Inhibition of Chromium(III) Oxidation through Manganese(IV) Oxide Passivation and Iron(II) Abiotic Reduction

Aiken, Miranda L.; Abernathy, Macon J.; Schaefer, Michael V.; Lee, Ilkeun; Ying, Samantha C.

doi:10.1021/acsearthspacechem.3c00141

Inhibition of Chromium(III) Oxidation through Manganese(IV) Oxide Passivation and Iron(II) Abiotic Reduction

Journal Article · Sun Nov 12 23:00:00 EST 2023 · ACS Earth and Space Chemistry

DOI:https://doi.org/10.1021/acsearthspacechem.3c00141· OSTI ID:2404890

^[1]; ^[2]; ^[3]; ^[4]; ^[5]

Chapman Univ., Orange, CA (United States); SLAC
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
New Mexico Institute of Mining and Technology, Socorro, NM (United States)
Univ. of California, Riverside, CA (United States)
Chapman Univ., Orange, CA (United States); Univ. of California, Riverside, CA (United States)

Manganese (Mn) oxides are strong oxidants that are ubiquitous in soils and can oxidize redox-active metals, including chromium (Cr). In soil environments, trivalent chromium (Cr(III)) is a benign, immobile micronutrient, whereas the hexavalent Cr(VI) form is present as a highly mobile, toxic chromate oxyanion. Although many studies have characterized the capacity of Mn(III/IV) oxides to oxidize Cr(III) to toxic Cr(VI), the oxidative capacity of Mn oxides in the presence of potentially passivating soil constituents, specifically reduced soluble iron (Fe(II)_aq), remains unresolved. We hypothesized that chemical processes at redox interfaces, such as diffusion-limited environments within soil aggregates, can lead to decreased Cr(VI) production from Mn oxide-driven oxidation due to passivation by Fe(II)_aq. A multichamber diffusion-limited reactor was used to simulate transport at soil redox interfaces and investigate the capacity of poorly crystalline and crystalline Mn oxides to oxidize solid Cr(III) minerals to Cr(VI) in the presence of Fe(II)_aq. As predicted, Cr(VI) was produced through the Mn oxide-catalyzed oxidation of Cr(III) at a rate controlled by the solubility of Cr(OH)₃. However, in the presence of Fe(II)_aq, the concentration of aqueous Cr(VI) decreased as a function of the Fe(II)_aq concentration, where high concentrations of Fe(II)_aq completely inhibited Cr(VI) production, likely through both the passivation of the Mn oxide and the direct reduction of Cr(VI) by Fe(II). At both low (14 μM) and high (100 μM) Fe(II)_aq concentrations, the iron oxide minerals hematite (Fe₂O₃) and goethite (α-FeOOH) were associated with the Mn oxides, which can cause surface passivation, a likely role that decreases Cr(III) oxidation. Additionally, the Cr(III) oxidation rate decreased with increasing crystallinity of the Mn oxides whether or not Fe(II) was present.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 2404890

Journal Information:: ACS Earth and Space Chemistry, Journal Name: ACS Earth and Space Chemistry Journal Issue: 12 Vol. 7; ISSN 2472-3452

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (68)

