Electron Transfer-Mediated Heavy Metal(loid) Bioavailability, Rice Accumulation, and Mitigation in Paddy Ecosystems: A Critical Review

Electron transfer (ET) is a foundational biogeochemical process in paddy soils, distinctively molded by alternating anaerobic-aerobic conditions from flooding-drainage cycles. Despite extensive research on heavy metal(loid) (denoted as “HM”, e.g., As, Cd, Cr, Hg) dynamics in paddies, ET has not been systematically synthesized as a unifying regulatory mechanism, and the trade-offs of ET-based mitigation strategies remain unclear. These critical gaps have drastically controlled HMs’ mobility, which further modulates bioavailability and subsequent accumulation in rice (Oryza sativa L., a staple sustaining half the global population), posing substantial food safety risks. Alongside progress in electroactive microorganism (EAM) research, extracellular electron transfer (EET) mechanism delineation, and soil electrochemical monitoring, ET’s role in orchestrating paddy soil HM dynamics has garnered unparalleled attention. This review explicitly focuses on the linkage between ET processes and HM biogeochemistry in paddy ecosystems: (1) elucidates core ET mechanisms in paddy soils (microbial EET, Fe/Mn/S redox cycling, organic matter-mediated electron shuttling, rice root-associated electron exchange) and their acclimation to flooded conditions; (2) systematically unravels how ET drives HM valence transformation (e.g., As(V) to As(III), Cr(VI) to Cr(III)), speciation shifts (e.g., exchangeable Cd to oxide-bound Cd), and mobility changes; (3) expounds on ET-regulated HM bioavailability by modulating soil retention capacity and iron plaque formation; (4) synopsizes ET-modulated HM accumulation pathways in rice (root uptake, xylem/phloem translocation, grain sequestration); (5) evaluates key factors (water management, fertilization, straw return) impacting ET efficiency and associated HM risks. Ultimately, we put forward future avenues for ET-based mitigation strategies to uphold rice safety and paddy soil sustainability.