Hydrologic behavior and soil properties across forested landscapes with complex topography exhibit high variability. The interaction of groundwater with spatially distinct soils produces and transports solutes across catchments, however, the spatiotemporal relationships between groundwater dynamics and soil solute fluxes are difficult to directly evaluate. While whole-catchment export of solutes by shallow subsurface flow represents an integration of soil environments and conditions but many studies compartmentalize soil solute fluxes as hillslope vs. riparian, deep vs. shallow, or as individual soil horizon contributions. This potentially obscures and underestimates the hillslope variation and magnitude of solute fluxes and soil development across the landscape. This study determined the spatial variation and of shallow soil base cation fluxes associated with weathering reactions (Ca, Mg, and Na), soil elemental depletion, and soil saturation dynamics in upland soils within a small, forested watershed at the Hubbard Brook Experimental Forest, NH. Base cation fluxes were calculated using a combination of ion-exchange resins placed in shallow groundwater wells (0.3 – 1 m depth) located across hillslope transects (ridges to lower backslopes) and measurements of groundwater levels. Groundwater levels were also used to create metrics of annual soil saturation. Base cation fluxes were positively correlated with soil saturation frequency and were greatest in soil profiles where primary minerals were most depleted of base cations (i.e., highly weathered). Spatial differences in soil saturation across the catchment were strongly related to topographic properties of the upslope drainage area and are interpreted to result from spatial variations in transient groundwater dynamics. Results from this work suggest that the structure of a catchment defines the spatial architecture of base cation fluxes, likely reflecting the mediation of subsurface stormflow dynamics on soil development. Furthermore, this work highlights the importance of further compartmentalizing solute fluxes along hillslopes, where certain areas may disproportionately contribute solutes to the whole catchment. Refining catchment controls on base cation generation and transport could be an important tool for opening the black box of catchment elemental cycling.
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