Effects of Contaminant Concentration, Aging, and Soil Properties on the Bioaccessibility of Cr(III) and Cr(VI) in Soil

Abstract

Contaminated soils at numerous U.S. Department of Defense, Department of Energy, and other industrial facilities often contain huge inventories of toxic metals such as chromium. Ingestion of soil by children is often the primary risk factor that drives the need for remediation. Site assessments are typically based solely on total soil-metal concentrations and do not consider the potential for decreased bioaccessibility due to metal sequestration by soil. The objectives of this research are to investigate the effect of soil properties on the bioaccessibility of Cr(III) and Cr(VI) as a function of contaminant concentration and aging. The A and upper B horizons of two well-characterized soils, representative of Cr-contaminated soils in the southeastern United States, were treated with varying concentration of Cr(III) and Cr(VI) and allowed to age. The bioaccessibility of the contaminated soils was measured over a 200-d time period using a physiologically based extraction test (PBET) that was designed to simulate the digestive process of the stomach. The sorption of Cr(III) and Cr(VI) varied significantly as a function of soil type and horizon, and the oxidation state of the contaminant. Solid phase concentrations with Cr(III) were significantly greater than Cr(VI) for any given initial Cr concentration. This is consistent with the mechanisms of Cr(III) vs. Cr(VI) sequestration by the soils, where the formation of Cr(III)-hydroxides can result in the accumulation of large mass fractions of contaminant on mineral surfaces. Overall, Cr bioaccessibility decreased with duration of exposure for all soils and at all solid phase concentrations, with aging effects being more pronounced for Cr(III). The decrease in Cr bioaccessibility was rapid for the first 50 d and then slowed dramatically between 50 and 200 d. In general, the effects of Cr solid phase concentration on bioaccessibility was small, with Cr(III) showing the most pronounced effect; higher solid phase concentrations resulted in a decrease in bioaccessibility. Chemical extraction methods and X-ray Adsorption Spectroscopy analyses suggested that the bioaccessibility of Cr(VI) was significantly influenced by reduction processes catalyzed by soil organic carbon. Soils with sufficient organic carbon had lower Cr bioaccessibility values (∼10 to 20%) due to an enhanced reduction of Cr(VI) to Cr(III). In soils where organic carbon was limited and reduction processes were minimal, the bioaccessibility of Cr(VI) dramatically increased (∼60 to 70%).