Subsurface Storage Drives Hydrologic Connectivity and Spatial Variability in Stream Chemistry

ABSTRACT Understanding how subsurface water storage—created and structured by the geology and geomorphology of the critical zone—governs hydrologic connectivity between landscapes and streams is essential for explaining spatial and temporal variation in stream water chemistry. Most headwater studies have focused on high‐resolution stream water chemistry at the catchment outlet, rarely examining the spatial variability among tributaries and the main channel, or how these patterns relate to the underlying geology and geomorphology. Linking upstream spatial and temporal variability with chemical dynamics at the outlet over time is even less common. We conducted weekly synoptic sampling along Lookout Creek, located within the HJ Andrews Experimental Forest Long Term Ecological Research programme. Lookout Creek is in the volcanic terrain of the western Cascades, Oregon. The catchment spans multiple geologic units (e.g., lava flows) and geomorphic features (e.g., earthflows). We measured stream chemistry along the main stem and five tributaries to assess how varying degrees of hydrologic connectivity influence solute concentrations and transport across this geologic and geomorphologic template. To identify the timing and magnitude of hydrologic connectivity between tributaries, the main stem, and the catchment outlet, we analysed spatiotemporal patterns in stream chemistry using concentration‐discharge relationships, principal component analysis, and a metric of subcatchment synchrony. We found that in previously glaciated catchments with active earthflows, solute concentrations and base‐cation‐to‐silica ratios were higher, and more solutes had a chemostatic or mobilising behaviour, indicating high subsurface storage. This variability in subsurface storage, and its influence on hydrologic connectivity, ultimately determined the degree of chemical synchrony with the catchment outlet. Our findings suggest that, under future climate scenarios with shifts in precipitation phase and timing, headwater systems with substantial subsurface storage are likely to be more chemically resilient.