strong as the optical ones. In contrast the extreme weakness of the Balmer and Mg II lines is striking. For the first time, Fe I lines are identified in an extra-galactic object. The lines are narrow, with a FWHM of 1300 km s/sup -1/. The presence of Fe II UV lines and Fe I lines from the ground state requires moderate column densities. However Fe/sup 0/ can exist only in a region completely shielded from the UV continuum. The weakness of Mg II and H beta relative to Fe II lines is best explained by their thermalization. The emitting region is of high electron density n/sub e/ approximately=10/sup 12/ cm/sup -3/, low temperature T approximately=10000K, and has an optical depth in the Fe II UV lines tau /sub UV/ approximately=10/sup 3/-10/sup 4/. It is speculated that for higher densities all the lines wou...

Synthesis and Characterization of Multimetallic Fe(II) and Mn(II ...

African Journals Online (AJOL)

Iron(II) and Manganese(II) complexes of the resulting ligand were obtained from its reactions with Fe(II) and Mn(II) salts in absolute methanol for the metal to ligand ratio 2:3. These complexes were characterized by Solubility, Conductivity, IR and UV-VIS spectrometry, elemental analysis and mass spectrometry. Keywords: ...

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

Science.gov (United States)

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

2009-01-01

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

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

Spectrophotometric analysis of vitamin E using Cu(I)-Bathocuproine or/and Fe(II)-2,4,6-tris-(2'-pyridyl)-s-triazine complexes

International Nuclear Information System (INIS)

Devi, I.; Memon, S. A.; Khuhawar, M.Y.

2004-01-01

Vitamin E (tocopherols and tocotrienols) antioxidants are determined by reducing Cu(II) to Cu(I) or Fe(III) to Fe(II) in presence of vitamin E and subsequent complexation of Cu(I) with bathocuproine and/or Fe(II) with 2,4,6-tris-(2'-pyridyl)-s-triazine (TPTZ). Both the reactions are monitored separately, Cu(I)-bathocuproine at 479 nm where as, Fe(II)-(TPTZ) at 595 nm spectrophotometrically. Linear calibration curves are achieved for both complexes between I to 5mu g ml-1 for vitamin E. The methods were applied for the determination of vitamin E in pharmaceutical preparations and edible oils. Vitamin E, from edible oils, was solvent extracted into n-hexane prior to saponification. Furthermore, a single lined flow was also examined. A larger excess of Cu(II) or Fe =(II) with different concentrations of vitamin E in buffer pH 4 was run on the line and constant amounts of reagent bathocuproine or TPTZ in each case was injected through the injector. The peak height shows a linear relationship for vitamin E between 0.5 to 2.5 mu g ml-1 for both complexes. (author)

Fe-Ti/Fe (II)-loading on ceramic filter materials for residual chlorine removal from drinking water.

Science.gov (United States)

Man, Kexin; Zhu, Qi; Guo, Zheng; Xing, Zipeng

2018-06-01

Ceramic filter material was prepared with silicon dioxide (SiO 2 ), which was recovered from red mud and then modified with Fe (II) and Fe-Ti bimetal oxide. Ceramic filter material can be used to reduce the content of residual chlorine from drinking water. The results showed that after a two-step leaching process with 3 M hydrochloric acid (HCl) and 90% sulfuric acid (H 2 SO 4 ), the recovery of SiO 2 exceeded 80%. Fe (II)/Fe-Ti bimetal oxide, with a high adsorption capacity of residual chlorine, was prepared using a 3:1 M ratio of Fe/Ti and a concentration of 0.4 mol/L Fe 2+ . According to the zeta-potential, scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) analysis, Fe (II) and Fe-Ti bimetal oxide altered the zeta potential and structural properties of the ceramic filter material. There was a synergistic interaction between Fe and Ti in which FeOTi bonds on the material surface and hydroxyl groups provided the active sites for adsorption. Through a redox reaction, Fe (II) transfers hypochlorite to chloride, and FeOTiCl bonds were formed after adsorption. Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

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.

Hydroxyl Radical Formation from HULIS and Fe(II) Interactions: Fulvic Acid-Fe(II) Complexes in Simulated and Human Lung Fluids

Science.gov (United States)

Gonzalez, D.

2017-12-01

Inhalation of fine particulate matter (PM2.5) has long been associated with adverse health outcomes. However, the causative agents and underlying mechanisms for these health effects have yet to be identified. One hypothesis is that PM2.5 deposited in the alveoli produce an excess of highly reactive radicals, leading to oxidative stress. The OH radical may be the most physiologically damaging, capable of oxidizing of lipids, proteins and DNA. Due to the variability and uncertainty in PM2.5 composition, the components that contribute to OH formation are not well understood. Soluble Fe is a component of PM2.5that produces OH under physiological conditions. Humic-like substances are water soluble organics found in biomass burning and tobacco smoke. Humic-like substances are capable of binding to Fe and enhancing OH formation, but this chemistry is not well understood. In this work, we use soil derived fulvic acid as a surrogate for Humic-like substances and investigate its effect on OH formation from Fe(II) under conditions relevant to the lungs. We use a fluorescent OH trapping probe, chemical kinetics and thermodynamic modeling to investigate OH formation from fulvic acid and Fe(II) dissolved in simulated and human lung fluids. In simulated lung fluid, we find that fulvic acid binds to Fe(II) and enhances the rate of key reactions that form OH. When fulvic acid is added to human lung fluids containing Fe(II), an enhancement of OH formation is observed. In human lung fluid, fulvic acid and metal binding proteins compete for Fe binding. These metal binding proteins are typically not found in simulated lung fluids. Results show that fulvic acid strongly binds Fe(II) and catalyzes key reactions that form OH in both simulated and human lung fluids. These results may help explain the role of Humic-like substances and Fe in oxidative stress and adverse health outcomes. Furthermore, we suggest that future studies employ simulated lung fluids containing metal binding proteins

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.

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.

Efficiency of Chitosan for the Removal of Pb (II, Fe (II and Cu (II Ions from Aqueous Solutions

Directory of Open Access Journals (Sweden)

Soheil Sobhanardakani

2014-09-01

Full Text Available Background: Heavy metals have been recognized as harmful environmental pollutant known to produce highly toxic effects on different organs and systems of both humans and animals. The aim of this paper is to evaluate the adsorption potential of chitosan for the removal of Pb(II, Fe(II and Cu(II ions from aqueous solutions. Methods: This study was conducted in laboratory scale. In this paper chitosan has been used as an adsorbent for the removal of Pb(II, Fe(II and Cu(II from aqueous solution. In batch tests, the effects of parameters like pH solution (1.0-8.0, initial metal concentrations (100-1000 mgL-1, contact time (5.0-150 min and adsorbent dose (1.0-7.0 g on the adsorption process were studied. Results: The results showed that the adsorption of Pb(II, Fe(II and Cu(II ions on chitosan strongly depends on pH. The experimental isothermal data were analyzed using the Langmuir and Freundlich equations and it was found that the removal process followed the Langmuir isotherm and maximum adsorption capacity for the adsorption of Pb(II, Fe(II and Cu(II ions by the chitosan were 55.5mg g−1, 71.4 mg g−1 and 59 mg g−1, respectively, under equilibrium conditions at 25±1 ºC. The adsorption process was found to be well described by the pseudo-second-order rate model. Conclusion: The obtained results showed that chitosan is a readily, available, economic adsorbent and was found suitable for removing Pb(II, Fe(II and Cu(II ions from aqueous solution.

Voltammetric determination of Zn(II in Zn-Fe alloy electroplating baths using square-wave voltammetry

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Favaron Regiane

2001-01-01

Full Text Available A routine analytical method for zinc (II determination in Zn-Fe alloy galvanic baths was developed employing square-wave voltammetry with the static mercury drop electrode (SMDE as working electrode. Real alloy bath samples were analyzed by the standard addition method and recovery tests were undertaken. The supporting electrolytes used in the analyses were 1.0 mol L-1 NH3 / 0.2 mol L-1 NH4Cl or 0.1 mol L-1 citric acid (pH=3, presenting peak potentials for zinc (II, respectively, at -1.30 V and -0.99 V vs. Ag|AgCl (saturated KCl. The proposed voltammetric method showed a linear response range at 25 °C between 1.0 x 10-5 and 2.2 x 10-4 mol L-1 for zinc (II, in both electrolytes studied. The interference levels for some metals, such as Cu (II, Pb (II, Cr (III and Mn (II, which could prejudice Zn-Fe alloy deposition, were evaluated. These ions did not present significant degrees of interference in the zinc (II determination. The zinc (II recovery tests for the proposed method exhibited a good agreement with the reference method, showing relative errors lower than 3.0%.

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

International Nuclear Information System (INIS)

Fawcett, B.C.

1989-01-01

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

Multisensor system for determination of iron(II), iron(III), uranium(VI) and uranium(IV) in complex solutions

International Nuclear Information System (INIS)

Legin, A.V.; Seleznev, B.L.; Rudnitskaya, A.M.; Vlasov, Yu.G.; Tverdokhlebov, S.V.; Mack, B.; Abraham, A.; Arnold, T.; Baraniak, L.; Nitsche, H.

1999-01-01

Development and analytical evaluation of a multisensor system based on the principles of 'electronic tongue' for the determination of low contents of uranium(VI), uranium(IV), iron(II) and iron(III) in complex aqueous media have been carried out. A set of 29 different chemical sensors on the basis of all- solid-state crystalline and vitreous materials with enhanced electronic conductivity and redox and ionic cross-sensitivity have been incorporated into the sensor array. Multidimensional data have been processed by pattern recognition methods such as artificial neural networks and partial least squares. It has been demonstrated that Fe(II) and Fe(III) contents in the range from 10 -7 to 10 -4 mol L -1 of total iron concentration can be determined with the average precision of about 25 %. U(VI) and U(IV) contents can been determined with the average precision of 10-40% depending on the concentration. The developed multisensor system can be applied in future for the analysis of mining and borehole waters as well other contaminated natural media, including on-site measurements. (author)

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.

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

African Journals Online (AJOL)

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

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

Sorption and catalytic oxidation of Fe(II) at the surface of calcite

NARCIS (Netherlands)

Mettler, S.; Wolthers, M.; Charlet, L.; Von Gunten, U.

The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two distinguishable steps:

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

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Ceth W. Parker

2013-11-01

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

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.

Synthesis of Cd/(Al+Fe) layered double hydroxides and characterization of the calcination products

International Nuclear Information System (INIS)

Perez, M.R.; Barriga, C.; Fernandez, J.M.; Rives, V.; Ulibarri, M.A.

