Dual diffusive gradients in the thin films (DGT) probes provide insights into speciation and mobility of sediment chromium (Cr) from the Xizhi River basin, South China

Investigation of the speciation and remobilization mechanisms of chromium (Cr) in sediment is essential for accurate estimation of its ecological risks in aquatic systems. In this work, a three-step chemical extraction procedure and diffusive gradient in thin films (DGT) technique were combined to investigate the geochemical speciation, mobility potentials, and release characteristics of sediment Cr. The geochemical speciation of sediment Cr decreased in the following order: oxidizable > reducible > residual > acid-soluble fraction. Dissociation of OM-bound Cr(III) and oxidation by Mn oxides contributed to higher labile Cr(III) and Cr(VI) levels in winter, with the labile Cr(III) being the dominant species and accounting for 48.1%65.5% of the total concentration of labile Cr; whereas, reductive dissolution of Mn oxides was responsible for the remobilization of labile Cr(VI) in summer, leading to a shift in dominant Cr species to Cr(VI) (48.9%65.7%) due to rapid precipitation of Cr(III). Sediment acted as a major sink for labile Cr(VI) in two sampling campaigns. For labile Cr(III), sediment converted from source in winter to sink in summer. The diffusive release of labile Cr(III) deserves preferential concern due to its potential to be re-oxidized to more toxic Cr(VI) under the oxic conditions of river water in winter.