Effects of freeze-thaw action on in vivo and in vitro bioavailability of arsenic in soils from derelict industrial sites.

Arsenic is a metalloid with carcinogenic properties and has been classified as a Category I carcinogen by the International Agency for Research on Cancer (IARC). Freeze-thaw processes affect the migration and transformation of soil heavy metals, as well as adsorption/desorption and redox reactions. However, there is limited research directly addressing the impact of freeze-thaw processes on the bioavailability of soil heavy metals. In this study, we focused on As and selected As-contaminated soil samples from three types of legacy sites in heavy industrial areas. Under controlled freeze-thaw experimental conditions, we utilized both in vivo and in vitro bioavailability measurement methods to investigate whether and how freeze-thaw processes affect the bioavailability of soil As. The results of this study showed that freeze-thaw processes reduced soil pH (P < 0.05), CEC, SOM, and particle size, with decreases of 0.33, 1.2 cmol/kg, 5.2 g/kg, and 54 µm, respectively. It also increased weight specific surface area (BET) (P < 0.05), with an increase of 300 m/kg. Freeze-thaw processes increased the proportions of exchangeable (P < 0.05), carbonate-bound, and iron-manganese oxide-bound As (P < 0.05), but reduced the proportions of organic-bound and residual As (P < 0.05). Freeze-thaw processes significantly increased the relative bioavailability and bioaccessibility of As, with increases of 32 ± 9.6% and 13 ± 0.23%, respectively. Soil pH, SOM, BET and electronic conductivity (EC) were identified as factors which could contribute to the increased bioavailability of As due to freeze-thaw processes. These results provide new insights and evidence for refining the assessment of human health risks associated with heavy metal contamination in polluted soils.