Long-term data reveal patterns and controls on stream water chemistry in a forested stream: Walker Branch, Tennessee

We present 20 years of weekly stream water chemistry, hydrology, and climate data for the Walker Branch watershed in eastern Tennessee, USA. Since 1989, the watershed has experienced a similar to 1.08 degrees C increase in mean annual temperature, a similar to 20% decline in precipitation, and a similar to 30% increase in forest evapotranspiration rates. As a result, stream runoff has declined by similar to 34%. We evaluate long-term trends in stream water concentrations and fluxes for nine solutes and use wet deposition data to calculate approximate watershed input-output budgets. Dissolved constituents were classified as geochemical solutes (Ca2+, Mg2+, and SO42-) or nutrients (NH4+, NO3-, soluble reactive phosphorus [SRP], total soluble nitrogen [TSN], total soluble phosphorus [TSP], and dissolved organic carbon [DOC]). Geochemical solutes are predominantly controlled by discharge, and the long-term changes in catchment hydrology have led to significant trends in the concentrations and fluxes of these solutes. Further, the trends in geochemical solute concentrations indicate shifting soil flowpath contributions to streamflow generation through time, with deep groundwater having a greater proportional contribution in recent years. Despite dramatic changes in watershed runoff, there were no trends in inorganic nutrient concentrations (NH4+, NO3-, and SRP). While most nutrients entering the watershed are retained, stream fluxes of nutrient solutes have declined significantly as a result of decreasing runoff. Nutrient concentrations in the stream exhibit large seasonality controlled by in-stream biological uptake. Stream benthic communities are sensitive to hydrologic disturbance, and changes in the frequency or intensity of storm events through time can affect nutrient fluxes. Stream NO3- concentrations are also sensitive to drought, with concentrations decreasing (increasing) if conditions during the three years prior to the time of sampling were drier (wetter) than the long-term mean. Future changes in the incidence of storm events, as well as the number and duration of droughts, have the potential to significantly alter watershed nutrient losses. Our analysis indicates that changing climates can differentially affect watershed element cycles either through changes in biogeochemical process rates or through changes in catchment hydrology. Furthermore, climate change can include both long-term trending in mean climate variables, as well as changes in the frequency and intensity of storms and droughts, with each of these types of change having distinct effects on the biological and geochemical processes governing different solutes.