Climate change is expected to have a strong effect on the Eastern Siberian Arctic Shelf (ESAS) region, which includes 40% of the Arctic shelves and comprises the Laptev and East Siberian seas. The largest organic carbon pool, the dissolved organic carbon (DOC), may change significantly due to changes in both riverine inputs and transformation rates; however, the present DOC inventories and transformation patterns are poorly understood. Using samples from the International Siberian Shelf Study 2008, this study examines for the first time DOC removal in Arctic shelf waters with residence times that range from months to years. Removals of up to 10%-20% were found in the Lena River estuary, consistent with earlier studies in this area, where surface waters were shown to have a residence time of approximately 2 months. In contrast, the DOC concentrations showed a strong nonconservative pattern in areas with freshwater residence times of several years. The average losses of DOC were estimated to be 30%-50% during mixing along the shelf, corresponding to a first-order removal rate constant of 0.3 yr(-1). These data provide the first observational evidence for losses of DOC in the Arctic shelf seas, and the calculated DOC deficit reflects DOC losses that are higher than recent model estimates for the region. Overall, a large proportion of riverine DOC is removed from the surface waters across the Arctic shelves. Such significant losses must be included in models of the carbon cycle for the Arctic Ocean, especially since the breakdown of terrestrial DOC to CO2 in Arctic shelf seas may constitute a positive feedback mechanism for Arctic climate warming. These data also provide a baseline for considering the effects of future changes in carbon fluxes, as the vast northern carbon-rich permafrost areas draining into the Arctic are affected by global warming.

Ongoing permafrost thaw in the Arctic may remobilize large amounts of old organic matter. Upon transport to the Siberian shelf seas, this material may be degraded and released to the atmosphere, exported off-shelf, or buried in the sediments. While our understanding of the fate of permafrost-derived organic matter in shelf waters is improving, poor constraints remain regarding degradation in sediments. Here we use an extensive data set of organic carbon concentrations and isotopes (n=109) to inventory terrigenous organic carbon (terrOC) in surficial sediments of the Laptev and East Siberian Seas (LS + ESS). Of these similar to 2.7 Tg terrOC about 55% appear resistant to degradation on a millennial timescale. A first-order degradation rate constant of 1.5 kyr(-1) is derived by combining a previously established relationship between water depth and cross-shelf sediment-terrOC transport time with mineral-associated terrOC loadings. This yields a terrOC degradation flux of similar to 1.7Gg/year from surficial sediments during cross-shelf transport, which is orders of magnitude lower than earlier estimates for degradation fluxes of dissolved and particulate terrOC in the water column of the LS + ESS. The difference is mainly due to the low degradation rate constant of sedimentary terrOC, likely caused by a combination of factors: (i) the lower availability of oxygen in the sediments compared to fully oxygenated waters, (ii) the stabilizing role of terrOC-mineral associations, and (iii) the higher proportion of material that is intrinsically recalcitrant due to its chemical/molecular structure in sediments. Sequestration of permafrost-released terrOC in shelf sediments may thereby attenuate the otherwise expected permafrost carbon-climate feedback. Plain language summary Frozen soils in the Arctic contain large amounts of old organic matter. With ongoing climate change this previously freeze-locked carbon storage becomes vulnerable to transport and decay. Upon delivery to the shallow nearshore seas, it may either be directly degraded to carbon dioxide or methane and thereby fuel further warming or get buried and stored in sediments on the sea floor. Our understanding of the fate of carbon released from permafrost soils is increasing, yet uncertainties remain regarding its degradation in the sediment. Here we constrain how much land-derived organic carbon is deposited in the top layer of the sediment (the part that is prone to transport and exposed to oxygen-stimulated degradation) in the Laptev and East Siberian Seas. We find that more than half of this stock likely resists degradation, while the rest decays relatively slowly. Therefore, the amount of carbon released annually from degradation in surface sediments is much smaller than what was found to be emitted from overlying waters in earlier studies. We suspect that this difference is caused by a combination of mechanisms hindering degradation in sediments and thus conclude that the burial of land-derived carbon may help to dampen the climate impact of thawing permafrost.

