Perennial flow through convergent hillslopes explains chemodynamic solute behavior in a shale headwater catchment

We conclude that chemodynamic behavior at SSHCZO is driven by seasonally variable connectivity between the stream and hillslope soils. During the dry season, stream water derives from a shallow perched water table (interflow) that upwells to generate metal-rich stream headwaters. High concentrations of soluble Fe and Mn at low discharge occur when metal-rich headwaters are flushed to the catchment outlet during periodic rain events. Interflow during the dry season originates from water that infiltrates through organic-rich swales; thus, metals in the stream at low flow are ultimately derived from convergent hillslopes where biological processes have concentrated and/or mobilized these chemodynamic elements. In contrast, high concentrations of Ca2+ at low discharge are likely mobilized from stream sediments that contain secondary calcite precipitates. We infer that chemodynamic solutes are diluted at high discharge primarily due to increased flow through planar hillslopes. This study highlights how spatially heterogeneous biogeochemistry and seasonally variable flow paths regulate concentration-discharge behavior within catchments.