U.S. Department of Energy
Date of this Version
Chemical Geology 251 (2008) 1–7; doi:10.1016/j.chemgeo.2008.01.003
Batch U(VI) sorption/reduction experiments were completed on sterilized and non-sterilized sediment samples to elucidate biological and geochemical reduction mechanisms. Results from X-ray absorption nearedge structure (XANES) spectroscopy revealed that γ-sterilized sediments were actually better sorbents of U(VI), despite the absence of any measurable biological activity. These results indicate that γ-irradiation induced significant physico-chemical changes in the sediment which is contrary to numerous other studies identifying γ-sterilization as an effective and minimally invasive technique. To identify the extent and method of alteration of the soil as a result of γ-sterilization, untreated soil samples, physically separated size fractions, and chemically extracted fractions of the soil were analyzed pre- and post-sterilization. The effects of sterilization on mineralogy, pH, natural organic matter (NOM), cation exchange capacity (CEC), and iron oxidation state were determined. Results indicated that major mineralogy of the clay and whole sediment samples was unchanged. Sediment pH decreased only slightly with γ-irradiation; however, irradiation produced a significant decrease in CEC of the untreated sediments and affected both the organic and inorganic fractions. Mössbauer spectra of non-sterile and γ-sterilized sedimentsmeasuredmore reduced iron present in γ-sterilized sediments compared to non-sterile samples. Our results suggest that sterilization by γ-irradiation induced iron reduction that may have increased the sorption and/or reduction of U(VI) onto these sediments. However, Mössbauer and batch sorption data are somewhat contradictory, the former indicates that the iron oxide or iron hydroxide minerals are more significantly reduced while the later indicates that reduced clay minerals account for greater sorption of U(VI).