Methane emissions from natural wetlands tend to increase with temperature and therefore may lead to a positive feedback under future climate change. However, their temperature response includes confounding factors and appears to differ on different time scales. Observed methane emissions depend strongly on temperature on a seasonal basis, but if the annual mean emissions are compared between sites, there is only a small temperature effect. We hypothesize that microbial dynamics are a major driver of the seasonal cycle and that they can explain this apparent discrepancy. We introduce a relatively simple model of methanogenic growth and dormancy into a wetland methane scheme that is used in an Earth system model. We show that this addition is sufficient to reproduce the observed seasonal dynamics of methane emissions in fully saturated wetland sites, at the same time as reproducing the annual mean emissions. We find that a more complex scheme used in recent Earth system models does not add predictive power. The sites used span a range of climatic conditions, with the majority in high latitudes. The difference in apparent temperature sensitivity seasonally versus spatially cannot be recreated by the non-microbial schemes tested. We therefore conclude that microbial dynamics are a strong candidate to be driving the seasonal cycle of wetland methane emissions. We quantify longer-term temperature sensitivity using this scheme and show that it gives approximately a 12% increase in emissions per degree of warming globally. This is in addition to any hydrological changes, which could also impact future methane emissions.

Distinguishing the sources, ages, and fate of various terrestrial organic carbon (OC) pools mobilized from heterogeneous Arctic landscapes is key to assessing climatic impacts on the fluvial release of carbon from permafrost. Through molecular C-14 measurements, including novel analyses of suberin- and/or cutin-derived diacids (DAs) and hydroxy fatty acids (FAs), we compared the radiocarbon characteristics of a comprehensive suite of terrestrial markers (including plant wax lipids, cutin, suberin, lignin, and hydroxy phenols) in the sedimentary particles from nine major arctic and subarctic rivers in order to establish a benchmark assessment of the mobilization patterns of terrestrial OC pools across the pan-Arctic. Terrestrial lipids, including suberin-derived longer-chain DAs (C-24,C-26,C-28), plant wax FAs (C(24,26,2)8), and n-alkanes (C-27,C-29,C-31), incorporated significant inputs of aged carbon, presumably from deeper soil horizons. Mobilization and translocation of these "old" terrestrial carbon components was dependent on nonlinear processes associated with permafrost distributions. By contrast, shorter-chain (C-16,C-18) DAs and lignin phenols (as well as hydroxy phenols in rivers outside eastern Eurasian Arctic) were much more enriched in C-14, suggesting incorporation of relatively young carbon supplied by runoff processes from recent vegetation debris and surface layers. Furthermore, the radiocarbon content of terrestrial markers is heavily influenced by specific OC sources and degradation status. Overall, multitracer molecular C-14 analysis sheds new light on the mobilization of terrestrial OC from arctic watersheds. Our findings of distinct ages for various terrestrial carbon components may aid in elucidating fate of different terrestrial OC pools in the face of increasing arctic permafrost thaw.

Isotopic data provide powerful constraints on regional and global methane emissions and their source profiles. However, inverse modeling of spatially-resolved methane flux is currently constrained by a lack of information on the variability of source isotopic signatures. In this study, isotopic signatures of emissions in the Fennoscandian Arctic have been determined in chambers over wetland, in the air 0.3 to 3 m above the wetland surface and by aircraft sampling from 100 m above wetlands up to the stratosphere. Overall the methane flux to atmosphere has a coherent δ13C isotopic signature of -71 ± 1‰, measured in situ on the ground in wetlands. This is in close agreement with δ13C isotopic signatures of local and regional methane increments measured by aircraft campaigns flying through air masses containing elevated methane mole fractions. In contrast results from wetlands in Canadian boreal forest further south gave isotopic signatures of -67 ± 1 ‰.Wetland emissions dominate the local methane source measured over the European Arctic in summer. Chamber measurements demonstrate a highly variably methane flux and isotopic signature, but the results from air sampling within wetland areas show that emissions mix rapidly immediately above the wetland surface and methane emissions reaching the wider atmosphere do indeed have strongly coherent C isotope signatures. The study suggests that for boreal wetlands (>60°N) global and regional modeling can use an isotopic signature of -71‰ to apportion sources more accurately, but there is much need for further measurements over other wetlands regions to verify this.

