Willow Slough, a seasonally irrigated agricultural watershed in the Sacramento River valley, California, was sampled synoptically in order to investigate the extent to which dissolved organic carbon (DOC) concentrations and compositions from throughout the catchment are represented at the mouth. DOC concentrations ranged from 1.8 to 13.9 mg L⁻¹, with the lowest values in headwater 1st and 2nd order streams, and the highest values associated with flood irrigation. Carbon-normalized vanillyl phenols varied from 0.05 to 0.67 mg 100 mg OC⁻¹ (0.37 mean), indicative of considerable contributions from vascular plants. DOC concentrations and compositions at the mouth appear to be primarily influenced by land use (agriculture) in the lower reaches, and therefore very little of the headwater chemistry (1st and 2nd order streams) can be discerned from the chemistry at or near the mouth (3rd and 4th order streams), indicating the need for synoptic sampling to capture the breadth of organic carbon cycling within a catchment. Field sampling during irrigation showed the large impact that flood irrigation can have on DOC concentrations and compositions, likely a primary cause of significantly elevated Willow Slough DOC concentrations during the summer irrigation season. Optical proxies exhibited varying degrees of correlation with chemical measurements, with strongest relationships to DOC and dissolved lignin (r² = 0.95 and 0.73, respectively) and weaker relationships to carbon-normalized lignin yields and C:V (r² from 0.31 to 0.42). Demonstrating the importance of matching scale to processes, we found no relationship between dissolved lignin concentrations and total suspended sediments (TSS) across all sites, in contrast to the strong relationship observed in weekly samples at the mouth. As DOC concentrations and compositions at the mouth of Willow Slough are closely tied to anthropogenic activities within the catchment, future changes in land-use driven by climate change, water availability, and economic pressures on crop types will also bring about changes in the overall biogeochemistry.