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Title: Interactions Between Microbial Iron Reduction and Metal Geochemistry: Effect of Redox Cycling on Transition Metal Speciation in Iron Bearing Sediments

Abstract

Microbial iron reduction is an important biogeochemical process that can affect metal geochemistry in sediments through direct and indirect mechanisms. With respect to Fe(III) (hydr)oxides bearing sorbed divalent metals, recent reports have indicated that (1) microbial reduction of goethite/ferrihydrite mixtures preferentially removes ferrihydrite, (2) this process can incorporate previously sorbed Zn(II) into an authigenic crystalline phase that is insoluble in 0.5 M HCl, (3) this new phase is probably goethite, and (4) the presence of nonreducible minerals can inhibit this transformation. This study demonstrates that a range of sorbed transition metals can be selectively sequestered into a 0.5 M HCl insoluble phase and that the process can be stimulated through sequential steps of microbial iron reduction and air oxidation. Microbial reduction experiments with divalent Cd, Co, Mn, Ni, Pb, and Zn indicate that all metals save Mn experienced some sequestration, with the degree of metal incorporation into the 0.5 M HCl insoluble phase correlating positively with crystalline ionic radius at coordination number = 6. Redox cycling experiments with Zn adsorbed to synthetic goethite/ferrihydrite or iron-bearing natural sediments indicate that redox cycling from iron reducing to iron oxidizing conditions sequesters more Zn within authigenic minerals than microbial iron reduction alone. Inmore » addition, the process is more effective in goethite/ferrihydrite mixtures than in iron-bearing natural sediments. Microbial reduction alone resulted in a ~3× increase in 0.5 M HCl insoluble Zn and increased aqueous Zn (Zn-aq) in goethite/ferrihydrite, but did not significantly affect Zn speciation in natural sediments. Redox cycling enhanced the Zn sequestration by ~12% in both goethite/ferrihydrite and natural sediments and reduced Zn-aq to levels equal to the uninoculated control in goethite/ferrihydrite and less than the uninoculated control in natural sediments. These data suggest that in situ redox cycling may serve as an effective method for mitigating divalent metal contamination in subsurface environments.« less

Authors:
; ;
Publication Date:
Research Org.:
Idaho National Laboratory (INL)
Sponsoring Org.:
DOE - SC
OSTI Identifier:
912346
Report Number(s):
INL/JOU-05-00678
Journal ID: ISSN 0013-936X; ESTHAG; TRN: US200801%%781
DOE Contract Number:
DE-AC07-99ID-13727
Resource Type:
Journal Article
Resource Relation:
Journal Name: Environmental Science and Technology; Journal Volume: 40; Journal Issue: 6
Country of Publication:
United States
Language:
English
Subject:
36 - MATERIALS SCIENCE, 58 - GEOSCIENCES; AIR; BEARINGS; CONTAMINATION; COORDINATION NUMBER; GEOCHEMISTRY; GOETHITE; IRON; MIXTURES; OXIDATION; SEDIMENTS; TRANSITION ELEMENTS; metal; microbial; redox cycling; sediments

