Pan-Arctic Riverine Dissolved Organic Matter: Synchronous Molecular Stability, Shifting Sources and Subsidies

Climate change is dramatically altering Arctic ecosystems, leading to shifts in the sources, composition, and eventual fate of riverine dissolved organic matter (DOM) in the Arctic Ocean. Here we examine a 6-year DOM compositional record from the six major Arctic rivers using Fourier-transform ion cyclotron resonance mass spectrometry paired with dissolved organic carbon isotope data (Delta C-14, delta C-13) to investigate how seasonality and permafrost influence DOM, and how DOM export may change with warming. Across the pan-Arctic, DOM molecular composition demonstrates synchrony and stability. Spring freshet brings recently leached terrestrial DOM with a latent high-energy and potentially bioavailable subsidy, reconciling the historical paradox between freshet DOM's terrestrial bulk signatures and high biolability. Winter features undiluted baseflow DOM sourced from old, microbially degraded groundwater DOM. A stable core Arctic riverine fingerprint (CARF) is present in all samples and may contribute to the potential carbon sink of persistent, aged DOM in the global ocean. Future warming may lead to shifting sources of DOM and export through: (1) flattening Arctic hydrographs and earlier melt modifying the timing and role of the spring high-energy subsidy; (2) increasing groundwater discharge resulting in a greater fraction of DOM export to the ocean occurring as stable and aged molecules; and (3) increasing contribution of nitrogen/sulfur-containing DOM from microbial degradation caused by increased connectivity between groundwater and surface waters due to permafrost thaw. Our findings suggest the ubiquitous CARF (which may contribute to oceanic carbon sequestration) underlies predictable variations in riverine DOM composition caused by seasonality and permafrost extent.