2007-01-01

Layered double hydroxides (LDHs) containing Cd(II), Al(III), and Fe(III) in the brucite-like layers with different starting Fe/Al atomic ratios and with nitrate as counteranion have been prepared following the coprecipitation method at a constant pH value of 8. An additional Cd(II),Al(III)-LDH sample interlayered with hexacyanoferrate(III) ions has been prepared by ionic exchange at pH 9. The samples have been characterized by elemental chemical analysis, powder X-ray diffraction (PXRD), and FT-IR spectroscopy. Their thermal stability has been assessed by thermogravimetric and differential thermal analyses (TG-DTA) and mass spectrometric analysis of the evolved gases. The PXRD patterns of the solids calcined at 800 deg. C show diffraction lines corresponding to Cd(Al)O and spinel-type materials, which precise nature (CdAl 2 O 4 , Cd 1-x Fe 2+x O 4 , or Cd x Fe 2.66 O 4 ) depends on location and concentration of iron in the parent material or precursor. - Graphical abstract: Layered double hydroxides (LDHs) containing Cd(II), Al(III), and Fe(III) in the brucite-like layers with different starting Fe/Al atomic ratios and with nitrate as counteranion have been prepared following the coprecipitation method. An additional Cd(II),Al(III)-LDH sample interlayered with hexacyanoferrate(III) ions has been prepared by ionic exchange. Calcination at 800 deg. C shows diffraction lines corresponding to CdO and to spinel-type materials. SEM micrograph of sample CdAlFe-N-0

Atom exchange between aqueous Fe(II) and structural Fe in clay minerals.

Science.gov (United States)

Neumann, Anke; Wu, Lingling; Li, Weiqiang; Beard, Brian L; Johnson, Clark M; Rosso, Kevin M; Frierdich, Andrew J; Scherer, Michelle M

2015-03-03

Due to their stability toward reductive dissolution, Fe-bearing clay minerals are viewed as a renewable source of Fe redox activity in diverse environments. Recent findings of interfacial electron transfer between aqueous Fe(II) and structural Fe in clay minerals and electron conduction in octahedral sheets of nontronite, however, raise the question whether Fe interaction with clay minerals is more dynamic than previously thought. Here, we use an enriched isotope tracer approach to simultaneously trace Fe atom movement from the aqueous phase to the solid ((57)Fe) and from the solid into the aqueous phase ((56)Fe). Over 6 months, we observed a significant decrease in aqueous (57)Fe isotope fraction, with a fast initial decrease which slowed after 3 days and stabilized after about 50 days. For the aqueous (56)Fe isotope fraction, we observed a similar but opposite trend, indicating that Fe atom movement had occurred in both directions: from the aqueous phase into the solid and from the solid into aqueous phase. We calculated that 5-20% of structural Fe in clay minerals NAu-1, NAu-2, and SWa-1 exchanged with aqueous Fe(II), which significantly exceeds the Fe atom layer exposed directly to solution. Calculations based on electron-hopping rates in nontronite suggest that the bulk conduction mechanism previously demonstrated for hematite1 and suggested as an explanation for the significant Fe atom exchange observed in goethite2 may be a plausible mechanism for Fe atom exchange in Fe-bearing clay minerals. Our finding of 5-20% Fe atom exchange in clay minerals indicates that we need to rethink how Fe mobility affects the macroscopic properties of Fe-bearing phyllosilicates and its role in Fe biogeochemical cycling, as well as its use in a variety of engineered applications, such as landfill liners and nuclear repositories.

Reactions of H2O3 in the pulse-irradiated Fe(II)-O2 system

DEFF Research Database (Denmark)

Sehested, Knud; Bjergbakke, Erling; Lang Rasmussen, O.

1969-01-01

G(Fe(III)] is measured in pulse-irradiated O2-saturated solutions of 20 to 160 μMFe(II), at the p H's 0.46, 1.51, and 2.74 H2SO4 and HClO4 and with dose rates between 1 and 8 krad/1 μsec pulse. Based on homogeneous kinetics, the results are interpreted by a system of 18 reactions. The formation...

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

RESEARCH CONCERNING THE Fe CIRCUIT IN THE ENVIRONMENT

Directory of Open Access Journals (Sweden)

MARIOARA NICOLETA FILIMON

2007-01-01

Full Text Available The iron is an organogenous chemical element which, although in small quantities, is absolutely needed for live. The iron can be present in nature under 2 forms: bivalent or trivalent. Microorganism has an important role concerning the iron circuit in the biosphere. The iron cycle has 4 microbial processes: mineralizing the organic iron, forming the organic compounds with iron, the bivalent iron oxidity and the reduction of the trivalent iron. The Fe III and Fe II reduction, under the action of iron reductive bacteria, has a biological significance and a special a practical importance. Several proceedings used in mining, pottery and in the discovery of toxicity of certain compounds, at the level of anaerobic environment, are based on this process of reduction. The Fe III and Fe II reductive process can also have dangerous negative effects, due to the huge quantity of the accumulated Fe II. This huge quantity of Fe II is a big problem for the level of underground water, because Fe II compromises the water quality and the damaged metal plumbing. Under the action of microbial population, the trivalent iron is reduced to bivalent one, which is soluble. The bivalent iron is mostly evidenced with α,α-dipiridil reactive.

Analytical applications of N-phenyl-n-butyro hydroxamic and N-p-tolyl-n-butyro hydroxamic acids towards chromium (VI), copper (II), iron (III) and uranium (VI)

International Nuclear Information System (INIS)

Elkhadir, A. Y. F.

2001-05-01

Two aliphatic hydroxamic acids were prepared; N-phenyl-n-butyro hydroxamic acid and N-p-tolyl-n-butyro hydroxamic acid, by the reaction of β-phenylhydroxylamine and p-tolyl hydroxylamine with n-butyryl chloride. The acids were identified by: their melting points, characteristic reactions with acidic solutions of vanadium (V) and iron (III), infrared spectroscopy, nitrogen content and molecular weight determination. The extractability of these acids towards Cr (VI), Cu (II), Fe (III) and U (VI) were investigated at different pH values and molar acid concentrations. N-phenyl-n- butyro hydroxamic acid has a maximum extraction (98.80%) for Cr (VI) at 4 M H 2 SO 4 , (83.25%) for Cu (II) at pH 6, (99.17%) for Fe (III) at pH 5 and (99.76%) at 4 M HNO 3 for U (VI) respectively. N-p-tolyl-n-butyro hydroxamic acid has a maximum extraction (98.40%) for Cr (VI)at 4 M H 2 SO 4 , (81.30%) for Cu (II) at pH 6, (92.80%) for Fe (III) at pH 5 and (99.64%) for U (VI) at 4 M HNO 3 , respectively. The ratios of the metal to ligands were determined by job method (continuous variation method) and were found to be 1:2 for Cr (VI) and U (VI). (Author)

Analytical applications of N-phenyl-n-butyro hydroxamic and N-p-tolyl-n-butyro hydroxamic acids towards chromium (VI), copper (II), iron (III) and uranium (VI)

Energy Technology Data Exchange (ETDEWEB)

Elkhadir, A Y. F. [Department of Chemistry, Faculty of Science, University of Khartoum, Khartoum (Sudan)

2001-05-01

Two aliphatic hydroxamic acids were prepared; N-phenyl-n-butyro hydroxamic acid and N-p-tolyl-n-butyro hydroxamic acid, by the reaction of {beta}-phenylhydroxylamine and p-tolyl hydroxylamine with n-butyryl chloride. The acids were identified by: their melting points, characteristic reactions with acidic solutions of vanadium (V) and iron (III), infrared spectroscopy, nitrogen content and molecular weight determination. The extractability of these acids towards Cr (VI), Cu (II), Fe (III) and U (VI) were investigated at different pH values and molar acid concentrations. N-phenyl-n- butyro hydroxamic acid has a maximum extraction (98.80%) for Cr (VI) at 4 M H{sub 2}SO{sub 4}, (83.25%) for Cu (II) at pH 6, (99.17%) for Fe (III) at pH 5 and (99.76%) at 4 M HNO{sub 3} for U (VI) respectively. N-p-tolyl-n-butyro hydroxamic acid has a maximum extraction (98.40%) for Cr (VI)at 4 M H{sub 2} SO{sub 4}, (81.30%) for Cu (II) at pH 6, (92.80%) for Fe (III) at pH 5 and (99.64%) for U (VI) at 4 M HNO{sub 3}, respectively. The ratios of the metal to ligands were determined by job method (continuous variation method) and were found to be 1:2 for Cr (VI) and U (VI). (Author)

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.

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

Science.gov (United States)

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

2013-01-01

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

Fe(II)-induced transformation from ferrihydrite to lepidocrocite and goethite

International Nuclear Information System (INIS)

Liu Hui; Li Ping; Zhu Meiying; Wei Yu; Sun Yuhan

2007-01-01

The transformation of Fe(II)-adsorbed ferrihydrite was studied. Data tracking the formation of products as a function of pH, temperature and time is presented. The results indicate that trace of Fe(II) adsorbed on ferrihydrite can accelerate its transformation obviously. The products are lepidocrocite and/or goethite and/or hematite, which is different from those without Fe(II). That is, Fe(II) not only accelerates the transformation of ferrihydrite but also leads to the formation of lepidocrocite by a new path. The behavior of Fe(II) is shown in two aspects-catalytic dissolution-reprecipitation and catalytic solid-state transformation. The results indicate that a high temperature and a high pH(in the range from 5 to 9) are favorable to solid-state transformation and the formation of hematite, while a low temperature and a low pH are favorable to dissolution-reprecipitation mechanism and the formation of lepidocrocite. Special attentions were given to the formation mechanism of lepidocrocite and goethite. - Graphical abstract: Fe(II)-adsorbed ferrihydrite can rapidly transform into lepidocrocite or/and goethite or/and hematite. Which product dominates depends on the transformation conditions of ferrihydrite such as temperature, pH, reaction time, etc. In the current system, there exist two transformation mechanisms. One is dissolution/reprecipitation and the other is solid-state transformation. The transformation mechanisms from Fe(II)-adsorbed ferrihydrite to lepidocrocite and goethite were investigated

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

Science.gov (United States)

Tashyrev, O B; Govorukha, V M

2015-01-01

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

Spin Crossover in Fe(II)-M(II) Cyanoheterobimetallic Frameworks (M = Ni, Pd, Pt) with 2-Substituted Pyrazines.

