Department of Civil and Environmental Engineering, Colorado School of Mines, Golden, Colorado 80401, United States.
Environ Sci Technol. 2013 Jun 18;47(12):6214-22. doi: 10.1021/es304677c. Epub 2013 Jun 7.
This study focuses on the effects of fulvic acid (FA) on uranium(VI) sorption kinetics to a silica sand. Using a tritium-labeled FA in batch experiments made it possible to investigate sorption rates over a wide range of environmentally relevant FA concentrations (0.37-23 mg L(-1) TOC). Equilibrium speciation calculations were coupled with an evaluation of U(VI) and FA sorption rates based on characteristic times. This allowed us to suggest plausible sorption mechanisms as a function of solution conditions (e.g., pH, U(VI)/FA/surface site ratios). Our results indicate that U(VI) sorption onto silica sand can be either slower or faster in the presence of FA compared to a ligand-free system. This suggests a shift in the underlying mechanisms of FA effects on U(VI) sorption, from competitive sorption to influences of U(VI)-FA complexes, in the same system. Changes in metal sorption rates depend on the relative concentrations of metals, organic ligands, and mineral surface sites. Hence, these results elucidate the sometimes conflicting information in the literature about the influence of organic matter on metal sorption rates. Furthermore, they provide guidance for the selection of appropriate sorption equilibration times for experiments that are designed to determine metal distribution coefficients (Kd values) under equilibrium conditions.
本研究聚焦于富里酸(FA)对二氧化硅砂中铀(VI)吸附动力学的影响。使用氚标记的 FA 在批处理实验中,我们可以在广泛的环境相关 FA 浓度范围内(0.37-23 mg L(-1) TOC)研究吸附速率。平衡形态计算与 U(VI)和 FA 吸附速率的评估相结合,基于特征时间。这使我们能够根据溶液条件(例如 pH、U(VI)/FA/表面位点比)提出合理的吸附机制。我们的结果表明,与无配体体系相比,FA 的存在会使二氧化硅砂上的 U(VI)吸附变得更快或更慢。这表明在同一体系中,FA 对 U(VI)吸附影响的潜在机制从竞争吸附转变为 U(VI)-FA 配合物的影响。金属吸附速率的变化取决于金属、有机配体和矿物表面位点的相对浓度。因此,这些结果阐明了文献中关于有机物对金属吸附速率影响的有时相互矛盾的信息。此外,它们为在平衡条件下设计用于确定金属分配系数(Kd 值)的实验选择合适的吸附平衡时间提供了指导。