Ongoing 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 Gr ae nse. 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 Gr ae nse) 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 Gr ae nse stream. After the rain event, surface runoff modified the composition of Gr ae nse 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.

Soil organic carbon (SOC) rapidly accumulates during ecosystem primary succession in glacier foreland. This makes it an ideal model for studying soil carbon sequestration and stabilization, which are urgently needed to mitigate climate change. Here, we investigated SOC dynamics in the Kuoqionggangri glacier foreland on the Tibetan Plateau. The study area along a deglaciation chronosequence of 170-year comprising three ecosystem succession stages, including barren ground, herb steppe, and legume steppe. We quantified amino sugars, lignin phenols, and relative expression of genes associated with carbon degradation to assess the contributions of microbial and plant residues to SOC, and used FT-ICR mass spectroscopy to analyze the composition of dissolved organic matter. We found that herbal plant colonization increased SOC by enhancing ecosystem gross primary productivity, while subsequent legumes development decreased SOC, due to increased ecosystem respiration from labile organic carbon inputs. Plant residues were a greater contributor to SOC than microbial residues in the vegetated soils, but they were susceptible to microbial degradation compared to the more persistent and continuously accumulating microbial residues. Our findings revealed the organic carbon accumulation and stabilization process in early soil development, which provides mechanism insights into carbon sequestration during ecosystem restoration under climate change.

Climate warming is predicted to change the fluxes of dissolved organic matter and nitrate by increasing active layer thickness, plant productivity, and organic matter decomposition. These changes are hypothesized to in-crease mineral weathering and soil acidification rates. We investigated whether acidification rates and solute leaching fluxes are variable between permafrost-affected soils with different active layer thicknesses. We compared the fluxes of dissolved organic carbon (DOC) and total dissolved N and the ion fluxes associated with solute leaching and plant uptake to calculate proton budgets in the soils that differed in slope positions (upper slope and lower slope) and soil texture (clayey and sandy soils) in NW Canada. We found the wide variation in DOC and nitrate-N fluxes, depending on slope positions and soil texture. The nitrate-N fluxes were higher at the lower slope position of the sandy soil, compared to the upper slope position. Compared to sandy soils, the DOC fluxes from the organic horizons were higher in the clayey soils on shallower permafrost table. Organic acids were major proton sources in the organic horizons at all sites, but acidity was also contributed by nitrate (sandy and clayey soils at lower slope position) and carbonic acid (clayey soil at upper slope position). The weathering by carbonic acid lead to accumulation of short-range-order minerals in the clayey soils, while incipient podzolization of the sandy soils included the weathering of illite to vermiculite and the dissolution of short-range-order minerals. The shallower active layer thickness at the lower slope position resulted in lower plant productivity and acidification rates. In the permafrost-affected soils, the active layer thickness, the DOC and nitrate-N fluxes, and their contribution to acidification are dependent on the local variation in slope position and soil texture, as well as climate change.

Accelerated melting of mountain glaciers due to global warming has a significant impact on downstream biogeochemical evolution because a large amount of labile dissolved organic matter (DOM) is released. However, the DOM evolution processes from glacier to downstream are not well understood. To investigate these processes, samples from the glacial surface and terminating runoff of a mountain glacier on the Tibetan Plateau were collected simultaneously throughout the melting season. The samples were analyzed to determine the dissolved organic carbon (DOC) contents and chemical compositions by means of a combination of fluorescence excitation-emission matrix coupled with parallel factor analysis (EEM-PARAFAC) and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The results indicate that the DOC concentrations were higher in the snow samples than in the glacial runoff samples, although a significantly higher concentration of inorganic ions was found in the glacial runoff samples, suggesting the dominant source of DOM in the glacial runoff was the glacier. The EEM-PARAFAC revealed four fluorescent components in both the snow and glacial runoff samples. However, significantly different ratios between the four components of these two categories of samples suggested chemical, physical and/or biological evolution of DOM during transport. Molecular chemical composition analyses by FT-ICR MS revealed that the DOM composition varied dramatically between the glacier and the glacial runoff. More than 50 % of the molecules were transformed from aliphatic and peptide-like compounds in the snow samples into highly unsaturated and phenolic-like compounds in the glacial run-off samples. The potential chemical transformation of DOM was likely related to biological and/or photolytic evolution during transport. Our results suggest that chemical evolution of glacial DOM could occur during the downstream transport, which is expected to be useful for further research exploring the fate of DOM and carbon cycling from the ciyaspheric environment and evaluating the biogeochemical effects.

