Characterization of dissolved organic matter/nitrogen by fluorescence excitation-emission matrix spectroscopy and X-ray photoelectron spectroscopy for watershed management

Characterization of dissolved organic matter/nitrogen (DOM/DON) is critical in water quality assessment and nutrient management in watershed or ecosystem. This study was to investigate the link between DOM/DON and its source using fluorescence excitation-emission matrix (EEM) spectroscopy coupled with parallel factor analysis (PARAFAC). Water samples were collected from various aquatic systems in a watershed located in central Missouri, including rural watershed with various land use and land cover (LULC), landfill, and constructed wetland. PARAFAC results based on EEM spectroscopy revealed four DOM components: two humic/fulvic acid-like components, one xenobioic-like component, and one protein-like component (f4). The f4 score was found highly correlated to LULC, indicating its distinctive EEM structure in relation to source. It is believed that the f4 score could be used as a surrogate for DOM/DON source-tracking in complex ecosystems. The nitrogen 1s X-ray photoelectron spectroscopy (XPS) of the solid DOM showed a close relationship between N oxidation state and its origin. The classification of the sample origins by the N oxidation state confirmed the grouping by the f4 score of EEM/PARAFAC. This study demonstrated that EEM/PARAFAC could be used as a tool for DOM/DON source tracking, point or non-point source pollution control, and understanding of DOM/DON fate and transport in complex aquatic ecosystems.