Eutrophication and watershed characteristics shape changes in dissolved organic matter chemistry along two river-estuarine transects

Dissolved organic matter (DOM) plays a crucial role in the coastal carbon cycle. However, eutrophication-induced algal blooms and lateral transport from connected tidal marshes may significantly affect DOM cycling, which remains poorly understood. By combining a suite of bulk and optical techniques, and the Fourier transform ion cyclotron resonance mass spectrometry and ion mobility quadrupole time-of-flight mass spectrometry, we determined DOM concentration and composition along two typical river-estuary transects (namely Liao and Daliao rivers), Northeast China, with contrasting eutrophic state and distribution of tidal marshes. The Daliao River is characterized by a higher eutrophication degree and is surrounded with lower reed coverage than the Liao River. Compared to the Liao River, significantly higher dissolved organic carbon concentrations were observed in the Daliao River, where higher stable carbon isotope (δ13C) values and protein-like fluorescent components, characterized relatively higher autochthonous DOM. Further molecular analysis revealed higher peptide and sugar-like compounds but lower isomeric percentages of several molecular formulas in the Daliao River, suggesting higher molecular lability but lower isomeric complexity than the Liao River. Associations between optical and molecular signatures among all DOM samples revealed that a red-shifted humic-like C3 component was significantly correlated with molecular formulas with lower molecular weight and aromaticity, and higher H/C, indicating that C3 was likely a result of phytoplankton production coupled with further heterotrophic processing. Moreover, we found that reed marshes could introduce to both rivers a series of carboxylic-rich alicyclic compounds, highly unsaturated compounds, and polyphenols with high molecular weight and low H/C. This study suggests that eutrophication and reed marsh affect the DOM quality and can be a potential source of recalcitrant DOM compounds to coastal rivers and estuaries, which warrants further investigations considering the increasing worldwide eutrophication and sea-level rise in coastal delta environments.