The influence of pH, co-existing ions, ionic strength, and temperature on the adsorption and reduction of hexavalent chromium by undissolved humic acid

Abstract

The retention of Cr(VI) in subsurface environment is highly dependent on humic acid (HA), however, the undissolved form is poorly investigated, the amount of which can be of two magnitude higher compared with the dissolved one in soils and sediments. In this study, the effects of time, initial concentration, pH, ionic strength, ion species and temperature on the adsorption and reduction respective processes by undissolved self-extracted peat soil HA from Northeast China (EHA) and from Sigma Aldrich (CHA) were investigated by batch experiments. Cr(VI) removal rates by EHA were higher than CHA and the maximum Cr(VI) removal amount for EHA and CHA were 0.77 (±0.01) and 0.61 (±0.02) mmol/g. Of these, 98% and 54% were reduced to Cr(III) by EHA and CHA respectively, which were related to the phenolic group content of HA. With time, the adsorbed Cr(VI) on HA increased to a maximum level (equilibrium) beyond which Cr(VI) reduction dominated the removal process. Cr(VI) adsorption and reduction by undissolved HA increased as pH decreased. Co-existing ion species had varying effect on Cr(VI) adsorption and indirectly on reduction especially divalent cations which was suggestive of cation bridging between Cr anions and ionized carboxyl group of HA. The positive effect of ionic strength (Ca2+) on Cr(VI) adsorption through complexation corroborated the cation bridge effect of divalent cations. Temperature increased both Cr(VI) adsorption (complexation) and reduction with enhancing reduction rate constants and partitioning. ΔHo, ΔSo, and ΔG⁰ parameters showed that Cr(VI) adsorption and reduction processes were endothermic, irreversible and spontaneous.