Spatial and temporal variations of Cu and Cd mobility and their controlling factors in pore water of contaminated paddy soil under acid mine drainage: A laboratory column study.

Acid mine drainage (AMD) poses a potential threat to human health worldwide, due to its high content of inorganic contaminants including heavy metals. Nevertheless, AMD is commonly used for irrigation of paddy soils. To determine the extent to which AMD affects contaminant levels in such practices, the effect of continuous AMD flooding on pH, redox potential Eh and the migration of Cu and Cd in contaminated paddy soil was studied in column experiments. By means of simulated AMD, dynamic changes of Cu and Cd concentrations in pore water were measured and the controlling factors pH, Eh and presence of Fe, dissolved organic carbon and sulfate were determined over a period of 60 days. Minerals in the soil were assessed by means of an Eh-pH diagram and solid-phase mineral detection. During continuous flooding with AMD-simulated water the soil pH increased, while Eh decreased over time. After 60 days the soil pH stabilized. Cu and Cd concentrations in the pore water negatively correlated with pH and with sulfate concentrations. Five-step sequential extraction illustrated that the fraction of exchangeable Cu increased significantly during AMD flooding. The overall content of Cu increased from initially 0.29 mg/g to 0.41 mg/g, while the content of Cd decreased from 9.2 mg/g to approximately 7.2 mg/g. Mobility factors were calculated and these conformed that Cd mobility significantly increased in contaminated soils during continuous AMD flooding. Our findings indicate that the release of Cu and Cd under AMD flooding can increase potential environmental risks, even though they lead to formation of metal sulfide deposits under anaerobic conditions. The presented data improves our understanding of the impact of overlying water conditions on the mobility of toxic metals in contaminated paddy soils.

Arsenic behavior during gallic acid-induced redox transformation of jarosite under acidic conditions.

Jarosite is an important scavenger for arsenic (As) due to its strong adsorption capacity and ability to co-precipitate metal(loid)s in acid mine drainage (AMD) environments. When subjected to natural organic matter (NOM), metastable jarosite may undergo dissolution and transformation, affecting the mobility behavior of As. Therefore, the present study systematically explored the dissolution and transformation of jarosite, and the consequent redistribution of coprecipitated As(V) under anoxic condition in the presence of a common phenolic acid-gallic acid (GA). The results suggested that As(V) incorporating into the jarosite structure stabilized the mineral and inhibited the dissolution process. Jarosite persisted as the dominant mineral phase at pH 2.5 up to 60 d, though a large amount of structural Fe(III) was reduced by GA. However, at pH 5.5, jarosite mainly transformed to ferrohexahydrite (FeSO4·6H2O) with GA addition, while the principal end-product was goethite in GA-free system. The dissolution process enhanced As(V) mobilization into aqueous and surface-complexed phase at pH 2.5, while co-precipitated fraction of As(V) remained dominant under pH 5.5 condition. Result of XPS indicated that no reduction of As(V) occurred during the interaction between GA and As(V)-bearing jarosite, which would limit the toxicity to the environment. The reductive process involved that GA promoted the dissolution of jarosite via the synergistic effect of ligand and reduction, following by GA and release As(V) competing for active sites on mineral surface. The findings demonstrated that phenolic groups in NOM can exert great influence on the stability of jarosite and partitioning behavior of As(V).