Geochemistry and release risk for nutrients in lake sediments based on diffusive gradients in thin films

A comprehensive understanding of the mobility of both nitrogen (N) and phosphorus (P) and the inter-relationships between P, N, and iron (Fe) in sediments is important for controlling the "internal loadings" of nutrients in lakes. In this research, diffusive gradients in thin film (DGT) assemblies with binding layers (ZrO-AT, chelex, and ZrO) were designed for PO₄-P, Fe, ammonium (NH₄-N), and nitrate (NO₃-N) at sediment/water interface (SWI) in Western Lake Taihu (China). The biogeochemical processes of N and P related to the physicochemical properties, the dynamic P transfer, the distribution characteristics of P microniches, and the estimation of the release risks in sediments in Western Lake Taihu were simultaneously revealed by the passive sampling technique-DGT with the high spatial resolutions (millimeter and sub-millimeter). Based on DGT concentration (C_DGT) related to physicochemical properties in sediments, (1) P biogeochemical reactions included P release from Fe-bound P during Fe reduction, algae biomass decomposition, and phosphatase enzyme activity increased by NH₄-N; (2) denitrification and dissimilatory nitrate reduction to ammonium (DNRA) led to exchangeable ammonium (NH₄ex) enrichment and NH₄-N release; anammox depleted NH₄-N transfer; organic matter (OM) mineralization favored NH₄-N release; and (3) aerobic nitrification led to NO₃-N remobilization; denitrification and DNRA reduced NO₃-N release. Redox status, OM, Fe, aluminum, or calcium influenced mobilization of nutrients. The numerical model of DGT-induced fluxes in sediments was used for dynamic P transfers with resupply types ("slow" ~ "fast") controlled by labile P pool, resupply constant, response time, and Dspt rate. The formation of P microniches in two dimensions was revealed. Sediment P release risk index (0.49 ~ 36.85 [lg (nmol cm^-3 d^-1)]) with "light" ~ "high" risks and diffusive fluxes across SWI (µg m^-2 d^-1) of 15.0 ~ 639 (PO₄-P), - 1403 ~ 5010 (NH₄-N), and - 1395 ~ 149 (NO₃-N) were derived and lake management strategies were provided. The DGT technique provides the characterization of the mobilization of nutrients and evidence for biogeochemical processes at the fine spatial scales for control of internal loadings in sediments.