Bioavailability and diagenetic state of dissolved organic matter in riparian groundwater

Riparian groundwater can exhibit considerable patchiness in the concentration and reactivity of dissolved organic matter (DOM), which ultimately shapes subsurface biogeochemical transformations. Free and combined amino acids are bioavailable constituents of DOM, and their concentration and composition can provide valuable information about the diagenetic state of DOM. Based on riparian groundwater samples and relevant DOM end-member samples, we adapted the amino-acid-based marine DOM degradation index (DI) to groundwater. The groundwater DI was applied to evaluate the spatial and temporal variability in the bioavailability and diagenetic state of riparian DOM in a restored and a channelized section of the River Thur, Switzerland. Among different indicators for DOM diagenetic state (total hydrolysable amino acid concentrations, C-normalized yields, and the contribution of nonprotein amino acids), the groundwater DI correlated best with the activity of the enzyme leucine-aminopeptidase and bacterial secondary production in riparian groundwater. The "freshest" DOM was consistently found in the channel and during high-flow conditions in the groundwater of the restored riparian section and was spatially constrained to a zone inhabited by a dense willow population. The use of amino acid data and the newly developed DI for DOM in groundwater is a promising approach for characterizing the spatial and temporal dynamics of DOM reactivity and diagenesis within riparian groundwater.