Net ecosystem exchange (NEE) was estimated for an area of tundra near Abisko using both eddy covariance (EC) data and chamber measurements. This area of tundra is heterogeneous with six principal elements forming a landscape mosaic. Chamber measurements in patches of the individual mosaic elements were used to model NEE as a function of irradiance and temperature. The area around the EC mast was mapped, and a footprint model was used to simulate the varying source fraction attributable to each mosaic element. Various upscaling approaches were used to estimate NEE for comparison with NEE calculated from the EC observations. The results showed that EC measurements made for such a heterogeneous site are robust to the variations in NEE between mosaic elements that also vary substantially in their source fractions. However, they also revealed a large (?60%) bias in the absolute magnitude of the cumulative negative NEE for a 40-day study period simulated by various upscaling approaches when compared to the value calculated from the EC observations. The magnitude of this bias, if applied to estimates for the entire tundra region, is substantial in relation to other components of the global carbon budget. Various hypotheses to account for this bias are discussed and, where possible, evaluated. A need is identified for more systematic sampling strategies when performing chamber measurements in order to assess the extent to which subjectivity of chamber location may account for much of the observed bias. If this is the origin of the bias, then upscaling approaches using chamber measurements may generally overestimate CO2 uptake.

Current predictions of climate-related changes in high-latitude environments suggest major effects on the C export in streams and rivers. To what extent this will also affect the stream water CO2 concentrations is poorly understood. In this study we examined the spatiotemporal variation in partial pressure of CO2 (pCO2) and in stable isotopic composition of dissolved inorganic carbon (δ13C-DIC) in subarctic streams in northern Sweden. The selected watersheds are characterized by large variations in high-latitude boreal forest and tundra and differences in bedrock. We found that all streams generally were supersaturated in pCO2 with an average concentration of 850 µatm. The variability in pCO2 across streams was poorly related to vegetation cover, and carbonaceous bedrock influence was manifested in high DIC concentrations but not reflected in either stream pCO2 or δ13C-DIC. Stream water pCO2 values were highest during winter base flow when we also observed the lowest δ13C-DIC values, and this pattern is interpreted as a high contribution from CO2 from soil respiration. Summer base flow δ13C-DIC values probably are more affected by in situ stream processes such as aquatic production/respiration and degassing. A challenge for further studies will be to disentangle the origin of stream water CO2 and quantify their relative importance.

Stordalen Mire is a peatland in the discontinuous permafrost zone in arctic Sweden that exhibits a habitat gradient from permafrost palsa, to Sphagnum bog underlain by permafrost, to Eriophorum-dominated fully thawed fen. We used three independent approaches to evaluate the annual, multi-decadal, and millennial apparent carbon accumulation rates (aCAR) across this gradient: seven years of direct semi-continuous measurement of CO₂ and CH₄ exchange, and 21 core profiles for ²¹⁰Pb and ¹⁴C peat dating. Year-round chamber measurements indicated net carbon balance of −13 ± 8, −49 ± 15, and −91 ± 43 g C m⁻² y⁻¹ for the years 2012–2018 in palsa, bog, and fen, respectively. Methane emission offset 2%, 7%, and 17% of the CO₂ uptake rate across this gradient. Recent aCAR indicates higher C accumulation rates in surface peats in the palsa and bog compared to current CO₂ fluxes, but these assessments are more similar in the fen. aCAR increased from low millennial-scale levels (17–29 g C m⁻² y⁻¹) to moderate aCAR of the past century (72–81 g C m⁻² y⁻¹) to higher recent aCAR of 90–147 g C m⁻² y⁻¹. Recent permafrost collapse, greater inundation and vegetation response has made the landscape a stronger CO₂ sink, but this CO₂ sink is increasingly offset by rising CH₄ emissions, dominated by modern carbon as determined by ¹⁴C. The higher CH₄ emissions result in higher net CO_2-equivalent emissions, indicating that radiative forcing of this mire and similar permafrost ecosystems will exert a warming influence on future climate.

Volatile halogenated compounds (CHBr3, CH2Br2, CHBr2Cl, and CH2ClI) were measured in the water column and in sea ice brine across the Arctic Ocean, from Barrow, Alaska, to Svalbard, during the Beringia 2005 expedition (August-September) with RV/IB Oden. High concentrations of brominated compounds (up to 42 pmol kg(-1) of bromoform) were found under multiyear ice in the surface waters over the Makarov Basin and the Lomonosov Ridge, near the North Pole. Even higher concentrations (bromoform up to 160 pmol kg(-1)) were found in sea ice brine. We propose that the high load of riverine dissolved organic matter that is transported in the Transpolar Drift is a main factor responsible for the high concentration of brominated volatile compounds found in sea ice brine and upper waters and that cycles of freezing and thawing during the transport enhance the transfer of halocarbons to the seawater. The iodinated compound (CH2ClI) showed a completely different distribution with highest concentrations in water of Pacific origin in the mixed layer and upper halocline of the northern Canada Basin and over the Alpha Ridge. In the southern Canada Basin, low concentrations of halocarbons were found in upper waters. Higher concentrations in water of Pacific origin, especially on the continental shelf, indicate production in the shelf regions, likely in the Chukchi Sea and the East Siberian Sea.

