Sulfate-driven phosphorus mobilization in river sediments: Fe-S-P coupling modulated by sediment geochemistry

Sulfate-driven mobilization of endogenous phosphorus (P) in sediments drives eutrophication, but its biogeochemical mechanisms and environmental regulators remain incompletely understood. This study conducted controlled batch experiments with varied carbon sources, redox conditions, and sediment geochemistry to clarify the pathways and regulators of sulfate-driven endogenous P release. Results showed that sulfate reduction mobilizes sediment P via iron-sulfur-phosphorus (Fe-S-P) coupling, involving both biogenic sulfide-driven reductive dissolution of Fe(III) oxides-bound P (BD-P) and microbial mineralization of organic P (NaOH-NRP). Carbon sources critically regulated this process. Acetate maximized P release by intensifying sulfate reduction and sulfide-driven Fe(III) oxide dissolution, although excessive sulfide accumulation may inhibit microbial activity. Conversely, glucose triggered sequential Fe(III) reduction followed by sulfate reduction, promoting competitive P re-immobilization and yielding lower P release despite greater sulfate depletion. Oxalate minimized P mobilization by inhibiting both sulfate and Fe(III) reduction. Redox conditions also acted as a potent regulator, as aerobic conditions decreased P release by 89.5 % relative to anaerobic conditions via Fe(III) regeneration. Repeated redox cycles attenuated P release due to reactive iron depletion. Importantly, sediment geochemistry (e.g., the degree of P saturation (DPS), reactive oxide content (Fe_ox/Al_ox), and labile P fractions) was the primary control on P mobilization efficiency and pathways. These findings establish Fe-S-P coupling as the central mechanism of sulfate-induced sediment P release, providing a basis for assessing and managing internal P loading in sulfate-affected aquatic ecosystems.