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.

Organic matter, upon dissolution into the aqueous state as dissolved organic matter (DOM), can undergo mineralization by microbes. There has been increasing effort to characterize DOM released from thawing permafrost because it may perpetuate a permafrost carbon feedback. Permafrost-derived DOM often has a composition that can be highly susceptible to mineralization by microbes, but most studies to date that characterize permafrost-derived DOM have been limited to select regions, and tend to focus on a single type of permafrost (sometimes unspecified) that reflects a particular deposit type. Importantly, diversity in the nature of the deposit, formation of permafrost, and thaw modification processes leads to spatial and stratigraphic variability in its properties, but our understanding of variation in the composition of DOM derived from differing permafrost types (end-members) is poor. Here, we used ultrahigh-resolution mass spectrometry to characterize DOM composition derived from a series of permafrost end-member types that are commonly found within the thaw-vulnerable western Canadian Arctic, including: tills (glacially deposited), diamicton (thawed and remobilized material of mixed origin), lacustrine (lake basin sediments into which permafrost has aggraded), peat (partially decomposed organic material), and Yedoma (syngenetic silty loess) deposits. We identified marked variation in DOM composition among permafrost end-member types. Tills were compositionally dissimilar to all other permafrost end-members. Compounds unique to Yedoma were predominantly aliphatic, while compounds unique to peat, lacustrine, and diamicton spanned saturation and oxygenation gradients. All permafrost leachates were generally higher in aliphatics, lower in aromatics, and less oxygenated than active layer leachates. Compositional differences appear to reflect variation in permafrost parent materials, and particularly strong effects from past modification processes while in the unfrozen or thawed state. Constraining DOM composition and assessing its stratigraphic variability will become more pressing as the spatial and stratigraphic extent of thaw increases with future warming.

Recent studies have revealed the abundance of dissolved organic matter (DOM) in snow/glaciers of the Tibetan Plateau (TP). Here, we present a comprehensive study on the chemical compositions of snowpit samples collected from widely distributed eight glaciers in the western China (six from the TP) to investigate the spatial variation of deposited atmospheric aerosols. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was used to chemically characterize the DOM in snow samples which can offer chemical properties of DOM. Highest mass concentration of dissolved species mass was observed in Tienshan Baishui No 1 glacier (TS, 6.55 +/- 0.85 mg/L) close to Takalamagan Desert, whereas lowest (0.89 +/- 0.18 mg/L) was observed in Zadang Glacier (ZD) in the central TP. DOM (8-40%) and calcium as well as magnesium (9-67%) were generally the most abundant chemical species. Average DOM concentration in the TP glaciers among the investigated sites were comparable. DOM was found highly oxidized with an oxygen to carbon ratio (O/C ratio) ranging from 0.82 to 1.03. Highly oxidized DOM could have related with aerosol aqueous processes as illustrated by observed organic acids. This study provides insights into the spatial variations of the DOM and dissolved inorganic matter, as well as oxidized organic aerosol, were most likely due to local and regional contribution. (C) 2019 Elsevier B.V. All rights reserved.