Preferential flow descriptions for structured soils Gerke, Horst H. Journal of Plant Nutrition and Soil Science, Vol. 169, Issue 3 https://doi.org/10.1002/jpln.200521955	journal	June 2006
Aqueous geochemistry of chromium: A review Richard, Françoise C.; Bourg, Alain C. M. Water Research, Vol. 25, Issue 7 https://doi.org/10.1016/0043-1354(91)90160-R	journal	July 1991
Structural and compositional evolution of Cr/Fe solids after indirect chromate reduction by dissimilatory iron-reducing bacteria Hansel, C. M.; Wielinga, B. W.; Fendorf, Scott Geochimica et Cosmochimica Acta, Vol. 67, Issue 3 https://doi.org/10.1016/S0016-7037(02)01081-5	journal	February 2003
Secondary mineralization pathways induced by dissimilatory iron reduction of ferrihydrite under advective flow Hansel, Colleen M.; Benner, Shawn G.; Neiss, Jim Geochimica et Cosmochimica Acta, Vol. 67, Issue 16 https://doi.org/10.1016/S0016-7037(03)00276-X	journal	August 2003
Lead sorption efficiencies of natural and synthetic Mn and Fe-oxides O'Reilly, S. E.; Hochella, Michael F. Geochimica et Cosmochimica Acta, Vol. 67, Issue 23 https://doi.org/10.1016/S0016-7037(03)00413-7	journal	December 2003
Chromium oxidation by manganese (hydr)oxides in a California aquifer Ndung’u, Kuria; Friedrich, Stephan; Gonzalez, Ana R. Applied Geochemistry, Vol. 25, Issue 3 https://doi.org/10.1016/j.apgeochem.2009.12.004	journal	March 2010
Oxidation and competitive retention of arsenic between iron- and manganese oxides Ying, Samantha C.; Kocar, Benjamin D.; Fendorf, Scott Geochimica et Cosmochimica Acta, Vol. 96 https://doi.org/10.1016/j.gca.2012.07.013	journal	November 2012
Distributed microbially- and chemically-mediated redox processes controlling arsenic dynamics within Mn-/Fe-oxide constructed aggregates Ying, Samantha C.; Masue-Slowey, Yoko; Kocar, Benjamin D. Geochimica et Cosmochimica Acta, Vol. 104 https://doi.org/10.1016/j.gca.2012.08.020	journal	March 2013
Lithologic and redox controls on hexavalent chromium in vadose zone sediments of California’s Central Valley McClain, Cynthia N.; Fendorf, Scott; Johnson, Shane T. Geochimica et Cosmochimica Acta, Vol. 265 https://doi.org/10.1016/j.gca.2019.07.044	journal	November 2019
The effects of iron(II) on the kinetics of arsenic oxidation and sorption on manganese oxides Wu, Yun; Li, Wei; Sparks, Donald L. Journal of Colloid and Interface Science, Vol. 457 https://doi.org/10.1016/j.jcis.2015.07.022	journal	November 2015
Synthesis, characterization and stability of Cr(III) and Fe(III) hydroxides Papassiopi, N.; Vaxevanidou, K.; Christou, C. Journal of Hazardous Materials, Vol. 264 https://doi.org/10.1016/j.jhazmat.2013.09.058	journal	January 2014
Natural source of Cr(VI) in soil: The anoxic oxidation of Cr(III) by Mn oxides Ao, Ming; Sun, Shengsheng; Deng, Tenghaobo Journal of Hazardous Materials, Vol. 433 https://doi.org/10.1016/j.jhazmat.2022.128805	journal	July 2022
Arsenic and manganese exposure and children's intellectual function Wasserman, Gail A.; Liu, Xinhua; Parvez, Faruque NeuroToxicology, Vol. 32, Issue 4 https://doi.org/10.1016/j.neuro.2011.03.009	journal	August 2011
Manganese exposure from drinking water and children's academic achievement Khan, Khalid; Wasserman, Gail A.; Liu, Xinhua NeuroToxicology, Vol. 33, Issue 1 https://doi.org/10.1016/j.neuro.2011.12.002	journal	January 2012
