The redox behavior of iron (Fe) significantly impacts the biogeochemical cycle of arsenic (As), with iron minerals serving as major reservoirs for phosphate (P). The cycle of As inherently associates with its species. However, the effect of Fe
P coupling on As species in lake sediments remain largely unknown, especially during the ice-bound period. The novelty of this study is to explore the effect of Fe
P coupling on As speciation during an ice-bound period using PLS-SEM model based on As、Fe and P species as well as environmental factors monitoring in sediments. Our findings revealed that Fe
P coupling accounts for 95.7 % of As speciation variability, playing a pivotal role in As transformation and partitioning, particularly in labile As pool that contained adsorbed As, moderately labile As pool that closely related to iron species, and pyrite-coprecipitated As. The significant influence of Fe
P coupling on the reductive transformation and re-distribution of amorphous and crystalline iron oxides, which in turn affects As adsorption-desorption processes. This interaction subsequently influences the speciation of Fe and P, as well as the release and ecotoxicity of As. Notably, exchangeable phosphorus, iron-bound P fraction and organic P fraction (OP) were identified as the primary P species mediating the effects of Fe
P coupling on As speciation. Interesting, OP also play the major role in the effect of Fe
P coupling on As species, potentially releasing As adsorbed on crystalline Fe hydroxides during organic matter mineralization. Results emphasize the importance of Fe(hydro)oxides and P in controlling As partitioning, with iron (hydro)oxides being particularly critical in P behavior and its interaction with As. This work provides insights into the cycling of As and the enrichment of P and As in sediment-water systems, providing a reference for environmental monitoring and remediation in sedimentary environments facing dual risks of As pollution and eutrophication.
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