Past studies on concentration-discharge (C-Q) relationships have focused on short-term or low-temporal resolution data. While advancing understanding of catchment processes, these studies provided limited insight on catchment response over time or to climate change. Using 15 solutes from 1992 to 2015 at Sleepers River Research Watershed, Vermont, we compared C-Q relationships over decades, years, and seasons to elucidate controls on stream chemical variation. We applied end-member mixing analysis (EMMA) to identify solute sources and flow path routing. EMMA identified three end-members: near-surface runoff (NSR), riparian groundwater, and hillslope hollow groundwater. Shifting mixing proportions of these end-members accounted for the temporal variability of conservative (no chemical reaction en route from source to stream) solutes in streamflow. For example, an increase in NSR fraction, typical of high flow, caused flushing (increased concentrations) of NO3−, DOC, Al, and Fe, which were greatest in NSR, dilution of specific conductance and base cation, SO42−, Si, Sr, Ba, and Mn concentrations, which were greatest in the two groundwater end-members. This behaviour is reflected in the b-coefficient of the C-Q relation (C = aQb), which indicates the strength of dilution (b 0.1) effects. For conservative solutes, the b-coefficient decreased significantly (p