⁵⁴ Mn Radiotracers Demonstrate Continuous Dissolution and Reprecipitation of Vernadite (δ-MnO ₂ ) during Interaction with Aqueous Mn(II) Elzinga, Evert J. Environmental Science & Technology, Vol. 50, Issue 16 https://doi.org/10.1021/acs.est.6b02874	journal	July 2016
Quantifying Cr(VI) Production and Export from Serpentine Soil of the California Coast Range McClain, Cynthia N.; Fendorf, Scott; Webb, Samuel M. Environmental Science & Technology, Vol. 51, Issue 1 https://doi.org/10.1021/acs.est.6b03484	journal	December 2016
Hexavalent Chromium Generation within Naturally Structured Soils and Sediments Hausladen, Debra M.; Fendorf, Scott Environmental Science & Technology, Vol. 51, Issue 4 https://doi.org/10.1021/acs.est.6b04039	journal	February 2017
Rates of Cr(VI) Generation from Cr _x Fe _{1– x} (OH) ₃ Solids upon Reaction with Manganese Oxide Pan, Chao; Liu, Huan; Catalano, Jeffrey G. Environmental Science & Technology, Vol. 51, Issue 21 https://doi.org/10.1021/acs.est.7b04097	journal	October 2017
Hexavalent Chromium Sources and Distribution in California Groundwater Hausladen, Debra M.; Alexander-Ozinskas, Annika; McClain, Cynthia Environmental Science & Technology, Vol. 52, Issue 15 https://doi.org/10.1021/acs.est.7b06627	journal	June 2018
Understanding the Roles of Dissolution and Diffusion in Cr(OH) ₃ Oxidation by δ-MnO ₂ Pan, Chao; Liu, Huan; Catalano, Jeffrey G. ACS Earth and Space Chemistry, Vol. 3, Issue 3 https://doi.org/10.1021/acsearthspacechem.8b00129	journal	January 2019
Influence of Fe(II) on Arsenic(III) Oxidation by Birnessite in Diffusion-Limited Systems Mock, Rebecca Pettit; Schaefer, Michael V.; Pacheco, Juan Lezama ACS Earth and Space Chemistry, Vol. 3, Issue 4 https://doi.org/10.1021/acsearthspacechem.8b00184	journal	February 2019
Chromium(III) oxidation by .delta.-manganese oxide (MnO2). 1. Characterization Fendorf, Scott E.; Zasoski, Robert J. Environmental Science & Technology, Vol. 26, Issue 1 https://doi.org/10.1021/es00025a006	journal	January 1992
Iron Promoted Reduction of Chromate by Dissimilatory Iron-Reducing Bacteria Wielinga, Bruce; Mizuba, Midori M.; Hansel, Colleen M. Environmental Science & Technology, Vol. 35, Issue 3 https://doi.org/10.1021/es001457b	journal	February 2001
Chromium Diffusion and Reduction in Soil Aggregates Tokunaga, Tetsu K.; Wan, Jiamin; Firestone, Mary K. Environmental Science & Technology, Vol. 35, Issue 15 https://doi.org/10.1021/es010523m	journal	August 2001
Arsenic(III) Oxidation and Arsenic(V) Adsorption Reactions on Synthetic Birnessite Manning, Bruce A.; Fendorf, Scott E.; Bostick, Benjamin Environmental Science & Technology, Vol. 36, Issue 5 https://doi.org/10.1021/es0110170	journal	March 2002
Natural Occurrence of Hexavalent Chromium in the Aromas Red Sands Aquifer, California Gonzalez, A. R.; Ndung'u, K.; Flegal, A. R. Environmental Science & Technology, Vol. 39, Issue 15 https://doi.org/10.1021/es048835n	journal	August 2005
Chromate Reduction and Retention Processes within Arid Subsurface Environments Ginder-Vogel, Matthew; Borch, Thomas; Mayes, Melanie A. Environmental Science & Technology, Vol. 39, Issue 20 https://doi.org/10.1021/es050535y	journal	October 2005
Competing Fe(II)-Induced Mineralization Pathways of Ferrihydrite Hansel, Colleen M.; Benner, Shawn G.; Fendorf, Scott Environmental Science & Technology, Vol. 39, Issue 18 https://doi.org/10.1021/es050666z	journal	September 2005
