Linking the unique molecular complexity of dissolved organic matter to flood period in the Yangtze River mainstream.

Large rivers transport a significant amount of terrestrially derived dissolved organic matter (DOM) to coastal oceans, consisting of a critical component of the global biogeochemical cycle. Although high flow events usually introduce more terrestrial DOM than baseflow, the underlying molecular complexity and lability of DOM during high discharge are not well constrained, especially in large river ecosystems. By combining ultraviolet and fluorescent spectroscopy, and ultrahigh-resolution mass spectrometry, we found that stronger terrestrial DOM signal was detected during high discharge than normal discharge in the Yangtze River mainstream. The averaged DOC concentration was higher during high discharge than normal discharge. Optical properties confirmed higher aromaticity and relatively higher humic-like fluorescent components in DOM during high discharge. The molecular composition showed significantly higher molecular complexity, averaged molecular weight, aromaticity, relative abundances of polyphenols and highly unsaturated compounds of DOM during high discharge than normal discharge. A large set of unique molecular formulae (up to 4927) was only detected during high discharge. These unique molecular formulae were mostly lignin degradation products, likely due to more intensive soil leaching during high discharge. By comparing with incubation experiments and the Yangtze River mouth and East China Sea DOM molecular composition, some of these unique molecular formulae during high discharge are resistant to both bio- and photo-degradation, and persist during their transport to the East China Sea. Therefore, we suggest that high discharge will additionally introduce a relatively recalcitrant pool of DOM into the Yangtze River mainstream and persist during its journey to the ocean. Considering the projected increase of flood frequency, this study provides a preliminary foundation for further studies to better assess the underlying mechanisms how hydrology affect the biogeochemical cycling of DOM in large rivers.