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Hexavalent Chromium Generation within Naturally Structured Soils and Sediments

Journal Article · · Environmental Science and Technology

Chromium(VI) produced from the oxidation of indigenous Cr(III) minerals is increasingly being recognized as a threat to groundwater quality. A critical determinant of Cr(VI) generation within soils and sediments is the necessary interaction of two low-solubility phases$$-$$Cr(III) silicates or (hydr)oxides and Mn(III/IV) oxides—that lead to its production. Here in this paper, we investigate the potential for Cr(III) oxidation by Mn oxides within fixed solid matrices common to soils and sediments. Artificial aggregates were constructed from Cr(OH)3- and Cr0.25Fe0.75(OH)3-coated quartz grains and either mixed with synthetic birnessite or inoculated with the Mn(II)-oxidizing bacterium Leptothrix cholodnii. In aggregates simulating low organic carbon environments, we observe Cr(VI) concentrations within advecting solutes at levels more than twenty-times the California drinking water standard. Chromium(VI) production is highly dependent on Cr-mineral solubility; increasing Fe-substitution (x = 0 to x = 0.75) decreases the solubility of the solid and concomitantly decreases total Cr(VI) generation by 37%. In environments with high organic carbon, reducing conditions within aggregate cores (microbially) generate sufficient Fe(II) to suppress Cr(VI) efflux. Our results illustrate Cr(VI) generation from reaction with Mn oxides within structured media simulating soils and sediments and provide insight into how fluctuating hydrologic and redox conditions impact coupled processes controlling Cr and Mn cycling.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); National Science Foundation (NSF)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1353183
Journal Information:
Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 4 Vol. 51; ISSN 0013-936X
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (81)