Science.gov (United States)

Kucheriv, Olesia I; Shylin, Sergii I; Ksenofontov, Vadim; Dechert, Sebastian; Haukka, Matti; Fritsky, Igor O; Gural'skiy, Il'ya A

2016-05-16

Discovery of spin-crossover (SCO) behavior in the family of Fe(II)-based Hofmann clathrates has led to a "new rush" in the field of bistable molecular materials. To date this class of SCO complexes is represented by several dozens of individual compounds, and areas of their potential application steadily increase. Starting from Fe(2+), square planar tetracyanometalates M(II)(CN)4(2-) (M(II) = Ni, Pd, Pt) and 2-substituted pyrazines Xpz (X = Cl, Me, I) as coligands we obtained a series of nine new Hofmann clathrate-like coordination frameworks. X-ray diffraction reveals that in these complexes Fe(II) ion has a pseudo-octahedral coordination environment supported by four μ4-tetracyanometallates forming its equatorial coordination environment. Depending on the nature of X and M, axial positions are occupied by two 2X-pyrazines (X = Cl and M(II) = Ni (1), Pd (2), Pt (3); X = Me and M(II) = Ni (4), Pd (5)) or one 2X-pyrazine and one water molecule (X = I and M(II) = Ni (7), Pd (8), Pt (9)), or, alternatively, two distinct Fe(II) positions with either two pyrazines or two water molecules (X = Me and M(II) = Pt (6)) are observed. Temperature behavior of magnetic susceptibility indicates that all compounds bearing FeN6 units (1-6) display cooperative spin transition, while Fe(II) ions in N5O or N4O2 surrounding are high spin (HS). Structural changes in the nearest Fe(II) environment upon low-spin (LS) to HS transition, which include ca. 10% Fe-N distance increase, lead to the cell expansion. Mössbauer spectroscopy is used to characterize the spin state of all HS, LS, and intermediate phases of 1-9 (see abstract figure). Effects of a pyrazine substituent and M(II) nature on the hyperfine parameters in both spin states are established.

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

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

Science.gov (United States)

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

2014-07-01

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

Oral Assessment Kit, Levels II & III. Draft.

Science.gov (United States)

Agrelo-Gonzalez, Maria; And Others

The assessment packet includes a series of oral tests to help develop speaking as an integral part of second language instruction at levels II and III. It contains: 8 mini-tests for use at level II; 9 mini-tests for use at level III; a rating scale and score sheet masters for evaluating performance on these tests; and a collection of suggested…

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

Science.gov (United States)

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

2017-11-01

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

Crystal structures and magnetic properties of iron (III)-based phosphates: Na4NiFe(PO4)3 and Na2Ni2Fe(PO4)3

International Nuclear Information System (INIS)

Essehli, Rachid; Bali, Brahim El; Benmokhtar, Said; Bouziane, Khalid; Manoun, Bouchaib; Abdalslam, Mouner Ahmed; Ehrenberg, Helmut

2011-01-01

Graphical abstract: A perspective view of the Na 2 Ni 2 Fe(PO 4 ) 3 structure along the [0 0 1] direction. Both compounds seem to exibit antiferromagnetic interactions between magnetic entities at low temperature. Display Omitted Research highlights: → Nasicon and Alluaudite compounds, Iron(III)-based phosphates, Crystal structures of Na 4 NiFe(PO 4 ) 3 and Na 2 Ni 2 Fe(PO 4 ) 3 . → Magnetism behaviours of Na 4 NiFe(PO 4 ) 3 and Na 2 Ni 2 Fe(PO 4 ) 3 . → Antiferromagnetism interactions. → Mossbauer spectroscopy. - Abstract: Crystal structures from two new phosphates Na 4 NiFe(PO 4 ) 3 (I) and Na 2 Ni 2 Fe(PO 4 ) 3 (II) have been determined by single crystal X-ray diffraction analysis. Compound (I) crystallizes in a rhombohedral system (S. G: R-3c, Z = 6, a = 8.7350(9) A, c = 21.643(4) A, R 1 = 0.041, wR 2 =0.120). Compound (II) crystallizes in a monoclinic system (S. G: C2/c, Z = 4, a = 11.729(7) A, b = 12.433(5) A, c = 6.431(2) A, β = 113.66(4) o , R 1 = 0.043, wR 2 =0.111). The three-dimensional structure of (I) is closely related to the Nasicon structural type, consisting of corner sharing [(Ni/Fe)O 6 ] octahedra and [PO 4 ] tetrahedra forming [NiFe(PO 4 ) 3 ] 4+ units which align in chains along the c-axis. The Na + cations fill up trigonal antiprismatic sites within these chains. The crystal structure of (II) belongs to the alluaudite type. Its open framework results from [Ni 2 O 10 ] units of edge-sharing [NiO 6 ] octahedra, which alternate with [FeO 6 ] octahedra that form infinite chains. Coordination of these chains yields two distinct tunnels in which site Na + . The magnetization data of compound (I) reveal antiferromagnetic (AFM) interactions by the onset of deviations from a Curie-Weiss behaviour at low temperature as confirmed by Moessbauer measurements performed at 4.2 K. The corresponding temperature dependence of the reciprocal susceptibility χ -1 follows a typical Curie-Weiss behaviour for T > 105 K. A canted AFM state is proposed for

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.

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.

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.

Chelation of Cu(II, Zn(II, and Fe(II by Tannin Constituents of Selected Edible Nuts

Directory of Open Access Journals (Sweden)

Magdalena Karamać

2009-12-01

Full Text Available The tannin fractions isolated from hazelnuts, walnuts and almonds were characterised by colorimetric assays and by an SE-HPLC technique. The complexation of Cu(II and Zn(II was determined by the reaction with tetramethylmurexide, whereas for Fe(II, ferrozine was employed. The walnut tannins exhibited a significantly weaker reaction with the vanillin/HCl reagent than hazelnut and almond tannins, but the protein precipitation capacity of the walnut fraction was high. The SE-HPLC chromatogram of the tannin fraction from hazelnuts revealed the presence of oligomers with higher molecular weights compared to that of almonds. Copper ions were most effectively chelated by the constituents of the tannin fractions of hazelnuts, walnuts and almonds. At a 0.2 mg/assay addition level, the walnut tannins complexed almost 100% Cu(II. The Fe(II complexation capacities of the tannin fractions of walnuts and hazelnuts were weaker in comparison to that of the almond tannin fraction, which at a 2.5 mg/assay addition level, bound Fe(II by ~90%. The capacity to chelate Zn(II was quite varied for the different nut tannin fractions: almond tannins bound as much as 84% Zn(II, whereas the value for walnut tannins was only 8.7%; and for hazelnut tannins, no Zn(II chelation took place at the levels tested.

Competition of dipositive metal ions for Fe (III) binding sites in chelation therapy of Iron Load

International Nuclear Information System (INIS)

Rehmani, Fouzia S.

2005-01-01

Iron overload is a condition in which excessive iron deposited in the liver, kidney and spleen of human beings in the patients of beta thalassemia and sickle cell anemia. Instead of its importance iron could be toxic when in excess, it damages the tissues. For the treatment of iron overload, a drug desferrioxamine mesylate has been used. It is linear trihydroxamic acid, a natural siderophore produced by streptomyces which removes the extra iron from body. Salicylhydroxamate type siderphore. In present research salicylhydroxamate was used for the complexation with dipositive metal ions which are available in biological environments such as Mn (II), Co (II), Ni (II) and Cu (II). The aim of our work was to study the competition reactions between Fe (III) and other dipositive ions; to calculate the thermodynamic data of chelation of these metal ions complexes with hydroxamate by computer program and comparison with hydroxamate complexes. (author)

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

International Nuclear Information System (INIS)

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

2014-01-01

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

Fe(II)/Cu(II) interaction on goethite stimulated by an iron-reducing bacteria Aeromonas Hydrophila HS01 under anaerobic conditions.

Science.gov (United States)

Tao, Liang; Zhu, Zhen-Ke; Li, Fang-Bai; Wang, Shan-Li

2017-11-01

Copper is a trace element essential for living creatures, but copper content in soil should be controlled, as it is toxic. The physical-chemical-biological features of Cu in soil have a significant correlation with the Fe(II)/Cu(II) interaction in soil. Of significant interest to the current study is the effect of Fe(II)/Cu(II) interaction conducted on goethite under anaerobic conditions stimulated by HS01 (a dissimilatory iron reduction (DIR) microbial). The following four treatments were designed: HS01 with α-FeOOH and Cu(II) (T1), HS01 with α-FeOOH (T2), HS01 with Cu(II) (T3), and α-FeOOH with Cu(II) (T4). HS01 presents a negligible impact on copper species transformation (T3), whereas the presence of α-FeOOH significantly enhanced copper aging contributing to the DIR effect (T1). Moreover, the violent reaction between adsorbed Fe(II) and Cu(II) leads to the decreased concentration of the active Fe(II) species (T1), further inhibiting reactions between Fe(II) and iron (hydr)oxides and decelerating the phase transformation of iron (hydr)oxides (T1). From this study, the effects of the Fe(II)/Cu(II) interaction on goethite under anaerobic conditions by HS01 are presented in three aspects: (1) the accelerating effect of copper aging, (2) the reductive transformation of copper, and (3) the inhibition effect of the phase transformation of iron (hydr)oxides. Copyright © 2017 Elsevier Ltd. All rights reserved.

Immobilization of 99-Technetium (VII) by Fe(II)-Goethite and Limited Reoxidation

International Nuclear Information System (INIS)

Um, Wooyong; Chang, Hyun-Shik; Icenhower, Jonathan P.; Lukens, Wayne W.; Serne, R. Jeffrey; Qafoku, Nikolla; Westsik, Joseph H.; Buck, Edgar C.; Smith, Steven C.

2011-01-01

Synthesized goethite was successfully used with addition of Fe(II) to sequester Tc present in both deionized water and simulated off-gas scrubber waste solutions. Pertechnetate concentration in solution decreased immediately when the pH was raised above 7 by addition of sodium hydroxide. Removal of Tc(VII) from solution occurred most likely as a result of heterogeneous surface-catalyzed reduction to Tc(IV) and subsequent co-precipitation onto the goethite. The final Tc-bearing solid was identified as goethite-dominated Fe(III)-(oxy)hydroxide based on XRD analysis, confirming the widespread observation of its characteristic acicular habit by TEM/SEM images. Analysis of the solid precipitate by XAFS showed that the dominant oxidation state of Tc was Tc(IV) and was in octahedral coordination with Tc-O, Fe-O, and Tc-Fe bond distances that are consistent with direct substitution of Tc for Fe in the goethite structure. In some experiments the final Tc-goethite product was subsequently armored with additional layers of freshly precipitated goethite. Successful incorporation of Tc(IV) within the goethite mineral lattice and subsequent goethite armoring can limit re-oxidation of Tc(IV) and its subsequent release from Tc-goethite waste forms, even when the final product is placed in oxidizing environments that typify shallow waste burial facilities.

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

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Muhammad Ali Inam

2018-04-01

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

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

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...

Iodometric determination of peroxydiphosphate in the presence of copper(II) or iron(II) as catalyst.

