Algal blooms decay affects the mobility, bioavailability, and toxicity of arsenic (As) in aquatic environments. The decaying process alters aquatic redox conditions and also introduces ample organic matter, conditions favorable for microbial reduction to simulate As release and As species transformation. This study investigated the role of algae (Microcystis aeruginosa (MA)) blooms decay on the dynamics of labile As and elements associated with its release, such as iron (Fe), manganese (Mn) and sulfide (S), at the sediment-water surface (SWI) of a shallow lake (Lake Taihu) in China, applying mesocosm incubation. A combined AgI/ZrO-Chelex diffusive gradients in thin films (DGT) technology was used to examine labile As, Fe, Mn, and S variations in sediments during none-MA, low-MA, and high-MA treatments. High-MA blooms decay generated strong anoxic conditions, which are favorable for the release of labile As, Fe, Mn, and S from sediment. Labile S produced from the reduction of sulfate caused by decaying MA was likely removed by labile Fe through the formation of Fe-sulfides under reducing conditions. Furthermore, this condition facilitated arsenate (As(V)) reduction to arsenite (As(III)), which was weakly adsorbed by Fe-sulfides and thus mobilized to the aqueous phase. An increase in the sediment resupply of solids As to pore water along with MA blooms decay was also revealed by the DGT-induced fluxes in sediment model, coupled with the average desorption rate constant increasing from 0.27 × 10-6 s-1 to 3.41 × 10-6 s-1, and the average response time decreasing from 7859 s to 1538 s.