Citation Formats

D. Craig Cooper, Flynn W. Picardal, and Aaron J. Coby. Interactions Between Microbial Iron Reduction and Metal Geochemistry: Effect of Redox Cycling on Transition Metal Speciation in Iron Bearing Sediments. United States: N. p., 2006. Web. doi:10.1021/es051778t.
D. Craig Cooper, Flynn W. Picardal, & Aaron J. Coby. Interactions Between Microbial Iron Reduction and Metal Geochemistry: Effect of Redox Cycling on Transition Metal Speciation in Iron Bearing Sediments. United States. doi:10.1021/es051778t.
D. Craig Cooper, Flynn W. Picardal, and Aaron J. Coby. Wed . "Interactions Between Microbial Iron Reduction and Metal Geochemistry: Effect of Redox Cycling on Transition Metal Speciation in Iron Bearing Sediments". United States. doi:10.1021/es051778t.
@article{osti_912346,
title = {Interactions Between Microbial Iron Reduction and Metal Geochemistry: Effect of Redox Cycling on Transition Metal Speciation in Iron Bearing Sediments},
author = {D. Craig Cooper and Flynn W. Picardal and Aaron J. Coby},
abstractNote = {Microbial iron reduction is an important biogeochemical process that can affect metal geochemistry in sediments through direct and indirect mechanisms. With respect to Fe(III) (hydr)oxides bearing sorbed divalent metals, recent reports have indicated that (1) microbial reduction of goethite/ferrihydrite mixtures preferentially removes ferrihydrite, (2) this process can incorporate previously sorbed Zn(II) into an authigenic crystalline phase that is insoluble in 0.5 M HCl, (3) this new phase is probably goethite, and (4) the presence of nonreducible minerals can inhibit this transformation. This study demonstrates that a range of sorbed transition metals can be selectively sequestered into a 0.5 M HCl insoluble phase and that the process can be stimulated through sequential steps of microbial iron reduction and air oxidation. Microbial reduction experiments with divalent Cd, Co, Mn, Ni, Pb, and Zn indicate that all metals save Mn experienced some sequestration, with the degree of metal incorporation into the 0.5 M HCl insoluble phase correlating positively with crystalline ionic radius at coordination number = 6. Redox cycling experiments with Zn adsorbed to synthetic goethite/ferrihydrite or iron-bearing natural sediments indicate that redox cycling from iron reducing to iron oxidizing conditions sequesters more Zn within authigenic minerals than microbial iron reduction alone. In addition, the process is more effective in goethite/ferrihydrite mixtures than in iron-bearing natural sediments. Microbial reduction alone resulted in a ~3× increase in 0.5 M HCl insoluble Zn and increased aqueous Zn (Zn-aq) in goethite/ferrihydrite, but did not significantly affect Zn speciation in natural sediments. Redox cycling enhanced the Zn sequestration by ~12% in both goethite/ferrihydrite and natural sediments and reduced Zn-aq to levels equal to the uninoculated control in goethite/ferrihydrite and less than the uninoculated control in natural sediments. These data suggest that in situ redox cycling may serve as an effective method for mitigating divalent metal contamination in subsurface environments.},
doi = {10.1021/es051778t},
journal = {Environmental Science and Technology},
number = 6,
volume = 40,
place = {United States},
year = {Wed Feb 01 00:00:00 EST 2006},
month = {Wed Feb 01 00:00:00 EST 2006}
}
  • Technetium is an important environmental contaminant introduced by the processing and disposal of irradiated nuclear fuel and atmospheric nuclear tests. Under oxic conditions technetium is soluble and exists as pertechnatate anion (TcO4-), while under anoxic conditions Tc is usually insoluble and exists as precipitated Tc(IV). Here we investigated abiotic Tc(VII) reduction in mineralogically heterogeneous, Fe(II)-containing sediments. The sediments were collected from a 55 m borehole that sampled a semi-confined aquifer at the Hanford Site, USA that contained a dramatic redox transition zone. One oxic facies (18.0-18.3 m) and five anoxic facies (18.3-18.6 m, 30.8-31.1 m, 39.0-39.3 m, 47.2-47.5 m andmore » 51.5-51.8 m) were selected for this study. Chemical extractions, X-ray diffraction, electron microscopy, and Mössbauer spectroscopy were applied to characterize the Fe(II) mineral suite that included: Fe(II)-phyllosilicates, pyrite, magnetite and siderite. The Fe(II) mineral phase distribution differed between the sediments. Sediment suspensions were adjusted to the same 0.5 M HCl extracted Fe(II) concentration (0.6 mM) for Tc(VII) reduction experiments. Aqueous Fe was low in all sediment suspensions (<2 μM) and below the Fe(II)aq detection limit (10 μM). Technetium(VII) reduction occurred in all anoxic sediments at depths greater than 18.3 m and reaction time differed significantly between the sediments (8-219 d). Mössbauer analysis of the Tc-reacted, 30.8-31.1 m sediment confirmed that Tc(VII) was reduced by solid-phase Fe(II), with siderite and Fe(II)-containing phyllosilicates implicated as redox reactive phases. Technetium-XAS analysis demonstrated that Tc associated with sediments was in the Tc(IV) valence state and immobilized as clusters of a TcO2·nH2O-like phase. The speciation of redox product Tc(IV) was not affected by reduction rate or Fe(II) mineralogy.« less