Science.gov (United States)

Kapoor, S; Sharma, P D; Gupta, Y K

1975-09-01

Peroxydiphosphate can be determined iodometrically in the presence of a large excess of potassium iodide with copper(II) or iron(II) as catalyst through the operation of the Cu(II)/Cu(I) or Fe(II)/Fe(III) cycle. The method is applicable in HClO(4), H(2)SO(4), HCl and CH(3)COOH acid media in the range 0.1-1.0M studied. Nickel, manganese(II), cobalt(II), silver, chloride and phosphate are without effect.

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

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Is Fatimah

2015-01-01

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

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.

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

Determination of Fe²⁺ and Fe³⁺ species by FIA-CRC-ICP-MS in Antarctic ice samples

DEFF Research Database (Denmark)

Spolaor, A; Vallelonga, Paul Travis; Gabrieli, J

2012-01-01

contexts depends strongly on its oxidation state. Solubility in water and the capacity to form complexes are just two important characteristics that are species dependent. Distinguishing between the two iron species, Fe(II) and Fe(III), is necessary to evaluate bioavailability, as Fe(II) is more soluble...... detection limit is 0.01 ng g-1. A chelating resin, Ni-NTA Superflow, was used to separate the Fe species: At pH 2 the resin is capable of retaining Fe3+ with no retention of Fe2+. After the initial separation, we oxidized the Fe2+ using H2O2, and determined the Fe2+ concentration as the difference between...

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

Science.gov (United States)

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

2000-04-17

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

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

Science.gov (United States)

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

2001-08-14

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

Coumarin-Based Fluorescent Probes for Dual Recognition of Copper(II and Iron(III Ions and Their Application in Bio-Imaging

Directory of Open Access Journals (Sweden)

Olimpo García-Beltrán

2014-01-01

Full Text Available Two new coumarin-based “turn-off” fluorescent probes, (E-3-((3,4-dihydroxybenzylideneamino-7-hydroxy-2H-chromen-2-one (BS1 and (E-3-((2,4-dihydroxybenzylideneamino-7-hydroxy-2H-chromen-2-one (BS2, were synthesized and their detection of copper(II and iron(III ions was studied. Results show that both compounds are highly selective for Cu2+ and Fe3+ ions over other metal ions. However, BS2 is detected directly, while detection of BS1 involves a hydrolysis reaction to regenerate 3-amino-7-hydroxycoumarin (3 and 3,4-dihydroxybenzaldehyde, of which 3 is able to react with copper(II or iron(III ions. The interaction between the tested compounds and copper or iron ions is associated with a large fluorescence decrease, showing detection limits of ca. 10−5 M. Preliminary studies employing epifluorescence microscopy demonstrate that Cu2+ and Fe3+ ions can be imaged in human neuroblastoma SH-SY5Y cells treated with the tested probes.

Valence-delocalization of the mixed-valence oxo-centered trinuclear iron propionates [FeIII2FeIIO(C2H5CO2)6(py)3[npy; n = 0, 1.5

International Nuclear Information System (INIS)

Nakamoto, Tadahiro; Katada, Motomi; Kawata, Satoshi; Kitagawa, Susumu; Sano, Hirotoshi; Konno, Michiko

1994-01-01

Mixed-valence trinuclear iron propionates [Fe III 2 Fe II O(C 2 H 5 CO 2 ) 6 (py) 3 [npy, where n = 0, 1.5, were synthesized and the structure of the pyridine-solvated complex was determined by single-crystal X-ray diffraction. Moessbauer spectra of the solvated propionate complex showed a temperature-dependent mixed-valence state related to phase transitions, reaching an almost delocalized valence state at room temperature. On the other hand, the non-solvated propionate showed a remarkable change of the spectral shape related to a phase transition, remaining in a localized valence state at higher temperatures up to room temperature. (orig.)

Adsorption of Pb(II), Cu(II), Cd(II), Zn(II), Ni(II), Fe(II), and As(V) on bacterially produced metal sulfides.

Science.gov (United States)

Jong, Tony; Parry, David L

2004-07-01

The adsorption of Pb(II), Cu(II), Cd(II), Zn(II), Ni(II), Fe(II) and As(V) onto bacterially produced metal sulfide (BPMS) material was investigated using a batch equilibrium method. It was found that the sulfide material had adsorptive properties comparable with those of other adsorbents with respect to the specific uptake of a range of metals and, the levels to which dissolved metal concentrations in solution can be reduced. The percentage of adsorption increased with increasing pH and adsorbent dose, but decreased with increasing initial dissolved metal concentration. The pH of the solution was the most important parameter controlling adsorption of Cd(II), Cu(II), Fe(II), Ni(II), Pb(II), Zn(II), and As(V) by BPMS. The adsorption data were successfully modeled using the Langmuir adsorption isotherm. Desorption experiments showed that the reversibility of adsorption was low, suggesting high-affinity adsorption governed by chemisorption. The mechanism of adsorption for the divalent metals was thought to be the formation of strong, inner-sphere complexes involving surface hydroxyl groups. However, the mechanism for the adsorption of As(V) by BPMS appears to be distinct from that of surface hydroxyl exchange. These results have important implications to the management of metal sulfide sludge produced by bacterial sulfate reduction.

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.

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-04-15

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

Characterization of β-FeSi II films as a novel solar cell semiconductor

Science.gov (United States)

Fukuzawa, Yasuhiro; Ootsuka, Teruhisa; Otogawa, Naotaka; Abe, Hironori; Nakayama, Yasuhiko; Makita, Yunosuke

2006-04-01

β-FeSi II is an attractive semiconductor owing to its extremely high optical absorption coefficient (α>10 5 cm -1), and is expected to be an ideal semiconductor as a thin film solar cell. For solar cell use, to prepare high quality β-FeSi II films holding a desired Fe/Si ratio, we chose two methods; one is a molecular beam epitaxy (MBE) method in which Fe and Si were evaporated by using normal Knudsen cells, and occasionally by e-gun for Si. Another one is the facing-target sputtering (FTS) method in which deposition of β-FeSi II films is made on Si substrate that is placed out of gas plasma cloud. In both methods to obtain β-FeSi II films with a tuned Fe/Si ratio, Fe/Si super lattice was fabricated by varying Fe and Si deposition thickness. Results showed significant in- and out-diffusion of host Fe and Si atoms at the interface of Si substrates into β-FeSi II layers. It was experimentally demonstrated that this diffusion can be suppressed by the formation of template layer between the epitaxial β-FeSi II layer and the substrate. The template layer was prepared by reactive deposition epitaxy (RDE) method. By fixing the Fe/Si ratio as precisely as possible at 1/2, systematic doping experiments of acceptor (Ga and B) and donor (As) impurities into β-FeSi II were carried out. Systematical changes of electron and hole carrier concentration in these samples along variation of incorporated impurities were observed through Hall effect measurements. Residual carrier concentrations can be ascribed to not only the remaining undesired impurities contained in source materials but also to a variety of point defects mainly produced by the uncontrolled stoichiometry. A preliminary structure of n-β-FeSi II/p-Si used as a solar cell indicated a conversion efficiency of 3.7%.

Synthesis, characterization and performance in arsenic removal of iron-doped activated carbons prepared by impregnation with Fe(III) and Fe(II)

International Nuclear Information System (INIS)

Muniz, G.; Fierro, V.; Celzard, A.; Furdin, G.; Gonzalez-Sanchez, G.; Ballinas, M.L.

2009-01-01

Arsenic removal from natural well water from the state of Chihuahua (Mexico) is investigated by adsorption using a commercial activated carbon (AC). The latter is used as such, or after oxidation by several chemicals in aqueous solution: nitric acid, hydrogen peroxide, and ammonium persulphate. Raw and oxidised activated carbons are fully characterised (elementary analysis, surface chemistry, pore texture parameters, pH ZC , and TEM observation). Adsorption of As is measured in the aforementioned water, containing ca. 300 ppb of arsenic: removal of As is poor with the raw AC, and only the most oxidised carbons exhibit higher performances. By contrast, iron-doped ACs are much more efficient for that purpose, though their As uptake strongly depends on their preparation conditions: a number of samples were synthesised by impregnation of raw and oxidised ACs with HCl aqueous solutions of either FeCl 3 or FeCl 2 at various concentrations and various pH. It is shown that iron(II) chloride is better for obtaining high iron contents in the resultant ACs (up to 8.34 wt.%), leading to high As uptake, close to 0.036 mg As/g C. In these conditions, 100% of the As initially present in the natural well water is removed, as soon as the Fe content of the adsorbent is higher than 2 wt.%.

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

Energy Technology Data Exchange (ETDEWEB)

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

2018-02-01

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

The influence of Fe(II) competition on the sorption and migration of Ni(II) in MX-80 bentonite

International Nuclear Information System (INIS)

Pfingsten, Wilfried; Bradbury, Mike; Baeyens, Bart

2011-01-01

Highlights: → We model the diffusion of Ni(II) through bentonite using different sorption models. → We examine sorption competition of Fe(II) and Ni(II) at different concentrations. → Ni(II) breakthrough is 15 times earlier with Fe(II) sorption competition. → Ni(II) sorption is non-linear and depends on the Fe(II) concentration levels. → Sorption competition is important and has to be modelled by reactive transport codes. - Abstract: The results from batch sorption experiments on montmorillonite systems have demonstrated that bivalent transition metals compete with one another for sorption sites. For safety analysis studies of high level radioactive waste repositories with compacted bentonite near fields, the importance of competitive sorption on the migration of radionuclides needs to be evaluated. Under reducing conditions, the bentonite porewater chosen has a Fe(II) concentration of ∼5.3 x 10 -5 M through saturation with siderite. The purpose of this paper is to assess the influence of such high Fe(II) concentrations on the transport of Ni(II) through compacted bentonite, Ni(II) was chosen as an example of a bivalent transition metal. The one-dimensional calculations were carried out at different Ni(II) equilibrium concentrations at the boundary (Ni(II) EQBM ) with the reactive transport code MCOTAC incorporating the two site protolysis non electrostatic surface complexation/cation exchange sorption model, MCOTAC-sorb. At a Ni(II) EQBM level of 10 -7 M without Fe(II) competition, the reactive transport calculations using a constant K d approach and the MCOTAC-sorb calculation yielded the same breakthrough curves. At higher Ni(II) EQBM (10 -5 M), the model calculations with MCOTAC-sorb indicated a breakthrough which was shifted to later times by a factor of ∼5 compared with the use of the constant K d approach. When sorption competition was included in the calculations, the magnitude of the influence depended on the sorption characteristics of the

Biosorption of copper(II), lead(II), iron(III) and cobalt(II) on Bacillus sphaericus-loaded Diaion SP-850 resin

International Nuclear Information System (INIS)

Tuzen, Mustafa; Uluozlu, Ozgur Dogan; Usta, Canan; Soylak, Mustafa

2007-01-01

The biosorption of copper(II), lead(II), iron(III) and cobalt(II) on Bacillus sphaericus-loaded Diaion SP-850 resin for preconcentration-separation of them have been investigated. The sorbed analytes on biosorbent were eluted by using 1 mol L -1 HCl and analytes were determined by flame atomic absorption spectrometry. The influences of analytical parameters including amounts of pH, B. sphaericus, sample volume etc. on the quantitative recoveries of analytes were investigated. The effects of alkaline, earth alkaline ions and some metal ions on the retentions of the analytes on the biosorbent were also examined. Separation and preconcentration of Cu, Pb, Fe and Co ions from real samples was achieved quantitatively. The detection limits by 3 sigma for analyte ions were in the range of 0.20-0.75 μg L -1 for aqueous samples and in the range of 2.5-9.4 ng g -1 for solid samples. The validation of the procedure was performed by the analysis of the certified standard reference materials (NRCC-SLRS 4 Riverine Water, SRM 2711 Montana soil and GBW 07605 Tea). The presented method was applied to the determination of analyte ions in green tea, black tea, cultivated mushroom, boiled wheat, rice and soil samples with successfully results

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.

