Catchment chemostasis revisited: Water quality responds differently to variations in weather and climate

Solute concentrations in streamflow typically vary systematically with stream discharge, and the resulting concentration-discharge relationships are important signatures of catchment biogeochemical processes. Solutes derived from mineral weathering often exhibit decreasing concentrations with increasing flows, suggesting dilution of a kinetically limited weathering flux by a variable flux of water. However, previous work showed that concentration-discharge relationships of weathering-derived solutes in 59 headwater catchments were much weaker than this simple dilution model would predict. Instead, catchments behaved as chemostats, with rates of solute production and/or mobilization that were nearly proportional to water fluxes, on both event and interannual timescales. Here, we re-examine these findings using data for a wider range of solutes from 2,186 catchments, ranging from similar to 10 to >1,000,000 km(2) in drainage area and spanning a wide range of lithologic and climatic settings. Concentration-discharge relationships among this much larger set of larger catchments are broadly consistent with the previously described chemostatic behaviour, at least on event and interannual timescales for weathering-derived solutes. Among these same catchments, however, site-to-site variations in mean concentrations of weathering-derived solutes exhibit strong negative correlations with long-term average precipitation and discharge, reflecting strong climatic control on long-term leaching of the critical zone. We use multiple regression of site characteristics including discharge to identify potential controls on long-term mean concentrations and find that lithologic and land cover controls are significant predictors for many analytes. The picture that emerges is one in which, on event and interannual timescales, weathering-derived stream solute concentrations are chemostatically buffered by groundwater storage and fast chemical reactions, but each catchment's chemostatic "set point" reflects site-to-site differences in climatically driven evolution of the critical zone. In contrast to these weathering products, some nutrients and particulates are often near-chemostatic across all timescales, and their long-term mean concentrations correlate more strongly with land use than climatic characteristics.