Time-dependent redistribution of soil arsenic induced by transformation of iron species during zero-valent iron biochar composites amendment: Effects on the bioaccessibility of As in soils.

Zero-valent iron biochar composites (ZVI/BC) are considered as effective amendments for arsenic (As)-contaminated soils. However, the mechanisms of transformation of various soil As species during ZVI/BC amendments remain unclear. This study investigated As transformation in four soils (namely, GX, ZJ, HB, and HN) treated with ZVI/BC for 65 days under two soil moisture conditions, unsaturated and oversaturated. Results showed that the 65-day treatment was divided into two stages based on the variation of labile As content. Within 2 days (stage 1), ZVI/BC addition quickly reduced labile As content by 5.91-90.3 % in soils under unsaturated conditions. During days 2-65 (stage 2), labile As ultimately decreased by 0.06-0.31 mg/kg in GX, ZJ, and HB while increasing by 22.1 mg/kg in HN soil, due to its lower pH value and Fe content. The variations of labile As were attributed to changes in multiple Fe minerals and associated As species. In stage 1, the corrosion of ZVI/BC generated amorphous Fe oxides to immobilize labile As, resulting in the accumulation of meta-stable As. In stage 2, amorphous Fe oxides were transformed into crystalline Fe oxides, resulting in the release and re-precipitation of As along with transformation, thus redistributing immobilized As into labile and stable As, which was evidenced by multiple methods, including chemical extraction, XRD, and TEM-EDX. The elevated soil moisture condition would enhance the corrosion of ZVI/BC in stage 1, further forming a reductive environment to facilitate the transformation of Fe minerals in stage 2. Besides, As bioaccessibility in soils was reduced by 10.8-38.7 % after ZVI/BC treatment in in-vitro gastrointestinal simulations. Overall, our study revealed the time-dependent transformation mechanism of soil As species and associated Fe minerals under different soil moisture with ZVI/BC treatments, and highlighted the effectiveness of ZVI/BC as a long-term amendment for As-contaminated soils.