Rapid radioimmunoassay of human apolipoproteins C-II and C-III

Energy Technology Data Exchange (ETDEWEB)

Gustafson, S; Oestlund-Lindqvist, A M; Vessby, B [Uppsala Univ. (Sweden)

1984-06-01

Apolipoprotein (apo) C-II is an activator of lipoprotein lipase, while apo C-III has the ability to inhibit apo C-II activated lipolysis. In order to study further the relationship between lipoprotein lipase mediated hydrolysis and the serum concentrations of apo C-II and apo C-III radioimmunoassays for these apolipoproteins have been developed. Formalin-treated Staphylococcus aureus Cowan I was used for immunoprecipitation and were shown to give rapid uptake of immune complexes that could easily be harvested by centrifugation. The assays were shown to be sensitive (10 ..mu..g/1), specific, precise (inter- and intra-assay coefficients of variation below 10%), rapid (completed in less than 6 h) and simple to perform. Delipidation of serum and lipoproteins had no effect on the results, indicating that the immunologically active sites of apo C-II and apo C-III are exposed to the aqueous environment under assay conditions. Serum apo C-II and apo C-III levels of normolipidaemic subjects were approximately 25 mg/1 and 110 mg/1, respectively. Highly significant positive correlations were found between VLDL apo C-II and VLDL apo C-III, respectively, and VLDL triglycerides, VLDL cholesterol and total serum TG. There was also a highly significant correlation between the HDL cholesterol concentration and the HDL apo C-III concentration.

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

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)

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

Science.gov (United States)

Ge, Liyun; Deng, Huanhuan

2015-04-01

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

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

International Nuclear Information System (INIS)

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

2012-01-01

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

Magnetic viscosity and texture in NdFeB magnets

International Nuclear Information System (INIS)

Martinez, J.C.; Missell, F.P.

1988-01-01

The dependence of the magnetic viscosity on texture can be used to study a model recently proposed by Givord and co-workers to describe the angular dependence of the coercive field in NdFeB magnets. We have measured the magnetic viscosity parameter S/sub v/ for samples of Magnequench (MQ) II and III as a function of magnetic field H and temperature T above room temperature. Near room temperature, S/sub v/ for MQ II is smaller than for MQ III, while for temperatures above ∼70 0 C, the opposite behavior is observed. This temperature dependence is discussed and compared with that observed in sintered NdFeB and NdDyFeB magnets

Position Assignment and Oxidation State Recognition of Fe and Co Centers in Heterometallic Mixed-Valent Molecular Precursors for the Low-Temperature Preparation of Target Spinel Oxide Materials

Energy Technology Data Exchange (ETDEWEB)

Lieberman, Craig M. [Department of Chemistry, University at Albany, Albany, New York 12222, United States; Barry, Matthew C. [Department of Chemistry, University at Albany, Albany, New York 12222, United States; Wei, Zheng [Department of Chemistry, University at Albany, Albany, New York 12222, United States; Rogachev, Andrey Yu. [Department; Wang, Xiaoping [Chemical and Engineering Materials Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States; Liu, Jun-Liang [CNRS, CRPP, UPR 8641, F-33600 Pessac, France; Univ. Bordeaux, UPR 8641, F-33600 Pessac, France; MOE Key Lab of Bioinorganic and Synthetic Chemistry,; Clérac, Rodolphe [CNRS, CRPP, UPR 8641, F-33600 Pessac, France; Univ. Bordeaux, UPR 8641, F-33600 Pessac, France; Chen, Yu-Sheng [ChemMatCARS, Center for Advanced Radiation; Filatov, Alexander S. [Department; Dikarev, Evgeny V. [Department of Chemistry, University at Albany, Albany, New York 12222, United States

2017-07-31

A series of mixed-valent, heterometallic (mixed-transition metal) diketonates that can be utilized as prospective volatile single-source precursors for the low-temperature preparation of M_xM'_3–xO₄ spinel oxide materials is reported. Three iron–cobalt complexes with Fe/Co ratios of 1:1, 1:2, and 2:1 were synthesized by several methods using both solid-state and solution reactions. On the basis of nearly quantitative reaction yields, elemental analyses, and comparison of metal–oxygen bonds with those in homometallic analogues, heterometallic compounds were formulated as [Fe^III(acac)₃][Co^II(hfac)₂] (1), [Co^II(hfac)₂][Fe^III(acac)₃][Co^II(hfac)₂] (2), and [Fe^II(hfac)₂][Fe^III(acac)₃][Co^II(hfac)₂] (3). In the above heteroleptic complexes, the Lewis acidic, coordinatively unsaturated CoII/FeII centers chelated by two hexafluoroacetylacetonate (hfac) ligands maintain bridging interactions with oxygen atoms of acetylacetonate (acac) groups that chelate the neighboring Fe^III metal ion. Preliminary assignment of Fe and Co positions/oxidation states in 1–3 drawn from X-ray structural investigation was corroborated by a number of complementary techniques. Single-crystal resonant synchrotron diffraction and neutron diffraction experiments unambiguously confirmed the location of Fe and Co sites in the molecules of dinuclear (1) and trinuclear (2) complexes, respectively. Direct analysis in real time mass spectrometry revealed the presence of Fe^III- and Co^II-based fragments in the gas phase upon evaporation of precursors 1 and 2 as well as of Fe^III, Fe^II, and Co^II species for complex 3. Theoretical investigation of two possible “valent isomers”, [Fe^III(acac)₃][Co^II

Sorption-induced reversible oxidation of Fe(2) at the smectite/water interface under strictly anoxic conditions. A Moessbauer spectroscopy study

Energy Technology Data Exchange (ETDEWEB)

Gehin, A.; Charlet, L. [Laboratoire de Geophysique Interne et Tectonophysique (LGIT), Universite de Grenoble, 38 - Grenoble (France); Gehin, A. [Agence Nationale pour la Gestion des Dechets Radioactifs, ANDRA, 92 - Chatenay Malabry (France); Greneche, J.M. [Laboratoire de Physique de l' Etat Condense, UMR-CNRS 6087, 72 - Le Mans (France); Brendle, J. [Universite de Haute Alsace, Lab. des Materiaux Mineraux (LMM), 68 - Mulhouse (France); Rancourt, D.G. [Ottawa Univ., Dept. of Physics, Ontario (Canada)

2005-07-01

Previous studies of Fe(II) sorption onto montmorillonite have been performed with the mineral extracted from the MX80 bentonite. These studies have shown that Fe(II) can be sorbed onto clay minerals in cation exchange position. The affinity of montmorillonite for Fe(II) and Ca(II) is identical. Fe(II) may also be specifically adsorbed onto montmorillonite clay edges. Moessbauer spectroscopy confirmed the high affinity of clay surfaces for Fe(II) sorption and showed that this sorption is mainly due to a two step mechanism: Fe(II) specific adsorption, followed by oxidation of the Fe(II) sorbed. The identification of the oxidizing agent was prohibited due to the complex chemistry of the natural MX80 montmorillonite. Thus, synthetic iron-free montmorillonite was used (chemical formula: Ca{sub 0.3} (A{sub 1.4}Mg{sub 0.6}) (Si{sub 4}) O{sub 10}(OH){sub 2} ). {sup 57}Fe(II) sorption experiments were conducted in a N{sub 2} atmosphere gloves-box, in strictly anoxic conditions. Solid samples were synthesized in order to confirm the clay high affinity for Fe(II), in absence of structural oxidant, and to have a better comprehension of the sorption mechanism. Moessbauer spectra were recorded for each sample. Whereas no Fe(III) is detected in solution as pH was increased and then, a significant amount of surface sorbed Fe(III) was found to be reversibly produced, which amounts for 0-3% of total Fe in the pre-sorption edge acid region, up to 7% of total Fe when all Fe is sorbed in the neutral to alkaline pH range. From pH {approx_equal} 2 to pH {approx_equal} 7, a sorption edge plateau is observed. In this plateau, the sorbed-Fe(III)/sorbed-Fe ratio increases with pH, up to 45% at pH 7. Moessbauer spectra comparison with ferrous hydroxide, synthesized in the same redox conditions at higher pH, show that this oxidation can not be due to the trace amounts Oz in the suspension. The Moessbauer spectra components of both Fe(II) and Fe(III) appears as paramagnetic doublets: iron has

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

Platelet GP II b/III a inhibitors in neurointervention therapeutics

International Nuclear Information System (INIS)

Wang Kuizhong; Huang Qinghai; Liu Jianmin

2007-01-01

The platelet glucoprotein (GP) II b/III a inhibitors prossess inhibiting platelet aggregation effectly. As new drugs of antiplatelet, they are different in mechanism with action, application and dosage between the II b/III a inhibitors and other tradional antiplatelet drugs such as aspirin or clopidogrel. In familiar with the pharmacologic action and clinical application of II b/III a inhibitors is important for endovascular interventional radiology, especially with important significance for obtaining high quality neuro-endovascular stenting in the perioperative period. (authors)

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

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Subrata Pal

2014-01-01

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

Biosorption characteristics of copper (II), chromium (III), nickel (II), and lead (II) from aqueous solutions by Chara sp. and Cladophora sp.

