A new conceptual framework for the transformation of groundwater dissolved organic matterGroundwater comprises 95% of the liquid fresh water on Earth and contains a diverse mix of dissolved organic matter (DOM) molecules which play a significant role in the global carbon cycle. Currently, the storage times and degradation pathways of groundwater DOM are unclear, preventing an accurate estimate of groundwater carbon sources and sinks for global carbon budgets. Here we reveal the transformations of DOM in aging groundwater using ultra-high resolution mass spectrometry combined with radiocarbon dating. Long-term anoxia and a lack of photodegradation leads to the removal of oxidised DOM and a build-up of both reduced photodegradable formulae and aerobically biolabile formulae with a strong microbial signal. This contrasts with the degradation pathway of DOM in oxic marine, river, and lake systems. Our findings suggest that processes such as groundwater extraction and subterranean groundwater discharge to oceans could result in up to 13 Tg of highly photolabile and aerobically biolabile groundwater dissolved organic carbon released to surface environments per year, where it can be rapidly degraded. These findings highlight the importance of considering groundwater DOM in global carbon budgets.
From canopy to consumer: what makes and modifes terrestrial DOM in a temperate forestTo investigate how source and processing control the composition of “terrestrial” dissolved organic matter (DOM), we combine soil and tree leachates, tree DOM, laboratory bioincubations, and ultrahigh resolution Fourier-transform ion cyclotron resonance mass spectrometry in three common landscape types (upland forest, forested wetland, and poor fen) of Southeast Alaska’s temperate rainforest. Tree (Tsuga heterophylla and Picea sitchensis) needles and bark and soil layers from each site were leached, and tree stemflow and throughfall collected to examine DOM sources. Dissolved organic carbon concentrations were as high as 167 mg CL−1 for tree DOM, suggesting tree DOM fluxes may be substantial given the hypermaritime climate of the region. Condensed aromatics contributed as much as 38% relative abundance of spruce and hemlock bark leachates suggesting coniferous trees are potential sources of condensed aromatics to surface waters. Soil leachates showed soil wetness dictates DOM composition and processing, with wetland soils producing more aromatic formulae and allowing the preservation of traditionally biolabile, aliphatic formulae. Biodegradation impacted soil and tree DOM differently, and though the majority of source-specific marker formulae were consumed for all sources, some marker formulae persisted. Tree DOM was highly biolabile (> 50%) and showed compositional convergence where processing homogenized DOM from different tree sources. In contrast, wetland and upland soil leachate DOM composition diverged and processing diversified DOM from different soil sources during bioincubations. Increasing precipitation intensity predicted with climate change in Southeast Alaska will increase tree leaching and soil DOM flushing, tightening linkages between terrestrial sources and DOM export to the coastal ocean.