title: Long-term stability of organic carbon-stimulated chromate reduction in contaminated soils and its relation to manganese redox status.
abstract: In situ reduction of toxic Cr(VI) to less hazardous Cr(III) is becoming a popular strategy for remediating contaminated soils. However, the long-term stability of reduced Cr remains to be understood, especially given the common presence of Mn(III, IV) oxides that re-oxidize Cr(III). This 4.6 year laboratory study tracked Cr and Mn redox transformations in soils contaminated with Cr(VI), which were then treated with different amounts of organic carbon (OC). Changes in Cr and Mn oxidation states within soils were directly and nondestructively measured using micro-X-ray absorption near-edge structure spectroscopy. Chromate reduction was roughly first-order, and the extent of reduction was enhanced with higher OC additions. However, significant Cr(III) re-oxidation occurred in soils exposed to the highest Cr(VI) concentrations (2560 mg kg(-1)). Transient Cr(Ill) re-oxidation up to 420 mg kg(-1) was measured at 1.1 years after OC treatment, followed by further reduction. Chromate concentrations increased by 220 mg kg(-1) at the end of the study (4.6 years) in one soil. The causal role that the Mn oxidation state had in re-oxidizing Cr was supported by trends in Mn K-edge energies. These results provide strong evidence for long-term dependence of soil Cr oxidation states on balances between OC availability and Mn redox status.
authors.affiliation: Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, USA. tktokunaga@lbl.gov
authors.forename: Tetsu K
authors.initials: TK
authors.lastname: Tokunaga
authors.forename: Jiamin
authors.initials: J
authors.lastname: Wan
authors.forename: Antonio
authors.initials: A
authors.lastname: Lanzirotti
authors.forename: Steve R
authors.initials: SR
authors.lastname: Sutton
authors.forename: Matthew
authors.initials: M
authors.lastname: Newville
authors.forename: William
authors.initials: W
authors.lastname: Rao
mesh_terms: D002244:Carbon / Q000737:chemistry*; D002840:Chromates / Q000737:chemistry*; D004784:Environmental Monitoring; D052918:Environmental Restoration and Remediation; D006863:Hydrogen-Ion Concentration; D008345:Manganese / Q000737:chemistry*; D010084:Oxidation-Reduction; D012989:Soil Pollutants / Q000737:chemistry*; D013997:Time Factors
chemical_list: D002840:Chromates; D012989:Soil Pollutants; D008345:Manganese; D002244:Carbon