Science.gov (United States)

Elmaci, Ayşe; Yonar, Taner; Ozengin, Nihan

2007-09-01

The aim of this research was to expose individual removals of copper, chromium, nickel, and lead from aqueous solutions via biosorption using nonliving algae species, Chara sp. and Cladophora sp. Optimum pH values for biosorption of copper (II), chromium (III), nickel (II), and lead (II) from aqueous solutions were determined to be 6, 7, 7, and 3 for Cladophora sp. and 5, 3, 5, and 4 for Chara sp. respectively. Maximum adsorption capacities of Chara sp. [10.54 for chromium (III) and 61.72 for lead (II)] and Cladophora sp. [6.59 for chromium (III) and 16.75 and 23.25 for lead (II)] for chromium (III) and lead (II) are similar. On the other hand, copper (II) and nickel (II) biosorption capacity of Cladophora sp. [14.28 for copper (II) and 16.75 for nickel (II)] is greater than Chara sp. [6.506 for copper (II) and 11.76 for nickel (II)]. Significantly high correlation coefficients indicated for the Langmuir adsorption isotherm models can be used to describe the equilibrium behavior of copper, chromium, nickel, and lead adsorption onto Cladophora sp. and Chara sp.

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

International Nuclear Information System (INIS)

Roden, Eric E.

2001-01-01

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

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

International Nuclear Information System (INIS)

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

2010-01-01

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

A luminescent Cd(II)-based metal-organic framework for detection of Fe(III) ions in aqueous solution

Science.gov (United States)

Li, Fen-Fang; Zhu, Miao-Li; Lu, Li-Ping

2018-05-01

A novel Cd((II)-organic framework [Cd(Hcbic)]n (H3cbic = 1-(4-carboxybenz-yl)-1H-benzoim-idazole-5, 6-dicarboxylic acid) was assembled and characterized by X-ray single crystal analysis. The Cd-MOF features one-dimensional left and right-handed double helical chains with screw-pitch of about 4.727 Å and the 4-methyl benzoic acid groups of Hcbic2- ligands in MOF-1 play many ribbons distributing in the two sides of the 2D networks. It is found that MOF-1 shows high selectivity (KSV = 1.8 × 105 L / mol) for Fe3+ ions in water solution with luminescent quenching because of the existence of uncoordinated carboxyl groups within open frameworks, which indicates that MOF-1 is a simple and reliable detection sensing reagent for Fe3+ in practical applications.

One-step green synthesis of bimetallic Fe/Pd nanoparticles used to degrade Orange II

Energy Technology Data Exchange (ETDEWEB)

Luo, Fang; Yang, Die; Chen, Zuliang, E-mail: zuliang.chen@newcastle.edu.au; Megharaj, Mallavarapu; Naidu, Ravendra

2016-02-13

Highlights: • Green synthesis of bimetallic Fe/Pd NPs was firstly reported using the one-step method. • 98.0% of Orange II was removed by Fe/Pd NPs, but only 16.0% by Fe NPs. • Fe/Pd NPs with a diameter ranging from 10 to 100 nm were observed. • Removing Orange II using Fe/Pd NPs involved both adsorption and catalytic degradation. - Abstract: To reduce cost and enhance reactivity, bimetallic Fe/Pd nanoparticles (NPs) were firstly synthesized using grape leaf aqueous extract to remove Orange II. Green synthesized bimetallic Fe/Pd NPs (98.0%) demonstrated a far higher ability to remove Orange II in 12 h compared to Fe NPs (16.0%). Meanwhile, all precursors, e.g., grape leaf extract, Fe{sup 2+} and Pd{sup 2+}, had no obvious effect on removing Orange II since less than 2.0% was removed. Kinetics study revealed that the removal rate fitted well to the pseudo-first-order reduction and pseudo-second-order adsorption model, meaning that removing Orange II via Fe/Pd NPs involved both adsorption and catalytic reduction. The remarkable stability of Fe/Pd NPs showed the potential application for removing azo dyes. Furthermore, Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR) confirmed the changes in Fe/Pd NPs before and after reaction with Orange II. High Performance Liquid Chromatography–Mass Spectrum (HPLC–MS) identified the degraded products in the removal of Orange II, and finally a removal mechanism was proposed. This one-step strategy using grape leaf aqueous extract to synthesize Fe/Pd NPs is simple, cost-effective and environmentally benign, making possible the large-scale production of Fe/Pd NPs for field remediation.

Iron(III) and manganese(II) substituted hydroxyapatite nanoparticles: Characterization and cytotoxicity analysis

International Nuclear Information System (INIS)

Li Yan; Nam, C T; Ooi, C P

2009-01-01

Calcium hydroxyapatite (HA) is the main inorganic component of natural bones and can bond to bone directly in vivo. Thus HA is widely used as coating material on bone implants due to its good osteoconductivity and osteoinductivity. Metal ions doped HA have been used as catalyst or absorbents since the ion exchange method has introduced new properties in HA which are inherent to the metal ions. For example, Mn 2+ ions have the potential to increase cell adhesion while Fe 3+ ions have magnetic properties. Here, Fe(III) substituted hydroxyapatite (Fe-HA) and Mn(II) substituted hydroxyapatite (Mn-HA) were produced by wet chemical method coupled with ion exchange mechanism. Compared with pure HA, the colour of both Fe-HA and Mn-HA nanoparticles changed from white to brown and pink respectively. The intensity of the colours increased with increasing substitution concentrations. XRD patterns showed that all samples were single phased HA while the FTIR spectra revealed all samples possessed the characteristic phosphate and hydroxyl adsorption bands of HA. However, undesired adsorption bands of carbonate substitution (B-type carbonated HA) and H 2 O were also detected, which was reasonable since the wet chemical method was used in the synthesis of these nanoparticles. FESEM images showed all samples were elongated spheroids with small size distribution and of around 70 nm, regardless of metal ion substitution concentrations. EDX spectra showed the presence of Fe and Mn and ICP-AES results revealed all metal ion substituted HA were non-stoichiometric (Ca/P atomic ratio deviates from 1.67). Fe-HA nanoparticles were paramagnetic and the magnetic susceptibility increased with the increase of Fe content. Based on the extraction assay for cytotoxicity test, both Fe-HA and Mn-HA displayed non-cytotoxicity to osteoblast.

Electron Transfer Pathways Facilitating U(VI) Reduction by Fe(II) on Al- vs Fe-Oxides

Energy Technology Data Exchange (ETDEWEB)

Taylor, S. D. [Pacific Northwest National Laboratory, Physical Sciences Division, P.O. Box; Becker, U. [The University of Michigan, Department of Earth; Rosso, K. M. [Pacific Northwest National Laboratory, Physical Sciences Division, P.O. Box

2017-09-06

This study continues mechanistic development of heterogeneous electron transfer (ET) pathways at mineral surfaces in aquatic environments that enable the reduction U(VI) by surface-associated Fe(II). Using computational molecular simulation within the framework of Marcus Theory, our findings highlight the importance of the configurations and interaction of the electron donor and acceptor species with the substrate, with respect to influencing its electronic structure and thereby the ability of semiconducting minerals to facilitate ET. U(VI) reduction by surface-associated Fe(II) (adsorbed or structurally incorporated into the lattice) on an insulating, corundum (001) surface (α-Al2O3) occurs when proximal inner-sphere (IS) surface complexes are formed, such that ET occurs through a combination of direct exchange (i.e., Fe d- and U f-orbitals overlap through space) and superexchange via intervening surface oxygen atoms. U(VI) reduction by coadsorbed Fe(II) on the isostructural semiconducting hematite (α-Fe2O3) basal surface requires either their direct electronic interaction (e.g., IS complexation) or mediation of this interaction indirectly through the surface via an intrasurface pathway. Conceptually possible longer-range ET by charge-hopping through surface Fe atoms was investigated to determine whether this indirect pathway is competitive with direct ET. The calculations show that energy barriers are large for this conduction-based pathway; interfacial ET into the hematite surface is endothermic (+80.1 kJ/mol) and comprises the rate-limiting step (10–6 s–1). The presence of the IS adsorbates appears to weaken the electronic coupling between underlying Fe ions within the surface, resulting in slower intra-surface ET (10–5 s–1) than expected in the bulk basal plane. Our findings lay out first insights into donor-acceptor communication via a charge-hopping pathway through the surface for heterogeneous reduction of U(VI) by Fe(II) and help provide a basis

Iron(III) protoporphyrin IX-single-wall carbon nanotubes modified electrodes for hydrogen peroxide and nitrite detection

International Nuclear Information System (INIS)

Turdean, Graziella L.; Popescu, Ionel Catalin; Curulli, Antonella; Palleschi, Giuseppe

2006-01-01

Iron(III) protoporphyrin IX (Fe(III)P), adsorbed either on single-walled carbon nanotubes (SWCNT) or on hydroxyl-functionalized SWCNT (SWCNT-OH), was incorporated within a Nafion matrix immobilized on the surface of a graphite electrode. From cyclic voltammetric measurements, performed under different experimental conditions (pH and potential scan rate), it was established that the Fe(III)P/Fe(II)P redox couple involves 1e - /1H + . The heterogeneous electron transfer process occurred faster when Fe(III)P was adsorbed on SWCNT-OH (∼11 s -1 ) than on SWCNT (∼4.9 s -1 ). Both the SWCNT-Fe(III)P- and SWCNT-OH-Fe(III)P-modified graphite electrodes exhibit electrocatalytic activity for H 2 O 2 and nitrite reduction. The modified electrodes sensitivities were found varying in the following sequences: S SWCNT-OH-Fe(III)P = 2.45 mA/M ∼ S SWCNT-Fe(III)P = 2.95 mA/M > S Fe(III)P = 1.34 mA/M for H 2 O 2 , and S SWCNT-Fe(III)P = 3.54 mA/M > S Fe(III)P 1.44 mA/M > S SWCNT-OH-Fe(III)P = 0.81 mA/M for NO 2 -

Archform comparisons between skeletal class II and III malocclusions.

Directory of Open Access Journals (Sweden)

Wei Zou

Full Text Available The purpose of this cross-sectional research was to explore the relationship of the mandibular dental and basal bone archforms between severe Skeletal Class II (SC2 and Skeletal Class III (SC3 malocclusions. We also compared intercanine and intermolar widths in these two malocclusion types. Thirty-three virtual pretreatment mandibular models (Skeletal Class III group and Thirty-five Skeletal Class II group pretreatment models were created with a laser scanning system. FA (the midpoint of the facial axis of the clinical crownand WALA points (the most prominent point on the soft-tissue ridgewere employed to produce dental and basal bone archforms, respectively. Gained scatter diagrams of the samples were processed by nonlinear regression analysis via SPSS 17.0. The mandibular dental and basal bone intercanine and intermolar widths were significantly greater in the Skeletal Class III group compared to the Skeletal Class II group. In both groups, a moderate correlation existed between dental and basal bone arch widths in the canine region, and a high correlation existed between dental and basal bone arch widths in the molar region. The coefficient of correlation of the Skeletal Class III group was greater than the Skeletal Class II group. Fourth degree, even order power functions were used as best-fit functions to fit the scatter plots. The radius of curvature was larger in Skeletal Class III malocclusions compared to Skeletal Class II malocclusions (rWALA3>rWALA2>rFA3>rFA2. In conclusion, mandibular dental and basal intercanine and intermolar widths were significantly different between the two groups. Compared with Skeletal Class II subjects, the mandibular archform was more flat for Skeletal Class III subjects.

