Mechanism and modeling of hexavalent chromium interaction with a typical black soil: the importance of the relationship between adsorption and reduction.

Black soils have a significant retention effect on the migration of Cr(vi) towards groundwater, and Cr(vi) adsorption and reduction are both involved in this process. However, the adsorption and reduction of Cr(vi) were always investigated separately in previous studies resulting in an unclear relationship between them. In this study, the adsorption and reduction kinetic processes of Cr(vi) by a typical black soil were separately investigated under different initial Cr(vi) concentrations (40-400 mg L) and pH conditions (3.5-7.0) by the means of desorption treatment, and the equilibrium relationship between aqueous and adsorbed Cr(vi) was innovatively established based on the kinetic data. It was found that under pH 5.7 the adsorbed Cr(vi) content on soil particles was linearly correlated with the remaining Cr(vi) concentration in solution with time ( = 0.98), and the reduction rate of Cr(vi) in the reaction system was linearly correlated with the adsorbed Cr(vi) content on soil particles with time ( = 0.99). With pH decreasing from 7.0 to 3.5, the partition of Cr(vi) between solid and aqueous phases turned out to be of a non-linear nature, which can be fitted better by the Freundlich model. The retention of Cr(vi) by black soil was determined to follow the "adsorption-reduction" mechanism, where the Cr(vi) was first rapidly adsorbed onto the soil particles by a reversible adsorption reaction, and then the adsorbed Cr(vi) was gradually reduced into Cr(iii). A two-step kinetic model was developed accordingly, and the experimental data were fitted much better by the two-step adsorption-reduction kinetic model ( = 0.89 on average) compared with the traditional first-order and second-order kinetic models ( = 0.66 and 0.76 on average respectively). This paper highlights the novel two step kinetic model developed based on the proposed "adsorption-reduction" mechanism of Cr(vi) retention by a typical black soil.