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Title: Green rust formation from the bioreduction of {gamma}-FeOOH (lepidocrocite) : comparison of several Shewanella species.

Abstract

No abstract prepared.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC); USDOD
OSTI Identifier:
928910
Report Number(s):
ANL/BIO/JA-57920
Journal ID: ISSN 0149-0451; GEJODG; TRN: US200812%%386
DOE Contract Number:
DE-AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Geomicrobiol. J.; Journal Volume: 24; Journal Issue: 3-4 ; 2007
Country of Publication:
United States
Language:
ENGLISH
Subject:
58 GEOSCIENCES; IRON HYDROXIDES; BIODEGRADATION; MICROORGANISMS; COMPARATIVE EVALUATIONS; BIOGEOCHEMISTRY

Citation Formats

O'Loughlin, E. J., Larese-Casanova, P., Cook, R., Scherer, M., and Univ. of Iowa. Green rust formation from the bioreduction of {gamma}-FeOOH (lepidocrocite) : comparison of several Shewanella species.. United States: N. p., 2007. Web. doi:10.1080/01490450701459333.
O'Loughlin, E. J., Larese-Casanova, P., Cook, R., Scherer, M., & Univ. of Iowa. Green rust formation from the bioreduction of {gamma}-FeOOH (lepidocrocite) : comparison of several Shewanella species.. United States. doi:10.1080/01490450701459333.
O'Loughlin, E. J., Larese-Casanova, P., Cook, R., Scherer, M., and Univ. of Iowa. Mon . "Green rust formation from the bioreduction of {gamma}-FeOOH (lepidocrocite) : comparison of several Shewanella species.". United States. doi:10.1080/01490450701459333.
@article{osti_928910,
title = {Green rust formation from the bioreduction of {gamma}-FeOOH (lepidocrocite) : comparison of several Shewanella species.},
author = {O'Loughlin, E. J. and Larese-Casanova, P. and Cook, R. and Scherer, M. and Univ. of Iowa},
abstractNote = {No abstract prepared.},
doi = {10.1080/01490450701459333},
journal = {Geomicrobiol. J.},
number = 3-4 ; 2007,
volume = 24,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}
  • Microbial reduction of Fe(III) oxides results in the production of Fe(II) and may lead to the subsequent formation of Fe(II)-bearing secondary mineralization products including magnetite, siderite, vivianite, chukanovite (ferrous hydroxy carbonate (FHC)), and green rust; however, the factors controlling the formation of specific Fe(II) phases are often not well-defined. This study examined effects of (i) a range of inorganic oxyanions (arsenate, borate, molybdate, phosphate, silicate, and tungstate), (ii) natural organic matter (citrate, oxalate, microbial extracellular polymeric substances [EPS], and humic substances), and (iii) the type and number of dissimilatory iron-reducing bacteria on the bioreduction of lepidocrocite and formation of Fe(II)-bearingmore » secondary mineralization products. The bioreduction kinetics clustered into two distinct Fe(II) production profiles. 'Fast' Fe(II) production kinetics [19-24 mM Fe(II) d-1] were accompanied by formation of magnetite and FHC in the unamended control and in systems amended with borate, oxalate, gellan EPS, or Pony Lake fulvic acid or having 'low' cell numbers. Systems amended with arsenate, citrate, molybdate, phosphate, silicate, tungstate, EPS from Shewanella putrefaciens CN32, or humic substances derived from terrestrial plant material or with 'high' cell numbers exhibited comparatively slow Fe(II) production kinetics [1.8-4.0 mM Fe(II) d-1] and the formation of green rust. The results are consistent with a conceptual model whereby competitive sorption of more strongly bound anions blocks access of bacterial cells and reduced electron-shuttling compounds to sites on the iron oxide surface, thereby limiting the rate of bioreduction.« less