  • Microbial reduction of iron has been shown to be important in the transformation and remediation of contaminated sediments. Re-oxidation of microbially reduced iron may occur in sediments that experience oxidation-reduction cycling and can thus impact the extent of contaminant remediation. The purpose of this research was to quantify iron oxidation in a flow-through column filled with biologically-reduced sediment and to compare the iron phases in the re-oxidized sediment to both the pristine and biologically-reduced sediment. The sediment contained both Fe(III)-oxides (primarily goethite) and silicate Fe (illite/vermiculite) and was biologically reduced in phosphate buffered (PB) medium during a 497 day columnmore » experiment with acetate supplied as the electron donor. Long-term iron reduction resulted in partial reduction of silicate Fe(III) without any goethite reduction, based on Mössbauer spectroscopy measurements. This reduced sediment was treated with an oxygenated PB solution in a flow-through column resulting in the oxidation of 38% of the biogenic Fe(II). Additional batch experiments showed that the Fe(III) in the oxidized sediment was more quickly reduced compared to the pristine sediment, indicating that oxidation of the sediment not only regenerated Fe(III) but also enhanced iron reduction compared to the pristine sediment. Oxidation-reduction cycling may be a viable method to extend iron-reducing conditions during in-situ bioremediation.« less
  • Fe(III)-oxides and Fe(III)-bearing phyllosilicates are the two major iron sources utilized as electron acceptors by dissimilatory iron-reducing bacteria (DIRB) in anoxic soils and sediments. Although there have been many studies of microbial Fe(III)-oxide and Fe(III)-phyllosilicate reduction with both natural and specimen materials, no controlled experimental information is available on the interaction between these two phases when both are available for microbial reduction. In this study, the model DIRB Geobacter sulfurreducens was used to examine the pathways of Fe(III) reduction in Fe(III)-oxide stripped subsurface sediment that was coated with different amounts of synthetic high surface area goethite. Cryogenic (12K) 57Fe Mössbauermore » spectroscopy was used to determine changes in the relative abundances of Fe(III)-oxide, Fe(III)-phyllosilicate, and phyllosilicate-associated Fe(II) (Fe(II)-phyllosilicate) in bioreduced samples. Analogous Mössbauer analyses were performed on samples from abiotic Fe(II) sorption experiments in which sediments were exposed to a quantity of exogenous soluble Fe(II) (FeCl22H2O) comparable to the amount of Fe(II) produced during microbial reduction. A Fe partitioning model was developed to analyze the fate of Fe(II) and assess the potential for abiotic Fe(II)-catalyzed reduction of Fe(III)-phyllosilicatesilicates. The microbial reduction experiments indicated that although reduction of Fe(III)-oxide accounted for virtually all of the observed bulk Fe(III) reduction activity, there was no significant abiotic electron transfer between oxide-derived Fe(II) and Fe(III)-phyllosilicatesilicates, with 26-87% of biogenic Fe(II) appearing as sorbed Fe(II) in the Fe(II)-phyllosilicate pool. In contrast, the abiotic Fe(II) sorption experiments showed that 41 and 24% of the added Fe(II) engaged in electron transfer to Fe(III)-phyllosilicate surfaces in synthetic goethite-coated and uncoated sediment. Differences in the rate of Fe(II) addition and system redox potential may account for the microbial and abiotic reaction systems. Our experiments provide new insight into pathways for Fe(III) reduction in mixed Fe(III)-oxide/Fe(III)-phyllosilicate assemblages, and provide key mechanistic insight for interpreting microbial reduction experiments and field data from complex natural soils and sediments.« less
  • Dissimilatory microbial reduction of solid-phase Fe(III)-oxides and Fe(III)-bearing phyllosilicates (Fe(III)-phyllosilicates) is an important process in anoxic soils, sediments, and subsurface materials. Although various studies have documented the relative extent of microbial reduction of single-phase Fe(III)-oxides and Fe(III)-phyllosilicates, detailed information is not available on interaction between these two processes in situations where both phases are available for microbial reduction. The goal of this research was to use the model dissimilatory iron-reducing bacterium (DIRB) Geobacter sulfurreducens to study Fe(III)-oxide vs. Fe(III)-phyllosilicate reduction in a range of subsurface materials and Fe(III)-oxide stripped versions of the materials. Low temperature (12K) Mossbauer spectroscopy was usedmore » to infer changes in the relative abundances of Fe(III)-oxide, Fe(III)-phyllosilicate, and phyllosilicate-associated Fe(II) (Fe(II)-phyllosilicate). A Fe partitioning model was employed to analyze the fate of Fe(II) and assess the potential for abiotic Fe(II)-catalyzed reduction of Fe(III)-phyllosilicates. The results showed that in most cases Fe(III)- oxide utilization dominated (70-100 %) bulk Fe(III) reduction activity, and that electron transfer from oxide-derived Fe(II) played only a minor role (ca. 10-20 %) in Fe partitioning. In addition, the extent of Fe(III)-oxide reduction was positively correlated to surface area-normalized cation exchange capacity and the phyllosilicate-Fe(III)/total Fe(III) ratio, which suggests that the phyllosilicates in the natural sediments promoted Fe(III)-oxide reduction by binding of oxide-derived Fe(II), thereby enhancing Fe(III)-oxide reduction by reducing or delaying the inhibitory effect that Fe(II) accumulation on oxide and DIRB cell surfaces has on Fe(III)-oxide reduction. In general our results suggest that although Fe(III)-oxide reduction is likely to dominate bulk Fe(III) reduction in most subsurface sediments, Fe(II) binding by phyllosilicates is likely to play a key role in controlling the long-term kinetics of Fe(III)-oxide reduction.« less