Impact of chromium (VI) as a co-contaminant on the sorption and co-precipitation of uranium (VI) in sediments under mildly alkaline oxic conditions

Uranium (U) waste, generated at a variety of mines and nuclear production sites, migrates in the subsurface, posing a serious threat to contaminate groundwater systems. In this study, batch equilibrium and kinetic experiments, geochemical modeling and solid phase characterization were conducted to investigate the impact of Cr(VI), a common co-contaminant, on the adsorption of U(VI) to quartz, plagioclase feldspar, and carbonate -dominated sediment (<= 2 mm). Batch experiments were performed under slightly alkaline conditions (7.80 +/- 0.18) and in the presence of major groundwater components (Ca2+, Mg2+, Na+, K+, carbonate, chloride, and sulfate) at different U(VI):Cr(VI) molar ratios 10:1, 1:1, and 1:10 at lower U(VI) concentration (10.5 mu M [2.5 mg/ L)) and at U(VI):Cr(VI) molar ratios of 168:1.05, 168:10.5, 168:105, 1:1, and 1:10 at higher U(VI) concentration (168 mu M [40 mg/L)). At the low U(VI) concentration (10.5 mu M [2.5 mg/L)), the distribution coefficients (Kd) were unchanged for the 10:1 and 1:1 U:Cr molar ratios indicating an excess of available U(VI) adsorption sites on the sediment. However, the U(VI) Kd values in the presence of Cr(VI) at the 1:10 M ratio decreased suggesting competition between U(VI) and Cr(VI) for adsorption sites. At the higher U(VI) concentration (168 mu M [40 mg/ L)), the Kd values were unaffected by U(VI):Cr(VI) molar ratios of 168:1.05, 168:10.5, 168:105, again indicating an excess of available sediment adsorption sites. At U:Cr molar ratios 1:1 and 1:10, there was a slight increase in Kd for U(VI) possibly reflecting an increase in inner-sphere binding of uranyl carbonate complexes. The adsorption process followed pseudo second-order kinetic parameters. These results indicate the sediment affinity for U(VI) adsorption appears to be largely independent of Cr(VI) under our experimental conditions. The intraparticle diffusion modeling of U(VI) adsorption to the sediment suggests a multi-step process, including film and intraparticle diffusion. The intraparticle diffusion stage remained constant in the presence of Cr(VI) suggesting the rate determining factors for overall equilibrium adsorption process for U(VI) was independent of Cr (VI). Understanding the mobility of U(VI) under natural conditions as simulated in our study is critical in developing effective remediation strategies and effective monitored natural attenuation (MNA) following the remediation of contaminated sites.