Unraveling the photochemical reactivity of dissolved organic matter in the Yangtze river estuary: Integrating incubations with field observations.

Dissolved organic matter (DOM) sustains a substantial part of the organic matter transported seaward in large estuaries, where photochemical reactions significantly influence its transformation and fate. Irradiation experiments can provide valuable information on the photochemical reactivity (photo-labile, photo-resistant, and photo-product) of molecules. However, previous research paid less attention to exploring the controls of the initial DOM chemistry to irradiation experiments and examining the applicability of their further integration with field research. Here, we conducted irradiation experiments for samples from the freshwater and seawater endmember of the Yangtze River Estuary (YRE), which receives organic matter transport from the largest river in China, the Yangtze River. Molecules that occurred before and after irradiation experiments were characterized by the Fourier transform ion cyclotron resonance mass spectrometry. Results show that both post-irradiation samples have the lower aromaticity degree and reduced oxidation state, while the freshwater endmember sample exhibits more dramatic changes, indicating the controls of parent molecules to the effect of irradiation experiments. Integrating with the "molecular matching" approach, we compared the molecules occurring in field samples with the classified molecules (photo-resistant, photo-labile, and photo-product) acquired from performed irradiation experiments and correlated the relative intensity of photochemical reactivity types with salinity. When applying results from different experiments to conduct "molecular matching", the photo-resistant and photo-labile relative intensity possess consistently positive and negative trends with increasing salinity, respectively. This suggests their reliability for molecular matching applications, while the inconsistent trends for the photo-product relative intensity with salinity suggest its uncertainty in assessing the photo-induced effects. Moreover, the molecular composition within the photochemical reactivity types in field samples also evolved along the salinity gradient and showed similar trends with the DOM changes after experimental irradiation. Despite various factors influencing estimations, it is revealed that a fraction of aromatic molecules and majority of carboxyl-rich alicyclic molecules considered with biologically persistent nature in the YRE freshwater zone are simultaneously not susceptible to photochemical transformation to potentially constitute a long-term marine carbon sink. This study emphasizes the importance and limitations of the combination of field research and laboratory-controlled experiments to provide a better understanding of the crucial role of photochemical reactions in affecting carbon cycling in large estuaries.