Differential Adsorption of Dissolved Organic Matter and Phosphorus on Clay Mineral in Water-Sediment System.

ABSTRACT

Lake sediments connection to the biogeochemical cycling of phosphorus (P) and carbon (C) influences streamwater quality. However, it is unclear whether and how the type of sediment controls P and C cycling in water. Here, the adsorption behavior of montmorillonite (Mt) with different interlayer cations (Na+, Ca2+, or Fe3+) on dissolved organic matter (DOM) and P was investigated to understand the role of Mt in regulating the organic carbon-to-phosphate (OC/P) ratio within freshwater systems. The adsorption capacity of Fe-Mt for P was 3.2-fold higher than that of Ca-Mt, while it was 1/3 lower for DOM. This dissimilarity in adsorption led to an increased OC/P in Fe-Mt-dominated water and a decreased OC/P in Ca-Mt-dominated water. Moreover, an in situ atomic force microscope and high-resolution mass spectrometry revealed molecular fractionation mechanisms and adsorptive processes. It was observed that DOM inhibited the nucleation and crystallization processes of P on the Mt surface, and P affected the binding energy of DOM on Mt through competitive adsorption, thereby governing the interfacial P/DOM dynamics on Mt substrates at a molecular level. These findings have important implications for water quality management, by highlighting the role of clay minerals as nutrient sinks and providing new strategies for controlling P and C dynamics in freshwater systems.