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Abstract Biospheric particulate organic carbon (POC_bio) burial and rock petrogenic particulate organic carbon (POC_petro) oxidation are opposing long‐term controls on the global carbon cycle, sequestering and releasing carbon, respectively. Here, we examine how watershed glacierization impacts the POC source by assessing the concentration and isotopic composition (δ¹³C and Δ¹⁴C) of POC exported from four watersheds with 0%–49% glacier coverage across a melt season in Southeast Alaska. We used two mixing models (age‐weight percent and dual carbon isotope) to calculate concentrations of POC_bioand POC_petrowithin the bulk POC pool. The fraction POC_petrocontribution was highest in the heavily glacierized watershed (age‐weight percent: 0.39 ± 0.05; dual isotope: 0.42 (0.37–0.47)), demonstrating a glacial source of POC_petroto fjords. POC_petrowas mobilized via glacier melt and subglacial flow, while POC_biowas largely flushed from the non‐glacierized landscape by rain. Flow normalized POC_bioconcentrations exceeded POC_petroconcentrations for all streams, but surprisingly were highest in the heavily glacierized watershed (mean: 0.70 mgL⁻¹; range 0.16–1.41 mgL⁻¹), suggesting that glacier rivers can contribute substantial POC_bioto coastal waters. Further, the most heavily glacierized watershed had the highest sediment concentration (207 mgL⁻¹; 7–708 mgL⁻¹), and thus may facilitate long‐term POC_bioprotection via sediment burial in glacier‐dominated fjords. Our results suggest that continuing glacial retreat will decrease POC concentrations and increase POC_bio:POC_petroexported from currently glacierized watersheds. Glacier retreat may thus decrease carbon storage in marine sediments and provide a positive feedback mechanism to climate change that is sensitive to future changes in POC_petrooxidation. 

Abstract West Siberia contains some of the largest soil carbon stores on Earth owing to vast areas of peatlands and permafrost, with the region warming far faster than the global average. Organic matter transported in fluvial systems is likely to undergo distinct compositional changes as peatlands and permafrost warm. However, the influence of peatlands and permafrost on future dissolved organic matter (DOM) composition is not well characterized. To better understand how these environmental drivers may impact DOM composition in warming Arctic rivers, we used ultrahigh resolution Fourier‐transform ion cyclotron resonance mass spectrometry to analyze riverine DOM composition across a latitudinal gradient of West Siberia spanning both permafrost‐influenced and permafrost‐free watersheds and varying proportions of peatland cover. We find that peatland cover explains much of the variance in DOM composition in permafrost‐free watersheds in West Siberia, but this effect is suppressed in permafrost‐influenced watersheds. DOM from warm permafrost‐free watersheds was more heterogenous, higher molecular weight, and relatively nitrogen enriched in comparison to DOM from cold permafrost‐influenced watersheds, which were relatively enriched in energy‐rich peptide‐like and aliphatic compounds. Therefore, we predict that as these watersheds warm, West Siberian rivers will export more heterogeneous DOM with higher average molecular weight than at present. Such compositional shifts have been linked to different fates of DOM in downstream ecosystems. For example, a shift toward higher molecular weight, less energy‐rich DOM may lead to a change in the fate of this material, making it more susceptible to photochemical degradation processes, particularly in the receiving Arctic Ocean. 

Abstract Groundwater is projected to become an increasing source of freshwater and nutrients to the Arctic Ocean as permafrost thaws, yet few studies have quantified groundwater inputs to Arctic coastal waters under contemporary conditions. New measurements along the Alaska Beaufort Sea coast show that dissolved organic carbon and nitrogen (DOC and DON) concentrations in supra-permafrost groundwater (SPGW) near the land-sea interface are up to two orders of magnitude higher than in rivers. This dissolved organic matter (DOM) is sourced from readily leachable organic matter in surface soils and deeper centuries-to millennia-old soils that extend into thawing permafrost. SPGW delivers approximately 400–2100 m³of freshwater, 14–71 kg of DOC, and 1–4 kg of DON to the coastal ocean per km of shoreline per day during late summer. These substantial fluxes are expected to increase as massive stocks of frozen organic matter in permafrost are liberated in a warming Arctic. 

