Optical properties and molecular compositions of dissolved organic matter in multiple runoff components during rainfalls on the karst hillslope

Understanding the chemical composition, origin, and molecular structure of dissolved organic matter (DOM) in multi-interface runoff is essential for comprehending the fate of laterally transported DOM in complex soil-epikarst systems of karst hillslopes. Limited information, however, is available for the optical properties and molecular compositions of the transported OM in multiple runoff components on the karst hillslope in relation to land-uses and soil thicknesses. In this study, we conducted a study to observe the changes in the quantity and quality of DOM in multiple interface flow (surface, subsurface, and epikarst) during natural rainfall events in 2022 in karst hillslopes that are covered by different land uses (cropland and shrubland) and soil thicknesses (with mean depths of 66.0 cm for deeper soil and 35.4 cm for shallower soil) in the karst region of southwest China. chemcial compositions of runoff DOM were determined by optical analysis and microbial compositions in runoff were inferred with high-throughput sequencing. The results showed that the soil-epikarst structure was controlling the runoff DOM quantity and quality during rainfall events. A decrease in the aromaticity, humification, unsaturation, and oxidation degree and an increase in carbohydrate, aminosugars, protein, and lipid compounds were found from surface to epikarst flow, indicating that plant-and soil-derived carbon decreased, while the microbially-derived carbon increased. The results were further comfirmed by the higher bacterial richness and diversity, along with fungal diversity in the epikarst flow compared to other runoff components. The bio-labile protein materials (C2) were the most important component of runoff DOM output in karst hillslopes. In surface and subsurface flow, rainfall amount, runoff rate, and discharge significantly affected the DOM concentration and quality during rainfalls, indicating that the dynamics of DOM in runoff from karst hillslopes were predominantly influenced by hydrological processes. Furthermore, the runoff DOM quality in cropland was dominated by lower unsaturation and oxidation degrees and higher protein component, compared to those in shrubland. The compositions of DOM in runoff from hillslope plots with thicker soils were primarily characterized by microbially-derived materials. Our findings were conducive to understanding the mechanism governing the migration of DOM quality and quantity in discharge during multi-interface hydrological processes on karst hillslopes.