Potential transformations of chromium in natural waters journal January 1975
Physiology and ultrastructure of Leptothrix discophora SS-1 journal July 1986
Bioremediation of organic and metal contaminants with dissimilatory metal reduction journal February 1995
Chromium: History and nutritional importance journal January 1992
Natural hexavalent chromium in groundwaters interacting with ophiolitic rocks journal November 2002
Oxidative removal of Mn(II) from solution catalysed by the γ-FeOOH (lepidocrocite) surface journal December 1981
Oxidation state of Mn in the Mn oxide produced by Leptothrix discophora SS-1 journal August 1988
Surface reactions of chromium in soils and waters journal June 1995
X-ray absorption spectroscopic study of the sorption of Cr(III) at the oxide-water interface journal February 1992
Structural and compositional evolution of Cr/Fe solids after indirect chromate reduction by dissimilatory iron-reducing bacteria journal February 2003
Characterization of the manganese oxide produced by pseudomonas putida strain MnB1 journal July 2003
Solid phases in the cycling of manganese in eutrophic lakes: New insights from EXAFS spectroscopy journal January 1997
Natural chromium contamination of groundwater at León Valley, México journal April 2000
Oxidation and toxicity of chromium in ultramafic soils in Zimbabwe journal August 2002
Occurrence of hexavalent chromium in ground water in the western Mojave Desert, California journal July 2004
Chromium, chromium isotopes and selected trace elements, western Mojave Desert, USA journal May 2008
A regional-scale study of chromium and nickel in soils of northern California, USA journal August 2009
Chromium(VI) generation in vadose zone soils and alluvial sediments of the southwestern Sacramento Valley, California: A potential source of geogenic Cr(VI) to groundwater journal August 2011
Delta Chromium-53/52 isotopic composition of native and contaminated groundwater, Mojave Desert, USA journal April 2012
Origin and mobility of hexavalent chromium in North-Eastern Attica, Greece journal June 2012
Insights into controls on hexavalent chromium in groundwater provided by environmental tracers, Sacramento Valley, California, USA journal November 2015
Weathering and transport of chromium and nickel from serpentinite in the Coast Range ophiolite to the Sacramento Valley, California, USA journal October 2015
Cr(VI) occurrence and geochemistry in water from public-supply wells in California journal December 2015
Factors controlling the heterogeneous distribution of Cr(VI) in soil, plants and groundwater: Evidence from the Assopos basin, Greece journal January 2011
A comparative study of oxidation of Cr(III) in aqueous ions, complex ions and insoluble compounds by manganese-bearing mineral (birnessite) journal July 2009
Aggregate-scale spatial heterogeneity in reductive transformation of ferrihydrite resulting from coupled biogeochemical and physical processes journal May 2010
Alteration of ferrihydrite reductive dissolution and transformation by adsorbed As and structural Al: Implications for As retention journal February 2011
Distributed microbially- and chemically-mediated redox processes controlling arsenic dynamics within Mn-/Fe-oxide constructed aggregates journal March 2013
Cr(VI) genesis and dynamics in Ferralsols developed from ultramafic rocks: The case of Niquelândia, Brazil journal February 2013
The fate of chromium during tropical weathering: A laterite profile from Central Madagascar journal January 2014
Solid speciation and availability of chromium in ultramafic soils from Niquelândia, Brazil journal January 2006
Extent of oxidation of Cr(III) to Cr(VI) under various conditions pertaining to natural environment journal February 2006
Occurrence of Cr(VI) in drinking water of Greece and relation to the geological background journal January 2015
Geogenic Cr oxidation on the surface of mafic minerals and the hydrogeological conditions influencing hexavalent chromium concentrations in groundwater journal May 2015
Chromium(III) oxidation by .delta.-manganese oxide (MnO2). 1. Characterization journal January 1992
Reduction and dissolution of manganese(III) and manganese(IV) oxides by organics: 2. Survey of the reactivity of organics journal August 1984
Iron Promoted Reduction of Chromate by Dissimilatory Iron-Reducing Bacteria journal February 2001
Chromate removal from aqueous wastes by reduction with ferrous ion journal August 1988
Chromium Diffusion and Reduction in Soil Aggregates journal August 2001
Natural Occurrence of Hexavalent Chromium in the Aromas Red Sands Aquifer, California journal August 2005
Chromate Reduction and Retention Processes within Arid Subsurface Environments journal October 2005
Transport Implications Resulting from Internal Redistribution of Arsenic and Iron within Constructed Soil Aggregates journal January 2011
Chromium(III) Oxidation by Three Poorly-Crystalline Manganese(IV) Oxides. 1. Chromium(III)-Oxidizing Capacity journal October 2012
Cr(VI) Formation Related to Cr(III)-Muscovite and Birnessite Interactions in Ultramafic Environments journal August 2013
Cr(OH) 3 (s) Oxidation Induced by Surface Catalyzed Mn(II) Oxidation journal August 2014
XANES Evidence for Oxidation of Cr(III) to Cr(VI) by Mn-Oxides in a Lateritic Regolith Developed on Serpentinized Ultramafic Rocks of New Caledonia journal October 2009
Spatial Patterns and Modeling of Reductive Ferrihydrite Transformation Observed in Artificial Soil Aggregates journal September 2009
Kinetics of Chromate Reduction by Ferrous Iron journal January 1996
Surface-Catalyzed Chromium(VI) Reduction:  Reactivity Comparisons of Different Organic Reductants and Different Oxide Surfaces journal January 1996
Kinetics and pH Dependence of Chromium(VI) Reduction by Iron(II) journal May 1997
Reduction of Hexavalent Chromium by Amorphous Iron Sulfide journal July 1997
Solubility of amorphous chromium(III)-iron(III) hydroxide solid solutions journal July 1987
Genesis of hexavalent chromium from natural sources in soil and groundwater journal April 2007
Genetic identification of a respiratory arsenate reductase journal August 2003
Chromium Transformations in Natural Environments: The Role of Biological and Abiological Processes in Chromium(VI) Reduction journal August 2000
Stimulation of Mn2+ Oxidation in Leptothrix discophora SS-1 by Cu2+and Sequence Analysis of the Region Flanking the Gene Encoding Putative Multicopper Oxidase MofA journal October 2010
Identification and molecular analysis of the Leptothrix discophora SS‐1 mofA gene, a gene putatively encoding a manganese‐oxidizing protein with copper domains journal April 1997
In Situ Characterization of Heavy Metal Surface Reactions: The Chromium Case journal March 1992
Fungal oxidative dissolution of the Mn(II)-bearing mineral rhodochrosite and the role of metabolites in manganese oxide formation: Dissolution and oxidation of rhodochrosite by fungi journal November 2012
Hexavalent Chromium in the Ground Water in Paradise Valley, Arizona journal November 1975
Isolation, Cultural Maintenance, and Taxonomy of a Sheath-Forming Strain of Leptothrix discophora and Characterization of Manganese-Oxidizing Activity Associated with the Sheath journal January 1992
Production of Biogenic Mn Oxides by Leptothrix discophora SS-1 in a Chemically Defined Growth Medium and Evaluation of Their Pb Adsorption Characteristics journal January 1999
Isolation, Cultural Maintenance, and Taxonomy of a Sheath-Forming Strain of Leptothrix discophora and Characterization of Manganese-Oxidizing Activity Associated with the Sheath journal January 1992
Manganese oxidation by Leptothrix discophora. journal February 1987
Characterization of extracellular Mn2+-oxidizing activity and isolation of an Mn2+-oxidizing protein from Leptothrix discophora SS-1. journal January 1987
BIOGENIC MANGANESE OXIDES: Properties and Mechanisms of Formation journal May 2004
The synthesis of birnessite, cryptomelane, and some other oxides and hydroxides of manganese journal December 1971
Behavior of Chromium in Soils: III. Oxidation journal January 1979
Behavior of Chromium in Soils. VI. Interactions Between Oxidation‐Reduction and Organic Complexation journal April 1983
Distribution of Chromium Contamination and Microbial Activity in Soil Aggregates journal January 2003
Direct Measurement of Oxygen Profiles and Denitrification Rates in Soil Aggregates1 journal January 1985
Chromate Reduction by Subsurface Soils under Acidic Conditions journal May 1991
The structure of the manganese oxide on the sheath of the bacterium Leptothrix discophora : An XAFS study journal July 2004
Determination of Mn valence states in mixed-valent manganates by XANES spectroscopy journal May 2012
Kinetics of chromate reduction by ferrous ions derived from hematite and biotite at 25 degrees C journal February 1989
Chromium geochemistry in serpentinized ultramafic rocks and serpentine soils from the Franciscan complex of California journal January 2004
Chromium Geochemistry of Serpentine Soils journal February 2004
Mechanisms of Chromium Carcinogenicity and Toxicity journal January 1993
Toxicity and Carcinogenicity of Cr(VI) in Animal Models and Humans journal January 1997
Chromium species in the Columbia River and estuary1: Chromium species journal November 1980
The dominant role of structure for solute transport in soil: experimental evidence and modelling of structure and transport in a field experiment journal January 2006