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.

Synthesis, Characterization, and Biological Activity of Mn(II, Fe(II, Co(II, Ni(II, Cu(II, Zn(II, and Cd(II Complexes of N-Thiophenoyl-N′-Phenylthiocarbohydrazide

Directory of Open Access Journals (Sweden)

M. Yadav

2013-01-01

Full Text Available Mn(II, Fe(II, Co(II, Ni(II, Cu(II, Zn(II, and Cd(II complex of N-thiophenoyl -N′-phenylthiocarbohydrazide (H2 TPTH have been synthesized and characterized by elemental analysis, magnetic susceptibility measurements, infrared, NMR, electronic, and ESR spectral studies. The complexes were found to have compositions [Mn(H TPTH2], [Co(TPTH (H2O2], [Ni(TPTH (H2O2], [Cu(TPTH], [Zn(H TPTH], [Cd(H TPTH2], and [Fe(H TPTH2(EtOH]. The magnetic and electronic spectral studies suggest square planar geometry for [Cu(TPTH], tetrahedral geometry for [Zn(TPTH] and [Cd(H TPTH2], and octahedral geometry for rest of the complexes. The infrared spectral studies of the 1 : 1 deprotonated complexes suggest bonding through enolic oxygen, thiolato sulfur, and both the hydrazinic nitrogens. Thus, H2TPTH acts as a binegative tetradentate ligand. H2 TPTH and its metal complexes have been screened against several bacteria and fungi.

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.

Fe(II) oxidation kinetics and Fe hydroxyphosphate precipitation upon aeration of anaerobic (ground)water

NARCIS (Netherlands)

van der Grift, B.; Griffioen, J.; Behrends, T.; Wassen, M.J.; Schot, P.P.; Osté, Leonard

2015-01-01

Exfiltration of anaerobic Fe-rich groundwater into surface water plays an important role in controlling the transport of phosphate (P) from agricultural areas to the sea. Previous laboratory and field studies showed that Fe(II) oxidation upon aeration leads to effective immobilization of dissolved P

Effect of Dunaliella tertiolecta organic exudates on the Fe(II) oxidation kinetics in seawater.

Science.gov (United States)

González, A G; Santana-Casiano, J M; González-Dávila, M; Pérez-Almeida, N; Suárez de Tangil, M

2014-07-15

The role played by the natural organic ligands excreted by the green algae Dunaliella tertiolecta on the Fe(II) oxidation rate constants was studied at different stages of growth. The concentration of dissolved organic carbon increased from 2.1 to 7.1 mg L(-1) over time of culture. The oxidation kinetics of Fe(II) was studied at nanomolar levels and under different physicochemical conditions of pH (7.2-8.2), temperature (5-35 °C), salinity (10-37), and dissolved organic carbon produced by cells (2.1-7.1 mg L(-1)). The experimental rate always decreased in the presence of organic exudates with respect to that in the control seawater. The Fe(II) oxidation rate constant was also studied in the context of Marcus theory, where ΔG° was 39.31-51.48 kJ mol(-1). A kinetic modeling approach was applied for computing the equilibrium and rate constants for Fe(II) and exudates present in solution, the Fe(II) speciation, and the contribution of each Fe(II) species to the overall oxidation rate constant. The best fit model took into account two acidity equilibrium constants for the Fe(II) complexing ligands with pKa,1=9.45 and pKa,2=4.9. The Fe(II) complexing constants were KFe(II)-LH=3×10(10) and KFe(II)-L=10(7), and the corresponding computed oxidation rates were 68±2 and 36±8 M(-1) min(-1), respectively.

Lanthanide ions (III) as sensitizers of melatonin oxidation in reaction mixtures providing reactive species of oxygen and nitrogen

Energy Technology Data Exchange (ETDEWEB)

Kaczmarek, Małgorzata, E-mail: mkaczmar@amu.edu.pl

2015-06-15

Chemiluminescence (CL) of the reactive systems providing strong oxidants (reactive species of oxygen and nitrogen) containing lanthanide ions (III) and melatonin, was studied. Kinetic curves of emission decay and spectral distributions of chemiluminescence were obtained. Analysis of differences in the intensity of chemiluminescence and CL spectra proved that excitation of Tb(III) and Dy(III) ions takes place with the energy transfer from the products of melatonin oxidation: N{sup 1}-acetyl-N{sup 2}-formyl-5-methoxykynuramine (AFMK) and N{sup 1}-acetyl-5-methoxykynuramine (AMK) to the lanthanide ions. In the system Fe(II)/Fe(III)–H{sub 2}O{sub 2}–Mel–Tb(III) a linear correlation was established between the integrated CL intensity and melatonin concent. - Highlights: • Chemiluminescence (CL) of melatonin (Mel) oxidation by reactive species of oxygen and nitrogen. • Tb(III) and Dy(III) ions as sensitizers of a melatonin oxidation process. • New CL method for determination of melatonin in pharmaceutical preparations based on CL of Fe(II)/Fe(III)–H{sub 2}O{sub 2}–Mel–Tb(III) system.

THE SPECTRUM OF Fe II

Energy Technology Data Exchange (ETDEWEB)

Nave, Gillian [National Institute of Standards and Technology, Gaithersburg, MD 20899-8422 (United States); Johansson, Sveneric, E-mail: gillian.nave@nist.gov [Lund Observatory, University of Lund, Box 43, SE-22100 Lund (Sweden)

2013-01-15

The spectrum of singly ionized iron (Fe II) has been recorded using high-resolution Fourier transform (FT) and grating spectroscopy over the wavelength range 900 A to 5.5 {mu}m. The spectra were observed in high-current continuous and pulsed hollow cathode discharges using FT spectrometers at the Kitt Peak National Observatory, Tucson, AZ and Imperial College, London and with the 10.7 m Normal Incidence Spectrograph at the National Institute of Standards and Technology. Roughly 12,900 lines were classified using 1027 energy levels of Fe II that were optimized to measured wavenumbers. The wavenumber uncertainties of lines in the FT spectra range from 10{sup -4} cm{sup -1} for strong lines around 4 {mu}m to 0.05 cm{sup -1} for weaker lines around 1500 A. The wavelength uncertainty of lines in the grating spectra is 0.005 A. The ionization energy of (130,655.4 {+-} 0.4) cm{sup -1} was estimated from the 3d{sup 6}({sup 5}D)5g and 3d{sup 6}({sup 5}D)6h levels.

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...

Rational synthesis of high nuclearity Mo/Fe/S clusters: the reductive coupling approach in the convenient synthesis of (Cl(4)-cat)(2)Mo(2)Fe(6)S(8)(PR(3))(6) [R = Et, (n)Pr, (n)Bu] and the new [(Cl(4)-cat)(2)Mo(2)Fe(2)S(3)O(PEt(3))(3)Cl]-1/2(Fe(PEt(3))(2)(MeCN)(4)) and (Cl(4)-cat)(2)Mo(2)Fe(3)S(5)(PEt(3))(5) clusters.

Science.gov (United States)

Han, J; Koutmos, M; Ahmad, S A; Coucouvanis, D

2001-11-05

A general method for the synthesis of high nuclearity Mo/Fe/S clusters is presented and involves the reductive coupling of the (Et(4)N)(2)[(Cl(4)-cat)MoOFeS(2)Cl(2)] (I) and (Et(4)N)(2)[Fe(2)S(2)Cl(4)] (II) clusters. The reaction of I and II with Fe(PR(3))(2)Cl(2) or sodium salts of noncoordinating anions such as NaPF(6) or NaBPh(4) in the presence of PR(3) (R = Et, (n)Pr, or (n)Bu) affords (Cl(4)-cat)(2)Mo(2)Fe(6)S(8)(PR(3))(6) [R = Et (IIIa), (n)Pr (IIIb), (n)Bu (IIIc)], Fe(6)S(6)(PEt(3))(4)Cl(2) (IV) and (PF(6))[Fe(6)S(8)(P(n)Pr(3))(6)] (V) as byproducts. The isolation of (Et(4)N)[Fe(PEt(3))Cl(3)] (VI), NaCl, and SPEt(3) supports a reductive coupling mechanism. Cluster IV and V also have been synthesized by the reductive self-coupling of compound II. The reductive coupling reaction between I and II by PEt(3) and NaPF(6) in a 1:1 ratio produces the (Et(4)N)(2)[(Cl(4)-cat)Mo(L)Fe(3)S(4)Cl(3)] clusters [L = MeCN (VIIa), THF (VIIb)]. The hitherto unknown [(Cl(4)-cat)(2)Mo(2)Fe(2)S(3)O(PEt(3))(3)Cl](+) cluster (VIII) has been isolated as the 2:1 salt of the (Fe(PEt(3))(2)(MeCN)(4))(2+) cation after the reductive self-coupling reaction of I in the presence of Fe(PEt(3))(2)Cl(2). Cluster VIII crystallizes in the monoclinic space group P2(1)/c with a = 11.098(3) A, b = 22.827(6) A, c = 25.855(6) A, beta = 91.680(4) degrees, and Z = 4. The formal oxidation states of metal atoms in VIII have been assigned as Mo(III), Mo(IV), Fe(II), and Fe(III) on the basis of zero-field Mössbauer spectra. The Fe(PEt(3))(2)(MeCN)(4) cation of VIII is also synthesized independently, isolated as the BPh(4)(-) salt (IX), and has been structurally characterized. The reductive coupling of compound I also affords in low yield the new (Cl(4)-cat)(2)Mo(2)Fe(3)S(5)(PEt(3))(5) cluster (X) as a byproduct. Cluster X crystallizes in the monoclinic space group P2(1)/n with a = 14.811(3) A, b = 22.188(4) A, c = 21.864(4) A, beta = 100.124(3) degrees, and Z = 4 and the structure shows very short Mo-Fe

Biosorption of Fe (II) and Cd (II) ions from aqueous solution using a ...

African Journals Online (AJOL)

ADOWIE PERE

Biosorption of Fe (II) and Cd (II) ions from aqueous solution using a low cost ... human activities in the environment poses a lot of risk ... ion exchange or reverse osmosis, electrochemical treatment ..... is the adsorption coefficient, n indicates the.

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

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.

