Driving factors of colored dissolved organic matter dynamics across a complex urbanized estuary

The role of estuaries in sourcing and transforming dissolved organic matter - the largest reservoir of organic carbon in the ocean - still presents many unknowns for coastal biogeochemical cycles, and is further complicated by increasing human pressures and a changing climate. Here, we examined the major drivers of colored dissolved organic matter (CDOM) dynamics in Long Island Sound (LIS), a heavily urbanized estuary of National Significance with a storied water quality past. A comprehensive new optical dataset, including measurements of CDOM absorption and fluorescence signatures, was integrated with biological and hydrological measurements to capture the spatiotemporal heterogeneities of LIS, including its urban-to-rural gradient, dynamic river mouths, and blue carbon ecosystems across seasons, following episodic storm events, and over five years. Results reveal longitudinal gradients in both DOM amount and quality. While carbon-rich and humic terrigenous DOM was dominant in the heavily riverine-influenced Central to Eastern LIS, an uncoupling between CDOM absorption (a_CDOM) and dissolved organic carbon (DOC) concentration in Western LIS, and a stronger correlation with Chlorophyll-a, indicated increased autochthonous CDOM production. Closer to the New York City urban core, a_CDOM was highly correlated to turbidity, consistent with increased wastewater influences. Fluorescence PARAFAC analysis provided strong evidence for seasonal processing of CDOM in LIS, related to increased summertime photochemical degradation of humic-like components and shoulder-season microbial processing. Riverine CDOM export was influenced by discharge amount, residence time, and coastal wetlands acting as additional sources of strongly humic and aromatic organic matter. These measurements allowed us to assess how hydrologic, biological, and anthropogenic processes impact DOM dynamics and, subsequently, biogeochemical variability and trophic status in this complex urbanized estuary, with implications for water quality management and policy. Results discussed here are applicable beyond LIS, as urbanized estuaries globally face similar hydrological and anthropogenic forcings.