Abstract A portion of the charcoal and soot produced during combustion processes on land (e.g., wildfire, burning of fossil fuels) enters aquatic systems as dissolved black carbon (DBC). In terms of mass flux, rivers are the main identified source of DBC to the oceans. Since DBC is believed to be representative of the refractory carbon pool, constraining sources of marine DBC is key to understanding the long-term persistence of carbon in our global oceans. Here, we use compound-specific stable carbon isotopes (δ¹³C) to reveal that DBC in the oceans is ~6‰ enriched in¹³C compared to DBC exported by major rivers. This isotopic discrepancy indicates most riverine DBC is sequestered and/or rapidly degraded before it reaches the open ocean. Thus, we suggest that oceanic DBC does not predominantly originate from rivers and instead may be derived from another source with an isotopic signature similar to that of marine phytoplankton. 

Abstract Lateral transport of organic carbon (OC) to the coastal ocean is an important component of the global carbon cycle because rivers transport, mineralize, and bury significant amounts of OC. Glaciers drive water and sediment export from many high‐elevation and high‐latitude ecosystems, yet their role in watershed OC balances is poorly understood, particularly with regard to particulate OC. Here, we evaluate seasonal water, sediment, and comprehensive OC budgets, including both dissolved and particulate forms, for three watersheds in southeast Alaska that vary in glacier coverage. We show that glacier loss will shift the dominant size fraction of riverine OC from particulate toward dissolved and potentially alter the provenance of particulate OC. Glacier coverage also controls whether OC export is source (C stock) or transport (runoff) limited at the watershed scale. These findings provide insight into the future trajectory of riverine OC export in glacierized regions. 

Abstract 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. 

Abstract Pyrogenic organic residues from wildfires and anthropogenic combustion are ubiquitous in the environment and susceptible to leaching from soils into rivers, where they are known as dissolved black carbon (DBC). Here we quantified and isotopically characterized DBC from the second largest river on Earth, the Congo, using 12 samples collected across three annual hydrographs from 2010 to 2012. We find that the Congo River exports an average of 803 ± 84 Gg‐C as DBC per year, comprising 7.5% of the river's average annual dissolved organic carbon (DOC) flux (10.7 ± 1.2 Tg‐C yr⁻¹). Concentrations of DBC were strongly correlated with discharge and DOC concentration, indicating transport limitation for DBC flux from the Congo River Basin. Stable carbon isotopic signatures of DBC revealed a seasonal shift in pyrogenic source from forest dominant to an increasing contribution from savannah biomass, which derives from the North‐South bimodal hydrologic regime within the basin. Our results also indicate that black carbon produced within the Congo Basin is exported by the river on relatively short time scales and that total DBC export will increase with climate change predictions for the central African region. 

Abstract Dissolved organic carbon (DOC) and nitrogen (DON) are important energy and nutrient sources for aquatic ecosystems. In many northern temperate, freshwater systems DOC has increased in the past 50 years. Less is known about how changes in DOC may vary across latitudes, and whether changes in DON track those of DOC. Here, we present long‐term DOC and DON data from 74 streams distributed across seven sites in biomes ranging from the tropics to northern boreal forests with varying histories of atmospheric acid deposition. For each stream, we examined the temporal trends of DOC and DON concentrations and DOC:DON molar ratios. While some sites displayed consistent positive or negative trends in stream DOC and DON concentrations, changes in direction or magnitude were inconsistent at regional or local scales. DON trends did not always track those of DOC, though DOC:DON ratios increased over time for ~30% of streams. Our results indicate that the dissolved organic matter (DOM) pool is experiencing fundamental changes due to the recovery from atmospheric acid deposition. Changes in DOC:DON stoichiometry point to a shifting energy‐nutrient balance in many aquatic ecosystems. Sustained changes in the character of DOM can have major implications for stream metabolism, biogeochemical processes, food webs, and drinking water quality (including disinfection by‐products). Understanding regional and global variation in DOC and DON concentrations is important for developing realistic models and watershed management protocols to effectively target mitigation efforts aimed at bringing DOM flux and nutrient enrichment under control.