Transport Implications Resulting from Internal Redistribution of Arsenic and Iron within Constructed Soil Aggregates Masue-Slowey, Yoko; Kocar, Benjamin D.; Bea Jofré, Sergio Andrés Environmental Science & Technology, Vol. 45, Issue 2 https://doi.org/10.1021/es1027663	journal	January 2011
Competitive Microbially and Mn Oxide Mediated Redox Processes Controlling Arsenic Speciation and Partitioning Ying, Samantha C.; Kocar, Benjamin D.; Griffis, Sarah D. Environmental Science & Technology, Vol. 45, Issue 13 https://doi.org/10.1021/es200351m	journal	July 2011
Reductive Transformation of Birnessite by Aqueous Mn(II) Elzinga, Evert J. Environmental Science & Technology, Vol. 45, Issue 15 https://doi.org/10.1021/es2013038	journal	August 2011
Cr(VI) Formation Related to Cr(III)-Muscovite and Birnessite Interactions in Ultramafic Environments Rajapaksha, Anushka Upamali; Vithanage, Meththika; Ok, Yong Sik Environmental Science & Technology, Vol. 47, Issue 17 https://doi.org/10.1021/es4015025	journal	August 2013
Reductive Processes Controlling Arsenic Retention: Revealing the Relative Importance of Iron and Arsenic Reduction Tufano, Katharine J.; Reyes, Carolina; Saltikov, Chad W. Environmental Science & Technology, Vol. 42, Issue 22 https://doi.org/10.1021/es801059s	journal	November 2008
Spatial Patterns and Modeling of Reductive Ferrihydrite Transformation Observed in Artificial Soil Aggregates Pallud, Céline; Kausch, Matteo; Fendorf, Scott Environmental Science & Technology, Vol. 44, Issue 1 https://doi.org/10.1021/es901736t	journal	September 2009
Kinetics of Chromate Reduction by Ferrous Iron Fendorf, Scott E.; Li, Guangchao Environmental Science & Technology, Vol. 30, Issue 5 https://doi.org/10.1021/es950618m	journal	January 1996
Kinetics and pH Dependence of Chromium(VI) Reduction by Iron(II) Buerge, Ignaz J.; Hug, Stephan J. Environmental Science & Technology, Vol. 31, Issue 5 https://doi.org/10.1021/es960672i	journal	May 1997
Influence of Mineral Surfaces on Chromium(VI) Reduction by Iron(II) Buerge, Ignaz J.; Hug, Stephan J. Environmental Science & Technology, Vol. 33, Issue 23 https://doi.org/10.1021/es981297s	journal	December 1999
Chromium(III) hydrolysis constants and solubility of chromium(III) hydroxide Rai, Dhanpat; Sass, Bruce M.; Moore, Dean A. Inorganic Chemistry, Vol. 26, Issue 3 https://doi.org/10.1021/ic00250a002	journal	February 1987
Solubility of amorphous chromium(III)-iron(III) hydroxide solid solutions Sass, Bruce M.; Rai, Dhanpat Inorganic Chemistry, Vol. 26, Issue 14 https://doi.org/10.1021/ic00261a013	journal	July 1987
Relation between Catalytic Activity and Size of Particle Thiele, E. W. Industrial & Engineering Chemistry, Vol. 31, Issue 7 https://doi.org/10.1021/ie50355a027	journal	July 1939
Critical Evaluation and Selection of Standard State Thermodynamic Properties for Chromium Metal and Its Aqueous Ions, Hydrolysis Species, Oxides, and Hydroxides Ball, James W.; Nordstrom, D. Kirk Journal of Chemical & Engineering Data, Vol. 43, Issue 6 https://doi.org/10.1021/je980080a	journal	November 1998
Chromium in Drinking Water: Sources, Metabolism, and Cancer Risks Zhitkovich, Anatoly Chemical Research in Toxicology, Vol. 24, Issue 10 https://doi.org/10.1021/tx200251t	journal	October 2011