  • Electron transfer mediators (ETMs) such as low-molecular-mass quinones (e.g., juglone and lawsone) and humic substances are believed to play a role in many redox reactions involved in contaminant transformations and the biogeochemical cycling of many redox-active elements (e.g., Fe and Mn) in aquatic and terrestrial environments. This study examines the effects of a series of compounds representing major classes of natural and synthetic organic ETMs, including low-molecular-mass quinones, humic substances, phenazines, phenoxazines, phenothiazines, and indigo derivatives, on the bioreduction of lepidocrocite ({gamma}-FeOOH) by the dissimilatory Fe(III)-reducing bacterium Shewanella putrefaciens CN32. Although S. putrefaciens CN32 was able to reduce lepidocrocite inmore » the absence of exogenous ETMs, the addition of exogenous ETMs enhanced the bioreduction of lepidocrocite. In general, the rate of Fe(II) production correlated well with the reduction potentials of the ETMs. The addition of humic acids or unfractionated natural organic matter at concentrations of 10 mg organic C L{sup -1} resulted in, at best, a minimal enhancement of lepidocrocite bioreduction. This observation suggests that electron shuttling by humic substances is not likely to play a major role in Fe(III) bioreduction in oligotrophic environments such as subsurface sediments with low organic C contents.« less
  • Fe(II)-dependent nitrite reduction was studied in oxygen-free reaction flasks at pH values from 6.0 to 8.5 and in the presence and absence of the Fe(III) oxyhydroxide lepidocrocite ({gamma}-FeOOH). When ionic Fe{sup 2+} was added to flasks containing lepidocrocite, rapid Fe{sup 2+} consumption and release of H{sup +} took place. The solid phase turned dark and contained magnetite (Fe{sub 3}O{sub 4}). This reaction was independent of the presence of NO{sub 2}{sup {minus}}. However, rapid NO{sub 2}{sup {minus}} reduction primarily to N{sub 2}O was observed only after the Fe{sup 2+} binding to lepidocrocite was initiated; insignificant NO{sub 2}{sup {minus}} reduction was observedmore » in control flasks without lepidocrocite. Both Fe{sup 2+} binding and associated H{sup +} release and NO{sub 2}{sup {minus}} reduction were negligible at pH values of 7.0 and below, but increased dramatically as pH was raised to 8.5. The Fe(II) associated with a reactive complex formed during Fe{sup 2+} binding to lepidocrocite, and not the ionic Fe{sup 2+}, seemed responsible for the reduction of NO{sub 2}{sup {minus}}. The catalytic effect of Fe(III) oxyhydroxide may stimulate Fe(II)-dependent formation of N{sub 2}O from NO{sub 2}{sup {minus}} (chemodenitrification) in geochemical systems such as sediments and subsoils.« less
  • White and green rusts are the active chemical reagents of buried scrap iron pollutant remediation. In this work, a comparison of the initial electron-transfer step for the reduction of CrO{sub 4}{sup -2} by Fe{sub (aq)}{sup 2+} and Fe(OH){sub 2}(s) is presented. Using hybrid density functional theory and Hartree-Fock cluster calculations for the aqueous reaction, the rate constant for the homogeneous reduction of chromium by ferrous iron was determined to be 5 x 10{sup -2} M{sup -1} s{sup -1} for the initial electron transfer. Using a combination of Hartree-Fock slab and cluster calculations for the heterogeneous reaction, the initial electron transfermore » for the heterogeneous reduction of chromium by ferrous iron was determined to be 1 x 10{sup 2} s{sup -1}. The difference in rates is driven by the respective free energies of reaction: 33.4 vs -653.2 kJ/mol. This computational result is apparently the opposite of what has been observed experimentally, but further analysis suggests that these results are fully convergent with experiment. The experimental heterogeneous rate is limited by surface passivation from slow intersheet electron transfer, while the aqueous reaction may be an autocatalytic heterogeneous reaction involving the iron oxyhydroxide product. As a result, it is possible to produce a clear model of the pollutant reduction reaction sequence for these two reactants.« less
  • This investigation documents the formation of Green Rust (GR) and immobilization of Ni2+ in response to bacterial reduction of hydrous ferric oxide (HFO) reduction experiments provided evidence that the solid-phase partitioning of Ni2+ in GR extended from equilibrium solid-solution behavior.