Spatiotemporal dynamics of dissolved organic matter in subtropical karst cave waters identified by optical properties

Natural dissolved organic matter (DOM) is ubiquitous in aquatic environments and is an essential component in the carbon cycle in karst areas. To improve understanding of the carbon cycle in karst caves with heterogeneous hydrological processes, we examined the spatiotemporal variability of DOM composition and further uncovered its source and fate. Results may also provide insights into the feedbacks of organic carbon to carbon sinks in karst regions. In this study, concentrations and compositions of DOM, partial pressure of aqueous carbon dioxide (pCO2), dissolved inorganic carbon, and other physicochemical parameters were investigated in a karst cave at Mahuang, Southwest China. Ultraviolet-visible absorption spectroscopy was coupled with multiple statistical analyses to identify the compositional variations and potential fates of DOM in cave waters. The results showed that DOM dynamics were regulated by both terrigenous and biogenic drivers under the control of meteorological conditions. With higher air temperature, precipitation, and microbial activity, fulvic fractions were consumed to generate CO2, leading to the accumulation of refractory DOM in cave waters and changing the hydrochemical features. When temperature and precipitation decreased, DOM was dominated by lignin fractions, which served as an indicator of terrestrial inputs and vascular plants, suggesting variation in the preferential fraction of biological consumption. In addition, different hydrological path patterns influenced DOM properties in cave waters due to differences in recharging, the leaching process, and subsurface reworking. Thus, hydrology could serve as an important constraint on the coupling between dissolved organic and inorganic carbon.