Linkages Between Optical and Molecular Signatures of Dissolved Organic Matter Along the Yangtze River Estuary-to-East China Sea Continuum

Changes in the molecular composition of dissolved organic matter (DOM) and its light-absorbing component (CDOM) along the river–coastal ocean continuum are crucial for better understanding the source and fate of DOM in coastal oceans. Both optical (absorbance and fluorescence) techniques and ultrahigh-resolution mass spectrometry have been widely used to trace DOM cycling. However, to the best of our knowledge, the linkage between these two techniques is rarely investigated along the river–coastal ocean continuum. In this regard, bulk characterization, optical techniques, and ultrahigh-resolution mass spectrometry [Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS)] were applied to determine the DOM chemistry along a spatial transect from the Yangtze River Estuary (YRE) to the East China Sea. The results showed that DOM in the YRE was mainly controlled by the mixing of freshwater and seawater. Besides terrestrial input, multiple sources (tributary input from the Huangpu River, wastewater input, and sediment resuspension and subsequent release at the turbidity maximum zone) have been identified. In addition, the linkages between CDOM and thousands of formulas were developed based on Spearman’s rank correlations between optical parameters and FT-ICR MS peaks. The linkages showed that the molecular groups associated with the optical parameters generally agreed with conventional biogeochemical interpretations. Nevertheless, each technique has its unique advantage and weakness in interpreting DOM composition. Therefore, the combination of the untargeted FT-ICR MS approach and optical techniques could be valuable for studying the DOM sources and transformation in large river estuarine systems.