Hexavalent chromium, Cr(VI), is a highly toxic carcinogen occurring in natural and industrial environments. Pathways to economical reduction to the more benign trivalent form, Cr(III), are necessary for treatment of contaminated groundwater. Magnetite’s (Fe3O4) mixture of Fe(II) and Fe(III) make it a promising material for remediation. This study investigated the mechanisms for reduction of Cr(VI) catalyzed by Fe3O4as a redox mediator in the presence of oxalic acid in HClO4and SO42−solutions, a system where the interactions among these species are not fully understood. The reduction of Cr(VI) in different anion environments is first measured on an Au rotating disk electrode. SO42−inhibits the formation of a passivation layer and Cl-partially inhibits passivation. The reduction of Cr(VI) on Fe3O4is limited by the availability of Fe(II) surface sites. Addition of oxalic acid works synergistically through liberation of Fe(II)-oxalate and soluble Cr(III)-oxalate products. A combination of Fe3O4activated by exposure to oxalic acid and use of an oxalic acid solution as a medium for reduction of Cr(VI) produces over 97% removal of Cr(VI). These results provide relevant insights regarding interactions of Fe3O4with organic acids and the anion environment which lead to the effective reduction of Cr(VI).
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Dissolution of Mn-bearing dolomite drives elevated Cr( vi ) occurrence in a Permian redbed aquifer
Municipalities in central Oklahoma, U.S.A. increasingly rely on water drawn from the Central Oklahoma Aquifer (COA) as surface water resources have not grown in proportion to population and current water demands. However, water drawn from certain regions of the COA frequently contains elevated levels of naturally occurring hexavalent chromium. Rock samples from the Norman Arsenic Test Hole Core (NATHC) were investigated to identify the mineralogic host(s) of Cr and mechanisms of Cr( vi ) release via bulk mineralogy and chemistry measurements, selective chemical extractions, and microscale elemental analyses. Results demonstrate most COA Cr is contained in Fe oxides and clays as isomorphic substitutions for Fe( iii ). Analyses of regional groundwater data, including hierarchical clustering methods and GIS, demonstrate the most intense Cr( vi ) occurrence is linked to cation exchange with Na-clays at depth. Cation exchange allows dissolution of Mn-bearing dolomite, which in turn produces Mn oxides in otherwise dolomite-saturated groundwaters. Mn oxides in turn are known to oxidize Cr( iii ) to Cr( vi ). In general, co-occurrence of Mn-bearing carbonates and exchangeable clays in any aquifer, particularly those with Cr( iii ) present in iron oxide cements, serve as ingredients for groundwater occurrences of oxidizable trace metals.
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- Award ID(s):
- 2114225
- PAR ID:
- 10460890
- Date Published:
- Journal Name:
- Environmental Science: Processes & Impacts
- Volume:
- 24
- Issue:
- 12
- ISSN:
- 2050-7887
- Page Range / eLocation ID:
- 2419 to 2436
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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