Stormflow generation in headwater catchments dominated by subsurface flow has been studied extensively, yet catchments dominated by surface flow have received less attention.
We addressed this by testing whether stormflow chemistry is controlled by either (a) the event-water signature of overland flow, or (b) the pre-event water signature of return flow. We used a high-resolution hydrochemical data set of stormflow and end-members of multiple storms in an end-member mixing analysis to determine the number of end-members needed to explain stormflow, characterize and identify potential end-members, calculate their contributions to stormflow, and develop a conceptual model of stormflow. The arrangement and relative positioning of end-members in stormflow mixing space suggest that saturation excess overland flow (26–48%) and return flow from two different subsurface storage pools (17–53%) are both similarly important for stormflow. These results suggest that pipes and fractures are important flow paths to rapidly release stored water and highlight the value of within-event resolution hydrochemical data to assess the full range and dynamics of flow paths.