Release and Redistribution of Arsenic Associated with Ferrihydrite Driven by Aerobic Humification of Exogenous Soil Organic Matter

Humification of exogenous soil organic matter (ESOM) remodels the organic compositions and microbial communities of soil, thus exerting potential impacts on the biogeochemical transformation of iron (hydr)oxides and associated trace metals. Here, we conducted a 70-day incubation experiment to investigate how aerobic straw humification influenced the repartitioning of arsenic (As) associated with ferrihydrite in paddy soil. Results showed that the humification was characterized by rapid OM degradation (1-14 days) and subsequent slow maturation (14-70 days). During the degradation stage, considerable As (13.1 mg·L^-1) was released into the aqueous phase, which was reimmobilized to the solid phase in the maturation stage. Meanwhile, the low-crystalline structural As/Fe was converted to a more stable species, with a subtle crystalline phase transformation. The generated highly unsaturated and phenolic compounds and enriched <i>Enterobacter</i> and <i>Sphingomonas</i> induced ferrihydrite (∼3.1%) and As(V) reduction, leading to As release during the degradation stage. In the maturation stage, carboxylic-rich alicyclic molecules facilitated the aqueous As reimmobilization. Throughout the humification process, organo-mineral complexes formed between OM and ferrihydrite via C-O-Fe bond contributed to the solid-phase As/Fe stabilization. Collectively, this work highlighted the ESOM humification-driven iron (hydr)oxide transformation and associated As redistribution, advancing our understanding of the coupled biogeochemical behaviors of C, Fe, and As in soil.