Increased permafrost thaw due to climate change in northern high-latitudes has prompted concern over impacts on soil and stream biogeochemistry that affect the fate of dissolved organic carbon (DOC). Few studies to-date have examined the link between molecular composition and biolability of dissolved organic matter (DOM) mobilized from different soil horizons despite its importance in understanding carbon turnover in aquatic systems. Additionally, the effect of mixed DOM sources on microbial metabolism (e.g., priming) is not well understood. No studies to-date have addressed potential priming effects in northern high-latitude or permafrost-influenced aquatic ecosystems, yet these ecosystems may be hot spots of priming where biolabile, ancient permafrost DOC mixes with relatively stable, modern stream DOC. To assess biodegradability and priming of DOC in permafrost-influenced streams, we conducted 28 day bioincubation experiments utilizing a suite of stream samples and leachates of fresh vegetation and different soil horizons, including permafrost, from Interior Alaska. The molecular composition of unamended DOM samples at initial and final time points was determined by ultrahigh resolution mass spectrometry. Initial molecular composition was correlated to DOC biodegradability, particularly the contribution of energy-rich aliphatic compounds, and stream microbial communities utilized 50-56% of aliphatics in permafrost-derived DOM within 28 days. Biodegradability of DOC followed a continuum from relatively stable stream DOC to relatively biolabile DOC derived from permafrost, active layer organic soil, and vegetation leachates. Microbial utilization of DOC was similar to 3-11% for stream bioincubations and ranged from 9% (active layer mineral soil-derived) to 66% (vegetation-derived) for leachate bioincubations. To investigate the presence or absence of a priming effect, bioincubation experiments included treatments amended with 1% relative carbon concentrations of simple, biolabile organic carbon substrates (i.e., primers). The amount of DOC consumed in primed treatments was not significantly different from the control in any of the bioincubation experiments after 28 days, making it apparent that the addition of biolabile permafrost-derived DOC to aquatic ecosystems will likely not enhance the biodegradation of relatively modern, stable DOC sources. Thus, future projections of carbon turnover in northern high-latitude region streams may not have to account for a priming effect.

This paper reviews the impacts of permafrost change on hydrological and related hydrochemical, particulate and organic fluxes in small Arctic catchments. While the emphasis is directed at High Arctic systems, literature and recent developments from other Arctic regions are also included. Hydrological change, particularly a shift from nival (snowmelt) dominance to increasing pluvial (rainfall) runoff contributions has important consequences for the timing and magnitude of hydrological fluxes. A key distinction is made between thermal perturbation, where changing melt season thaw conditions result in deep thaw with minimal geomorphic or surface hydrological effects, in contrast to physical perturbation, where permafrost change results in some form of thermokarst or physical disturbance such as mass movement or enhanced erosion. The latter disturbances are commonly expressed as localized thermo erosional gullies, active layer detachments and retrogressive thaw slumps. Results from recent research emphasise the importance of hydrological connectivity in terms of the downstream effect of a particular permafrost perturbation. Well-connected systems, either at the surface as channelized flows, or in the subsurface, through new or altered active layer flow pathways, result in substantial changes in downstream fluvial fluxes. Surface hydrological connectivity of localized permafrost disturbances increases transport of suspended sediment and particulate organic matter, the latter of which is often old and comparatively labile. Exposed ice in retrogressive thaw slumps sustains discharge during the melt season, further increasing fluxes. Thermal perturbation holds a substantially greater potential downstream impact due to widespread mobilization of solutes and dissolved organic carbon and nitrogen, and several studies point to rapid microbial alteration of carbon and inorganic nitrogen transformation in the shallow subsurface. Collectively, these results point to altered runoff, sediment transport and hydrochemical fluxes with spatial and hydrological controls.

Ongoing global temperature rise has caused significant thaw and degradation of permafrost soils on the Qinghai-Tibetan Plateau (QTP). Leaching of organic matter from permafrost soils to aquatic systems is highly complex and difficult to reproduce in a laboratory setting. We collected samples from natural seeps of active and permafrost layers in an alpine swamp meadow on the QTP to shed light on the composition of mobilized dissolved organic matter (DOM) by combining optical measurements, ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry, radiocarbon (C-14), and solid-state C-13 nuclear magnetic resonance spectroscopy. Our results show that even though the active layer soils contain large amounts of proteins and carbohydrates, there is a selective release of aromatic components, whereas in the deep permafrost layer, carbohydrate and protein components are preferentially leached during the thawing process. Given these different chemical characteristics of mobilized DOM, we hypothesize that photomineralization contributes significantly to the loss of DOM that is leached from the seasonally thawed surface layer. However, with continued warming, biodegradation will become more important since biolabile materials such as protein and carbohydrate are preferentially released from deep-layer permafrost soils. This transition in DOM leachate source and associated chemical composition has ramifications for downstream fluvial networks on the QTP particularly in terms of processing of carbon and associated fluxes.