Kinetic characteristics of mobile Mo associated with Mn, Fe and S redox geochemistry in estuarine sediments.

Estuarine sediments are crucial repositories and incubators of molybdenum (Mo) during its transport from rivers to the ocean. Here, Mo mobility and related processes in estuarine sediments were explored using high-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) techniques. Better correlations were observed between dissolved Mn and Mo than between dissolved Fe and Mo, implying that Mn geochemistry plays a key role in dissolved Mo mobility via molybdate adsorption onto abundant Mn oxides and its substantial release upon intense Mn reduction. As a result, oxic intertidal sediments functioned as Mo sinks, and anoxic subtidal sediments functioned as Mo sources. The opposite vertical distributions between DGT-Labile S and DGT-Labile Mo indicated that the availability of labile Mo can be blocked by aqueous sulfide. However, the corresponding high concentrations of DGT-Labile S and dissolved Mo at subtidal sites demonstrated that the abundant dissolved Mo remobilized via Mn reduction was not effectively solidified by sulfide. Simulation with the DIFS model further verified that redox conditions and induced physicochemical processes are crucial factors controlling Mo mobility, with relatively low dissolved Mo concentrations but an adequate and steady resupply capacity of the bioavailable molybdate in intertidal sediments.