Immobilization and Limited Reoxidation of Technetium-99 by Fe(II)-Goethite

International Nuclear Information System (INIS)

Um, Wooyong; Chang, Hyun-shik; Icenhower, Jonathan P.; Qafoku, Nikolla; Smith, Steven C.; Serne, R. Jeffrey; Buck, Edgar C.; Kukkadapu, Ravi K.; Bowden, Mark E.; Westsik, Joseph H.; Lukens, Wayne W.

2010-01-01

This report summarizes the methodology used to test the sequestration of technetium-99 present in both deionized water and simulated Hanford Tank Waste Treatment and Immobilization Plant waste solutions. Synthesized goethite, α-FeOOH, was successfully used with the addition of aqueous Fe(II) to sequester technetium (Tc) present in both deionized water and waste solutions simulated to represent tank waste solutions derived from low-activity-waste glass melter off-gas scrubbers used at the Hanford Tank Waste Treatment and Immobilization Plant (WTP). Perrhenate, Re(VII), was also tested as a nonradiological surrogate of pertechnetate (Tc(VII)). In a slurry of goethite and dissolved Fe(II), Tc(VII) concentrations in solution decreased immediately when the slurry pH was raised above 7.0 by adding sodium hydroxide (NaOH). The total amount of Tc present in the final solid as determined by acid digestion showed a high degree of Tc sequestration, 90% to 100%, in the final Tc-goethite solids. In contrast, a relatively small percentage (0% to 43%) of Re removal was found even though the Re-goethite solid was prepared by the same method as the Tc-goethite. The difference in sequestration is caused by the different Re solubility and redox potential vs pH. Removal of Tc(VII) from solution occurred most likely as a result of heterogeneous surface-catalyzed reduction to Tc(IV) and subsequent co-precipitation with newly formed magnetite or goethite during the Fe(II) treatment and pH adjustment. One of the final Tc-goethite products, Sample 2-5, was subsequently armored through a mineral transformation process that involved adding additional Fe(III) and NaOH to isolate the reduced Tc(IV) from future oxidizing agents. Although the dominant major mineral in Tc-goethite samples prepared without armoring was magnetite, the final Tc-bearing solid in Tc-goethite samples prepared with the additional armoring process was identified as goethite-dominated Fe(III)-(oxy)hydroxide based on x

THE Fe II EMISSION IN ACTIVE GALACTIC NUCLEI: EXCITATION MECHANISMS AND LOCATION OF THE EMITTING REGION

International Nuclear Information System (INIS)

Marinello, M.; Rodríguez-Ardila, A.; Garcia-Rissmann, A.; Sigut, T. A. A.; Pradhan, A. K.

2016-01-01

We present a study of Fe ii emission in the near-infrared region (NIR) for 25 active galactic nuclei (AGNs) to obtain information about the excitation mechanisms that power it and the location where it is formed. We employ an NIR Fe ii template derived in the literature and find that it successfully reproduces the observed Fe ii spectrum. The Fe ii bump at 9200 Å detected in all objects studied confirms that Lyα fluorescence is always present in AGNs. The correlation found between the flux of the 9200 Å bump, the 1 μm lines, and the optical Fe ii implies that Lyα fluorescence plays an important role in Fe ii production. We determined that at least 18% of the optical Fe ii is due to this process, while collisional excitation dominates the production of the observed Fe ii. The line profiles of Fe ii λ10502, O i λ11287, Ca ii λ8664, and Paβ were compared to gather information about the most likely location where they are emitted. We found that Fe ii, O i and Ca ii have similar widths and are, on average, 30% narrower than Paβ. Assuming that the clouds emitting the lines are virialized, we show that the Fe ii is emitted in a region twice as far from the central source than Paβ. The distance, though, strongly varies: from 8.5 light-days for NGC 4051 to 198.2 light-days for Mrk 509. Our results reinforce the importance of the Fe ii in the NIR to constrain critical parameters that drive its physics and the underlying AGN kinematics, as well as more accurate models aimed at reproducing this complex emission

THE Fe II EMISSION IN ACTIVE GALACTIC NUCLEI: EXCITATION MECHANISMS AND LOCATION OF THE EMITTING REGION

Energy Technology Data Exchange (ETDEWEB)

Marinello, M. [Universidade Federal de Itajubá, Rua Doutor Pereira Cabral 1303, 37500-903, Itajubá, MG (Brazil); Rodríguez-Ardila, A.; Garcia-Rissmann, A. [Laboratório Nacional de Astrofísica, Rua Estados Unidos 154, Itajubá, MG, 37504-364 (Brazil); Sigut, T. A. A. [The University of Western Ontario, London, ON N6A 3K7 (Canada); Pradhan, A. K., E-mail: murilo.marinello@gmail.com [McPherson Laboratory, The Ohio State University, 140 W. 18th Ave., Columbus, OH 43210-1173 (United States)

2016-04-01

We present a study of Fe ii emission in the near-infrared region (NIR) for 25 active galactic nuclei (AGNs) to obtain information about the excitation mechanisms that power it and the location where it is formed. We employ an NIR Fe ii template derived in the literature and find that it successfully reproduces the observed Fe ii spectrum. The Fe ii bump at 9200 Å detected in all objects studied confirms that Lyα fluorescence is always present in AGNs. The correlation found between the flux of the 9200 Å bump, the 1 μm lines, and the optical Fe ii implies that Lyα fluorescence plays an important role in Fe ii production. We determined that at least 18% of the optical Fe ii is due to this process, while collisional excitation dominates the production of the observed Fe ii. The line profiles of Fe ii λ10502, O i λ11287, Ca ii λ8664, and Paβ were compared to gather information about the most likely location where they are emitted. We found that Fe ii, O i and Ca ii have similar widths and are, on average, 30% narrower than Paβ. Assuming that the clouds emitting the lines are virialized, we show that the Fe ii is emitted in a region twice as far from the central source than Paβ. The distance, though, strongly varies: from 8.5 light-days for NGC 4051 to 198.2 light-days for Mrk 509. Our results reinforce the importance of the Fe ii in the NIR to constrain critical parameters that drive its physics and the underlying AGN kinematics, as well as more accurate models aimed at reproducing this complex emission.

Average [O II] nebular emission associated with Mg II absorbers: dependence on Fe II absorption

Science.gov (United States)

Joshi, Ravi; Srianand, Raghunathan; Petitjean, Patrick; Noterdaeme, Pasquier

2018-05-01

We investigate the effect of Fe II equivalent width (W2600) and fibre size on the average luminosity of [O II] λλ3727, 3729 nebular emission associated with Mg II absorbers (at 0.55 ≤ z ≤ 1.3) in the composite spectra of quasars obtained with 3 and 2 arcsec fibres in the Sloan Digital Sky Survey. We confirm the presence of strong correlations between [O II] luminosity (L_{[O II]}) and equivalent width (W2796) and redshift of Mg II absorbers. However, we show L_{[O II]} and average luminosity surface density suffer from fibre size effects. More importantly, for a given fibre size, the average L_{[O II]} strongly depends on the equivalent width of Fe II absorption lines and found to be higher for Mg II absorbers with R ≡W2600/W2796 ≥ 0.5. In fact, we show the observed strong correlations of L_{[O II]} with W2796 and z of Mg II absorbers are mainly driven by such systems. Direct [O II] detections also confirm the link between L_{[O II]} and R. Therefore, one has to pay attention to the fibre losses and dependence of redshift evolution of Mg II absorbers on W2600 before using them as a luminosity unbiased probe of global star formation rate density. We show that the [O II] nebular emission detected in the stacked spectrum is not dominated by few direct detections (i.e. detections ≥3σ significant level). On an average, the systems with R ≥ 0.5 and W2796 ≥ 2 Å are more reddened, showing colour excess E(B - V) ˜ 0.02, with respect to the systems with R < 0.5 and most likely trace the high H I column density systems.

Synthesis, structure, luminescent, and magnetic properties of carbonato-bridged Zn(II)2Ln(III)2 complexes [(μ4-CO3)2{Zn(II)L(n)Ln(III)(NO3)}2] (Ln(III) = Gd(III), Tb(III), Dy(III); L(1) = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, L(2) = N,N'-bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato).

Science.gov (United States)

Ehama, Kiyomi; Ohmichi, Yusuke; Sakamoto, Soichiro; Fujinami, Takeshi; Matsumoto, Naohide; Mochida, Naotaka; Ishida, Takayuki; Sunatsuki, Yukinari; Tsuchimoto, Masanobu; Re, Nazzareno

2013-11-04

Carbonato-bridged Zn(II)2Ln(III)2 complexes [(μ4-CO3)2{Zn(II)L(n)Ln(III)(NO3)}2]·solvent were synthesized through atmospheric CO2 fixation reaction of [Zn(II)L(n)(H2O)2]·xH2O, Ln(III)(NO3)3·6H2O, and triethylamine, where Ln(III) = Gd(III), Tb(III), Dy(III); L(1) = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, L(2) = N,N'-bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato. Each Zn(II)2Ln(III)2 structure possessing an inversion center can be described as two di-μ-phenoxo-bridged {Zn(II)L(n)Ln(III)(NO3)} binuclear units bridged by two carbonato CO3(2-) ions. The Zn(II) ion has square pyramidal coordination geometry with N2O2 donor atoms of L(n) and one oxygen atom of a bridging carbonato ion at the axial site. Ln(III) ion is coordinated by nine oxygen atoms consisting of four from the deprotonated Schiff-base L(n), two from a chelating nitrate, and three from two carbonate groups. The temperature-dependent magnetic susceptibilities in the range 1.9-300 K, field-dependent magnetization from 0 to 5 T at 1.9 K, and alternating current magnetic susceptibilities under the direct current bias fields of 0 and 1000 Oe were measured. The magnetic properties of the Zn(II)2Ln(III)2 complexes are analyzed on the basis of the dicarbonato-bridged binuclear Ln(III)-Ln(III) structure, as the Zn(II) ion with d(10) electronic configuration is diamagnetic. ZnGd1 (L(1)) and ZnGd2 (L(2)) show a ferromagnetic Gd(III)-Gd(III) interaction with J(Gd-Gd) = +0.042 and +0.028 cm(-1), respectively, on the basis of the Hamiltonian H = -2J(Gd-Gd)ŜGd1·ŜGd2. The magnetic data of the Zn(II)2Ln(III)2 complexes (Ln(III) = Tb(III), Dy(III)) were analyzed by a spin Hamiltonian including the crystal field effect on the Ln(III) ions and the Ln(III)-Ln(III) magnetic interaction. The Stark splitting of the ground state was so evaluated, and the energy pattern indicates a strong easy axis (Ising type) anisotropy. Luminescence spectra of Zn(II)2Tb(III)2 complexes were observed, while those