Temporal variation in end-member chemistry and its influence on runoff mixing patterns in a forested, Piedmont catchment

Runoff mixing patterns for base flow and 42 storm events were investigated for a 3 year period (20082010) in a 12 ha forested catchment in the mid-Atlantic, Piedmont region of the USA. Eleven distinct runoff sources were sampled independently and included: precipitation, throughfall, stemflow, litter leachate, wetland soil water, tension soil water, shallow groundwater, groundwater seeps, hyporheic water, riparian groundwater, and deep groundwater. A rigorous end-member mixing analysis (EMMA) was implemented and all base flow, storm-flow, and end-member chemistries were evaluated in a two-dimensional mixing space. End-members enclosed stream water chemistry and displayed a systematic continuum in EMMA space. Base-flow chemistry of stream waters was similar to groundwater seeps. Storm-event runoff was attributed to contributions from surficial sources (precipitation, throughfall, stemflow, and litter leachate) on the rising limb of the discharge hydrograph that was followed by soil and shallow groundwater sources on the recession limb of the hydrograph. The shapes of the storm-event hysteresis loops (wide versus tight, linear patterns) varied with hydrologic conditions from wet, hydrologically well-connected conditions to a dry, disconnected state. Detailed temporal data on end-member chemistry allowed us to explain the changes in stream water hysteresis patterns and runoff mixing space to shifts in end-member chemistry that occurred as the catchment became hydrologically disconnected. These results highlight the need to recognize the temporal variation in end-member chemistry as a function of catchment wetness and the need to collect high-frequency data on bothstream water as well as potential runoff end-members to better characterize catchment flow paths and mixing responses.