Mechanism and multi-step kinetic modelling of Cr(VI) adsorption, reduction and complexation by humic acid, humin and kerogen from different sources

Humin (HM) and kerogen (KG) are widespread in soils and sediments, which have strong retention effects on the migration and transformation of Cr(VI) in subsurface environment. Previous studies mainly focused on the interaction between Cr(VI) and soluble organic matter, such as humic acid (HA); however, the adsorption and reduction mechanism for Cr(VI) by insoluble HM and KG are still unclear, the processes of which might be quite different from HA due to their different sources and humification degrees. Consequently, in this study, HA, HM and KG extracted from different sources were used to explore the adsorption, reduction and complexation mechanisms of Cr(VI) in soils and sediments, based on which a multi-step kinetic model of Cr(VI) was carried out. According to the results, the retention of Cr(VI) by humus was found to obey a coupling mechanism of "adsorption-reduction-complexation", where Cr(VI) adsorption was by complexation with carboxylic groups by ligand exchange. The phenolic and hydroxylic groups were determined to be the main electron donor for Cr(VI) reduction. Notably, the Cr(III) produced was found to be adsorbed on the surface of humus by complexation on phenolic and hydroxylic groups, and the excesses were released into the liquid phase after the saturation of complexation sites. Based on the revealed mechanism, a multi-step kinetic model for simultaneously describing Cr(VI) adsorption and reduction and behaviour of Cr(III) was proposed producing a better fitting performance (R-2 >= 0.984) than the first-order and second-order kinetic models (R-2 <= 0.84 and 0.87, respectively) and hence could provide more factual understanding of Cr(VI) transformation in soils and sediments enriched in various types of humus.