Arsenic (As) detoxification in polluted soils by iron-based materials can be mediated by the endogenous soil organic matter (SOM), nevertheless the mechanisms remain unclear. Herein, endogenous SOM in a paddy soil was substantially removed to understand its roles on As immobilization by biochar-supported zero-valent iron (ZVI/BC). The results demonstrated that ZVI/BC application significantly decreased As bioavailability by 64.2% compared with the control soil under the anaerobic condition. XPS and HR-TEM suggested As immobilization by ZVI/BC mainly invoked the formation of ternary complexes (i.e., As-Fe-SOM). However, SOM depletion compromised the efficacy of ZVI/BC for As immobilization by 289.8%. This is likely because SOM depletion increased the fulvic acid and OH− contents in soils. Besides, ZVI/BC increased the proportion of As(III) in available As fraction, but SOM depletion altered the mechanisms associated with As(V) reduction. That is, As(V) reduction resulted from the reductive capacity of ZVI in the pristine soil, but the As(V)-reducing bacteria contributed greater to As(V) reduction in the SOM-depleted soil. Additionally, SOM depletion boosted the abundances of Fe(III)- and As(V)-reducing bacteria such as Bacillus and Ammoniphilus in soils, which enhanced the dissimilatory arsenate reduction. Thus, this work highlighted the importance of SOM in the remediation of As-contaminated soils by ZVI/BC.
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