Cited By (10)

Treatment of metal (loid) contaminated solutions using iron-peat as sorbent: is landfilling a suitable management option for the spent sorbent? journal May 2019
Oxidation of Cr(III)–Fe(III) Mixed-Phase Hydroxides by Chlorine: Implications on the Control of Hexavalent Chromium in Drinking Water journal May 2018
Effects of metal cation substitution on hexavalent chromium reduction by green rust journal February 2020
Emergent Properties of Microbial Activity in Heterogeneous Soil Microenvironments: Different Research Approaches Are Slowly Converging, Yet Major Challenges Remain journal August 2018
Products of Hexavalent Chromium Reduction by Green Rust Sodium Sulfate and Associated Reaction Mechanisms journal October 2018
Distribution, Ecological Risk Assessment, and Source Identification of Heavy Metals in River Sediments from Hai River and Its Tributaries, Tianjin, China journal January 2020
Effects of metal cation substitution on hexavalent chromium reduction by green rust text January 2020
Governing Constraints of Chromium(VI) Formation from Chromium(III)-Bearing Minerals in Soils and Sediments journal November 2019
Products of Hexavalent Chromium Reduction by Green Rust Sodium Sulfate and Associated Reaction Mechanisms text January 2018
Effects of metal cation substitution on hexavalent chromium reduction by green rust text January 2020

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