Formation of manganese oxides by bacterially generated superoxide Learman, D. R.; Voelker, B. M.; Vazquez-Rodriguez, A. I. Nature Geoscience, Vol. 4, Issue 2 https://doi.org/10.1038/ngeo1055	journal	January 2011
Organic buffers act as reductants of abiotic and biogenic manganese oxides Hausladen, Debra M.; Peña, Jasquelin Scientific Reports, Vol. 13, Issue 1 https://doi.org/10.1038/s41598-023-32691-5	journal	April 2023
Genesis of hexavalent chromium from natural sources in soil and groundwater Oze, C.; Bird, D. K.; Fendorf, S. Proceedings of the National Academy of Sciences, Vol. 104, Issue 16 https://doi.org/10.1073/pnas.0701085104	journal	April 2007
Manganese oxide minerals: Crystal structures and economic and environmental significance Post, J. E. Proceedings of the National Academy of Sciences, Vol. 96, Issue 7 https://doi.org/10.1073/pnas.96.7.3447	journal	March 1999
Cr(III) Oxidation and Cr Toxicity in Cultures of the Manganese(II)-OxidizingPseudomonas putidaStrain GB-1 Murray, Karen J.; Mozafarzadeh, Mylene L.; Tebo, Bradley M. Geomicrobiology Journal, Vol. 22, Issue 3-4 https://doi.org/10.1080/01490450590945988	journal	April 2005
Toxicity and Carcinogenicity of Chromium Compounds in Humans Costa, Max; Klein, Catherine B. Critical Reviews in Toxicology, Vol. 36, Issue 2 https://doi.org/10.1080/10408440500534032	journal	January 2006
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Anoxic oxidation of chromium Oze, Christopher; Sleep, Norman H.; Coleman, Robert G. Geology, Vol. 44, Issue 7 https://doi.org/10.1130/G37844.1	journal	June 2016
BIOGENIC MANGANESE OXIDES: Properties and Mechanisms of Formation Tebo, Bradley M.; Bargar, John R.; Clement, Brian G. Annual Review of Earth and Planetary Sciences, Vol. 32, Issue 1 https://doi.org/10.1146/annurev.earth.32.101802.120213	journal	May 2004
The synthesis of birnessite, cryptomelane, and some other oxides and hydroxides of manganese McKenzie, R. M. Mineralogical Magazine, Vol. 38, Issue 296 https://doi.org/10.1180/minmag.1971.038.296.12	journal	December 1971
Fe(II) reduction of pyrolusite (β-MnO2) and secondary mineral evolution Schaefer, Michael V.; Handler, Robert M.; Scherer, Michelle M. Geochemical Transactions, Vol. 18, Issue 1 https://doi.org/10.1186/s12932-017-0045-0	journal	December 2017
Measuring the impact of manganese exposure on children’s neurodevelopment: advances and research gaps in biomarker-based approaches Coetzee, Donna J.; McGovern, Patricia M.; Rao, Raghavendra Environmental Health, Vol. 15, Issue 1 https://doi.org/10.1186/s12940-016-0174-4	journal	August 2016
SIXPack a Graphical User Interface for XAS Analysis Using IFEFFIT Webb, S. M. Physica Scripta https://doi.org/10.1238/Physica.Topical.115a01011	journal	January 2005
Neurobehavioral Function in School-Age Children Exposed to Manganese in Drinking Water Oulhote, Youssef; Mergler, Donna; Barbeau, Benoit Environmental Health Perspectives, Vol. 122, Issue 12 https://doi.org/10.1289/ehp.1307918	journal	December 2014
Role of Manganese in the Oxidation of Arsenite by Freshwater Lake Sediments1 Oscarson, D. W. Clays and Clay Minerals, Vol. 29, Issue 3 https://doi.org/10.1346/CCMN.1981.0290308	journal	January 1981
Behavior of Chromium in Soils: III. Oxidation Bartlett, Richmond; James, Bruce Journal of Environmental Quality, Vol. 8, Issue 1 https://doi.org/10.2134/jeq1979.00472425000800010008x	journal	January 1979
