The Greenland Ice Sheet is currently not accounted for in Arctic mercury budgets, despite large and increasing annual runoff to the ocean and the socio-economic concerns of high mercury levels in Arctic organisms. Here we present concentrations of mercury in meltwaters from three glacial catchments on the southwestern margin of the Greenland Ice Sheet and evaluate the export of mercury to downstream fjords based on samples collected during summer ablation seasons. We show that concentrations of dissolved mercury are among the highest recorded in natural waters and mercury yields from these glacial catchments (521–3,300 mmol km−2 year−1) are two orders of magnitude higher than from Arctic rivers (4–20 mmol km−2 year−1). Fluxes of dissolved mercury from the southwestern region of Greenland are estimated to be globally significant (15.4–212 kmol year−1), accounting for about 10% of the estimated global riverine flux, and include export of bioaccumulating methylmercury (0.31–1.97 kmol year−1). High dissolved mercury concentrations (~20 pM inorganic mercury and ~2 pM methylmercury) were found to persist across salinity gradients of fjords. Mean particulate mercury concentrations were among the highest recorded in the literature (~51,000 pM), and dissolved mercury concentrations in runoff exceed reported surface snow and ice values. These results suggest a geological source of mercury at the ice sheet bed. The high concentrations of mercury and its large export to the downstream fjords have important implications for Arctic ecosystems, highlighting an urgent need to better understand mercury dynamics in ice sheet runoff under global warming.

Climate change is melting glaciers and altering watershed biogeochemistry across the globe, particularly in regions dominated by mountain glaciers, such as southeast Alaska. Glacier dominated watersheds exhibit distinct dissolved organic matter (DOM) characteristics compared to forested and vegetated watersheds.However, there is a paucity of information on how stream DOM composition changes as glaciers retreat and terrestrial ecosystem succession ensues. Importantly, it is unclear over what timescales these transformations occur. Here, we used bulk, isotopic and ultrahigh resolution molecular-level techniques to assess how streamwater DOM composition evolves in response to glacier retreat and subsequent terrestrial ecosystem succession. For this, water samples were collected from eleven streams across a chronosequence spanning a temporal gradient 0 to ~1,400 years since glacier retreat in coastal, southeast Alaska. During the first ~200 years since glacier retreat, stream DOM showed marked and consistent changes in bulk, isotopic, and molecular-level composition. In particular, there was a decreased abundance of ancient, energy-rich (e.g., elevated aliphatic contribution), low aromaticity (e.g., low SUVA254 and AImod) DOM and an increased abundance of soil and vegetation derived aromatic DOM (e.g., more depleted  13 C, elevated condensed aromatic and polyphenolic contribution) that had a modern radiocarbon age. After ~200 years of ecosystem development, DOM composition was comparable to that observed for other temperate and arctic forested watersheds without permafrost influence. These results underscore the timelines on which glacier retreat may have substantial impacts on watershed biogeochemistry and coastal ecosystems that receive DOM subsidies from these rapidly changing landscapes.

Dissolved organic matter (DOM) in glacier runoff is aliphatic‐rich, yet studies have proposed that DOM originates mainly from allochthonous, aromatic, and often aged material. Allochthonous organic matter (OM) is exposed to ultraviolet radiation both in atmospheric transport and post‐deposition on the glacier surface. Thus, we evaluate photochemistry as a mechanism to account for the compositional disconnect between allochthonous OM sources and glacier runoff DOM composition. Six endmember OM sources (including soils and diesel particulate matter) were leached and photo‐irradiated for 28 days in a solar simulator, until >90% of initial chromophoric DOM was removed. Ultrahigh‐resolution mass spectrometry was used to compare the molecular composition of endmember leachates pre‐ and post‐irradiation to DOM in supraglacial and bulk runoff from the Greenland Ice Sheet and Juneau Icefield (Alaska), respectively. Photo‐irradiation drove molecular level convergence between the initially aromatic‐rich leachates and aromatic‐poor glacial samples, selectively removing aromatic compounds (−80 ± 19% relative abundance) and producing aliphatics (+75 ± 35% relative abundance). Molecular level glacier runoff DOM composition was statistically indistinguishable to post‐irradiation leachates. Bray‐Curtis analysis showed substantial similarity in the molecular formulae present between glacier samples and post‐irradiation leachates. Post‐irradiation leachates contained 84 ± 7.4% of the molecular formulae, including 72 ± 17% of the aliphatic formulae, detected in glacier samples. Our findings suggest that photodegradation, either in transit to or on glacier surfaces, could provide a mechanistic pathway to account for the disconnect between proposed aromatic, aged sources of OM and the aliphatic‐rich fingerprint of glacial DOM.