Flooding and drainage induced abiotic reactions control metal solubility in soil of a contaminated industrial site

Intense industrialization has led to the increasing leaching risk of metals into groundwater at heavily polluted industrial sites. However, metal dissolution in polluted industrial soils has been neither fully investigated nor quantified before. In this study, the dissolution of Zn, Ni, and Cu in soil from a heavily contaminated industrial site during a flooding-drainage period was investigated by sequential extraction, geochemical modelling, and X-ray absorption near edge structure spectroscopy. The results showed a steady decrease in metal solubility during both reduction and oxidation stages. During reduction, with limited decrease in Eh (>100 mV), formation of carbonate precipitates rather than sulfide precipitates and adsorption on soil solids was responsible for Zn and Ni dissolution, whereas bound to soil organic matter (SOM) and iron oxides dominated Cu dissolution, due to its lower concentration and higher affinity to SOM and iron oxides compared to Zn and Ni. During oxidation, the acidity caused by ferrous oxidation was buffered by calcite dissolution, while metal precipitation ceased and adsorption on soil surface controlled metal solubility. The metal solubility and speciation during the flooding-drainage process were quantitatively predicted by geochemical model. The findings demonstrate that due to high metal concentrations and weak microbial effect in the industrial soil, metal release was largely regulated by abiotic reactions rather than biotic reactions, which is somehow different from that of the wetland or rice field soils.