Distribution of Chromium Contamination and Microbial Activity in Soil Aggregates Tokunaga, Tetsu K.; Wan, Jiamin; Hazen, Terry C. Journal of Environment Quality, Vol. 32, Issue 2 https://doi.org/10.2134/jeq2003.5410	journal	January 2003
Dependence of Arsenic Fate and Transport on Biogeochemical Heterogeneity Arising from the Physical Structure of Soils and Sediments Masue-Slowey, Yoko; Ying, Samantha C.; Kocar, Benjamin D. Journal of Environmental Quality, Vol. 42, Issue 4, p. 1119-1129 https://doi.org/10.2134/jeq2012.0253	journal	July 2013
Direct Measurement of Oxygen Profiles and Denitrification Rates in Soil Aggregates1 Sexstone, Alan J.; Revsbech, Niels Peter; Parkin, Timothy B. Soil Science Society of America Journal, Vol. 49, Issue 3 https://doi.org/10.2136/sssaj1985.03615995004900030024x	journal	January 1985
Chromate Reduction by Subsurface Soils under Acidic Conditions Eary, L. E.; Rai, Dhanpat Soil Science Society of America Journal, Vol. 55, Issue 3 https://doi.org/10.2136/sssaj1991.03615995005500030007x	journal	May 1991
Oxygen Concentration and Redox Potential Gradients in Unsaturated Model Soil Aggregates Zausig, Jörg; Stepniewski, Witold; Horn, Rainer Soil Science Society of America Journal, Vol. 57, Issue 4 https://doi.org/10.2136/sssaj1993.03615995005700040005x	journal	January 1993
Oxidation of Chromium(III) to (VI) by Manganese Oxides Kim, Jae Gon; Dixon, Joe B.; Chusuei, Charles C. Soil Science Society of America Journal, Vol. 66, Issue 1 https://doi.org/10.2136/sssaj2002.3060	journal	January 2002
The reactivity of seven Mn-oxides with Cr ³⁺ _aq : A comparative analysis of a complex, environmentally important redox reaction Weaver, Robert M.; Hochella, Michael F. American Mineralogist, Vol. 88, Issue 11-12 https://doi.org/10.2138/am-2003-11-1246	journal	November 2003
Determination of Mn valence states in mixed-valent manganates by XANES spectroscopy Manceau, A.; Marcus, M. A.; Grangeon, S. American Mineralogist, Vol. 97, Issue 5-6 https://doi.org/10.2138/am.2012.3903	journal	May 2012
Chromium Geochemistry of Serpentine Soils Oze, Christopher; Fendorf, Scott; Bird, Dennis K. International Geology Review, Vol. 46, Issue 2 https://doi.org/10.2747/0020-6814.46.2.97	journal	February 2004
The chromium cycle in a seasonally anoxic lake Johnson, C. Annette; Sigg, Laura; Lindauer, Ursula Limnology and Oceanography, Vol. 37, Issue 2 https://doi.org/10.4319/lo.1992.37.2.0315	journal	March 1992

Similar Records

Hexavalent Chromium Generation within Naturally Structured Soils and Sediments

Journal Article · Thu Jan 12 23:00:00 EST 2017 · Environmental Science and Technology · OSTI ID:1353183

Influence of organic ligands on chromium(VI) reduction by iron(II)

Journal Article · Wed Jul 15 00:00:00 EDT 1998 · Environmental Science and Technology · OSTI ID:655420

The reactivity of Fe(II) associated with goethite formed during short redox cycles toward Cr(VI) reduction under oxic conditions

Journal Article · Tue Aug 01 00:00:00 EDT 2017 · Chemical Geology · OSTI ID:1372256

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Cr(VI)
aggregates
birnessite
contamination
diffusion
hexavalent chromium
pyrolusite

Inhibition of Chromium(III) Oxidation through Manganese(IV) Oxide Passivation and Iron(II) Abiotic Reduction

Citation Formats

References (68)

Similar Records

Related Subjects