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Abstract The impact of seasonal fluctuations linked to monsoon and irrigation generates redox oscillations in the subsurface, influencing the release of arsenic (As) in aquifers. Here, the biogeochemical control on As mobility was investigated in batch experiments using redox cycling bioreactors and As- and SO 4 2−-amended sediment. Redox potential (E h) oscillations between anoxic (−300–0 mV) and oxic condition (0–500 mV) were implemented by automatically modulating an admixture of N 2 /CO 2 or compressed air. A carbon source (cellobiose, a monomer of cellulose) was added at the beginning of each reducing cycle to stimulate the metabolism of the native microbial community. Results show that successive redox cycles can decrease arsenic mobility by up to 92% during reducing conditions. Anoxic conditions drive mainly the conversion of soluble As(V) to As(III) in contrast to oxic conditions. Phylogenetic analyses of 16S rRNA amplified from the sediments revealed the presence of sulfate and iron – reducing bacteria, confirming that sulfate and iron reduction are key factors for As immobilization from the aqueous phase. As and S K-edge X-ray absorption spectroscopy suggested the association of Fe-(oxyhydr)oxides and the importance of pyrite (FeS 2(s)), rather than poorly ordered mackinawite (FeS (s)), for As sequestration under oxidizing and reducing conditions, respectively. Finally, these findings suggest a role for elemental sulfur in mediating aqueous thioarsenates formation in As-contaminated groundwater of the Mekong delta. Graphical abstract Unlabelled Image Highlights • Microbial sulfate reduction was found to contribute to arsenic (As) sequestration. • During anoxic conditions, the conversion of soluble As(V) to As(III) was observed. • The formation of pyrite, rather than mackinawite was observed in redox cycles. • Absorption/desorption of aqueous As on Fe-(oxyhydr)oxides and pyrite was observed. [ABSTRACT FROM AUTHOR]