Isotopic and chromatographic fingerprinting of the sources of dissolved organic carbon in a shallow coastal aquifer

The terrestrial subsurface is the largest source of freshwater globally. The organic carbon contained within it and processes controlling its concentration remain largely unknown. The global median concentration of dissolved organic carbon (DOC) in groundwater is low compared to surface waters, suggesting significant processing in the subsurface. Yet the processes that remove this DOC in groundwater are not fully understood. The purpose of this study was to investigate the different sources and processes influencing DOC in a shallow anoxic coastal aquifer. Uniquely, this study combines liquid chromatography organic carbon detection with organic (delta(13) CDoc) carbon isotope geochemical analyses to fingerprint the various DOC sources that influence the concentration, carbon isotopic composition, and character with respect to distance from surface water sources, depth below surface, and inferred groundwater residence time (using H-3 activities) in groundwater. It was found that the average groundwater DOC concentration was 5 times higher (5 mg L-1) than the global median concentration and that the concentration doubled with depth at our site, but the chromatographic character did not change significantly. The anoxic saturated conditions of the aquifer limited the rate of organic matter processing, leading to enhanced preservation and storage of the DOC sources from peats and palaeosols contained within the aquifer. All groundwater samples were more aromatic for their molecular weight in comparison to other lakes, rivers and surface marine samples studied. The destabilization or changes in hydrology, whether by anthropogenic or natural processes, could lead to the flux of up to 10 times more unreacted organic carbon from this coastal aquifer compared to deeper inland aquifers.