Elucidating the Composition and Transformation of Dissolved Organic Matter at the Sediment–Water Interface Using High-Resolution Mass Spectrometry

The exchange and transformation of dissolved organic matter (DOM) at the sediment–water interface are crucial factors in regulating watershed biogeochemistry, with the molecular composition of DOM serving as a pivotal determinant in elucidating this process. High-resolution mass spectrometry (HRMS) is an effective tool for resolving the composition of DOM. By analyzing the compositional characteristics of DOM at the sediment–water interface under three different salinities at the same latitude region in northern China, the findings indicate certain variations in component characteristics of DOM between low-salinity inland waters and high-salinity seawaters, with the former exhibiting greater molecular diversity and higher molecular weights, whereas the latter displayed a higher saturation and bioavailability. Notably, the presence of more CHOS substances in the low-salinity inland waters underscores the transformation of the DOM influenced by terrestrial inputs and anthropogenic activities. Conversely, the presence of more CHO and CHNO substances in high-salinity seawater underscores the microbial effects. The chemical transformation process from overlying water to pore water to sediments was characterized by methylation, hydrogenation, decarboxylation, and reduction, as determined by calculating the relations between the H/C and O/C ratios of different compound types. These findings indicate that HRMS can yield more refined results in revealing the process of DOM at the sediment–water interface under different environments, which provides a more reliable basis for a deeper understanding of the source–sink mechanism of sediment organic matter.