In situ high-resolution measurement of phosphorus, iron and sulfur by diffusive gradients in thin films in sediments of black-odorous rivers in the Pearl River Delta region, South China

The cycling of phosphorus (P), iron (Fe) and sulfur (S) in sediments has been previously investigated, but its impacts on the formation of black-odorous waterbodies remains unclear. Here, high-resolution (i.e., 2 mm for P and Fe, and 0.042 mm for S of 2D presentation) simultaneous measurements of P, Fe, and S profiles in river sediments based on the diffusive gradients in thin-films (DGT) technique were conducted in the Pearl River Delta region, South China. Similar distribution trends and significant positive correlations (R = 0.67-0.93, p < 0.01) were observed between Fe and P. Considering the high diffusion fluxes of Fe and P together, it revealed that P release was promoted by the Fe reduction. The two-dimensional labile S profiles showed that their concentrations in sediments were higher by factors of 1.6-20 than those in overlying water. The minor diffusion fluxes of S and the accumulation of acid volatile sulfide indicated that S^2- combining with Fe²⁺ occurred prior to diffusion. Furthermore, the formation mechanisms of black-odorous waterbodies were explored: (i) oxygen depletion by COD and NH₄⁺‒N and large amounts of sulfate input were the main exogenous driving factors. (ii) Reduction of Fe and S to form ferrous sulfide accompanied with P release in sediments were the dominant endogenous causes. These observations together with mechanism analysis can provide a basis for the governance of black-odorous rivers.