Compositional changes and molecular transformations of dissolved organic matter during the arctic spring floods in the lower Churchill watershed (Northern Manitoba, Canada)

The spring flood season in Northern aquatic systems is characterized by rapid changes in river discharge and fluxes of organic and inorganic species, yet remains under sampled. In this study, we examine the molecular characteristics and transformations of dissolved organic matter (DOM) during the Arctic spring season at three locations in the lower Churchill River watershed. Characteristics including dissolved organic carbon concentrations, optical properties (i.e. absorbance and, excitation-emission matrix fluorescence coupled with parallel factor analysis, EEM-PARAFAC) and molecular characterization using high resolution mass spectrometry (HR-MS) were assessed. As spring floods progressed, a significant reduction in DOM spectral slope (S₂₇₅₋₂₉₅) and an increase in absorbance (a₂₇₀) were observed suggesting an increase in DOM molecular weight and concentrations at all sampled locations. A maximum in HR-MS lignin-class compounds coincided with peak flow at all sampled locations, further validated with an increase in PARAFAC humic-like components and a minimum in S₂₇₅₋₂₉₅. Principal component analyses revealed that both protein and aromatic humic-like material measured by HR-MS and EEM-PARAFAC, respectively, were significantly correlated (ANOVA, p < 0.05), demonstrating similarities in both techniques. Based on network analysis of HR-MS assigned formula, the highest peak flow day was characterized by a maximum in homologous DOM of C₂H₂O and C₂H₄ additions, suggesting structural similarities in newly deposited lignin and humic material. Overall, the progression of the spring freshet shifted the lower Churchill River watershed from an environment rich in proteins and lipids to an aquatic system more abundant in lignin, aromatic and humic DOM.