Integrated experiments and numerical simulations for chromium (VI) surface complexation in natural unconsolidated sediments

This study focuses on the adsorption and transport of Cr (VI) on natural sediments from Qiqihar, China. Through batch and column experiments, we assessed the adsorption capacities influenced by factors such as contact time, initial concentration, pH, ionic strength, solid-to-solution ratio, coexisting ions in groundwater, sediment characteristics and flow rate. The adsorption kinetics of Cr (VI) follow the pseudo-first-order model well, while the isotherms of all three sediments are accurately represented by the Freundlich model. The adsorption edges reveal a strong pH dependence in Cr (VI) adsorption: the stronger the acidity, the more favorable it is for adsorption. The adsorption capacity decreases with an increasing solid-to-solution ratio, stabilizing at higher ratios. Coexisting ions in groundwater reduce Cr (VI) adsorption in loam under neutral pH. Additionally, Fourier transform infrared spectroscopy (FTIR) results indicate that the hydroxyl group is the primary reactive functional group in all three sediments. X-ray photoelectron spectroscopy (XPS) results further show partial adsorbed Cr (VI) was reduced to Cr (III) by organic matters. However, surface complexation reactions dominate the removal of Cr (VI). On the base above, we introduced a surface complexation model, optimizing equilibrium complexation constants by fitting adsorption edges. Subsequently, reactive transport models incorporating both surface complexation and reduction processes for Cr (VI) were established to simulate column experiments. As the flow rate decreases, the adsorption capacity and the amount of reduction reaction for Cr (VI) increase, while the reduction rate decreases. Specifically, the reduction for Cr (VI) was found to be more significant in loam compared to sand, correlating with the organic matter content. The results emphasize the existence of surface complexation reactions and the role of organic matters in electron transfer. Our study provides significant information for understanding Cr (VI) adsorption and transport behavior in natural aquifer sediments.