ABSTRACTOngoing and amplified climate change in the Arctic is leading to glacier retreat and to the exposure of an ever‐larger portion of non‐glaciated permafrost‐dominated landscapes. Warming will also cause more precipitation to fall as rain, further enhancing the thaw of previously frozen ground. Yet, the impact of those perturbations on the geochemistry of Arctic rivers remains a subject of debate. Here, we determined the geochemical composition of waters from various contrasting non‐glacial permafrost catchments and investigated their impact on a glacially dominated river, the Zackenberg River (Northeast Greenland), during late summer (August 2019). We also studied the effect of rainfall on the geochemistry of the Zackenberg River, its non‐glacial tributaries, and a nearby independent non‐glacial headwater stream Grænse. We analyzed water properties, quantified and characterized dissolved organic matter (DOM) using absorbance and fluorescence spectroscopy and radiocarbon isotopes, and set this alongside analyses of the major cations (Ca, Mg, Na, and K), dissolved silicon (Si), and germanium/silicon ratios (Ge/Si). The glacier‐fed Zackenberg River contained low concentrations of major cations, dissolved Si and dissolved organic carbon (DOC), and a Ge/Si ratio typical of bulk rock. Glacial DOM was enriched in protein‐like fluorescent DOM and displayed relatively depleted radiocarbon values (i.e., old DOM). Non‐glacial streams (i.e., tributaries and Grænse) had higher concentrations of major cations and DOC and DOM enriched in aromatic compounds. They showed a wide range of values for radiocarbon, Si and Ge/Si ratios associated with variable contributions of surface runoff relative to deep active layer leaching. Before the rain event, Zackenberg tributaries did not contribute notably to the solute export of the Zackenberg River, and supra‐permafrost ground waters governed the supply of solutes in Zackenberg tributaries and Grænse stream. After the rain event, surface runoff modified the composition of Grænse stream, and non‐glacial tributaries strongly increased their contribution to the Zackenberg River solute export. Our results show that summer rainfall events provide an additional source of DOM and Si‐rich waters from permafrost‐underlain catchments to the discharge of glacially dominated rivers. This suggests that the magnitude and composition of solute exports from Arctic rivers are modulated by permafrost thaw and summer rain events. This event‐driven solute supply will likely impact the carbon cycle in rivers, estuaries, and oceans and should be included into future predictions of carbon balance in these vulnerable Arctic systems.
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