Climate warming is expected to destabilize permafrost carbon (PF-C) by thaw-erosion and deepening of the seasonally thawed active layer and thereby promote PF-C mineralization to CO2 and CH4. A similar PF-C remobilization might have contributed to the increase in atmospheric CO2 during deglacial warming after the last glacial maximum. Using carbon isotopes and terrestrial biomarkers (Delta C-14, delta C-13, and lignin phenols), this study quantifies deposition of terrestrial carbon originating from permafrost in sediments from the Chukchi Sea (core SWERUS-L2-4-PC1). The sediment core reconstructs remobilization of permafrost carbon during the late Allerod warm period starting at 13,000 cal years before present (BP), the Younger Dryas, and the early Holocene warming until 11,000 cal years BP and compares this period with the late Holocene, from 3,650 years BP until present. Dual-carbon-isotope-based source apportionment demonstrates that Ice Complex Deposit-ice- and carbon-rich permafrost from the late Pleistocene (also referred to as Yedoma)-was the dominant source of organic carbon (66 +/- 8%; mean +/- standard deviation) to sediments during the end of the deglaciation, with fluxes more than twice as high (8.0 +/- 4.6 g.m(-2).year(-1)) as in the late Holocene (3.1 +/- 1.0 g.m(-2).year(-1)). These results are consistent with late deglacial PF-C remobilization observed in a Laptev Sea record, yet in contrast with PF-C sources, which at that location were dominated by active layer material from the Lena River watershed. Release of dormant PF-C from erosion of coastal permafrost during the end of the last deglaciation indicates vulnerability of Ice Complex Deposit in response to future warming and sea level changes.

Global warming triggers permafrost thaw, which increases the release of terrigenous organic matter (terr-OM) to the Arctic Ocean by coastal erosion and rivers. Terrigenous OM degradation in the Arctic Ocean contributes to greenhouse gas emissions and severe ocean acidification, yet the vulnerability of different terr-OM components is poorly resolved. Here, terr-OM degradation dynamics are studied with unprecedented spatial coverage over the World's largest shelf sea system-the East Siberian Arctic Shelf (ESAS), using a multi-proxy molecular biomarker approach. Mineral-surface-area-normalized concentrations of terr-OM compounds in surface sediments decreases offshore. Differences between terr-OM compound classes (lignin phenols, high-molecular weight [HMW] n-alkanes, n-alkanoic acids and n-alkanols, sterols, 3,5-dihydroxybenzoic acids, cutin acids) reflect contrasting influence of sources, propensity to microbial degradation and association with sedimenting particles, with lignin phenols disappearing 3-times faster than total terr-OM, and twice faster than other biomarkers. Molecular degradation proxies support substantial terr-OM degradation across the ESAS, with clearest trends shown by: 3,5-dihydroxybenzoic acid/vanillyl phenol ratios, acid-to-aldehyde ratios of syringyl and vanillyl phenols, Carbon Preference Indices of HMW n-alkyl compounds and sitostanol/β-sitosterol. The combination of terr-OM biomarker data with δ¹³C/Δ¹⁴C-based source apportionment indicates that the more degraded state of lignin is influenced by the relative contribution of river-transported terr-OM from surface soils, while HMW n-alkanoic acids and stigmasterol are influenced by erosion-derived terr-OM from Ice Complex deposits. Our findings demonstrate differences in vulnerability to degradation between contrasting terr-OM pools, and underscore the need to consider molecular properties for understanding and modeling of large-scale biogeochemical processes of the permafrost carbon-climate feedback.

The air‐water exchange of trace gases such as CO₂ is usually parameterized in terms of a gas transfer velocity, which can be derived from direct measurements of the air‐sea gas flux. The transfer velocity of poorly soluble gases is driven by near‐surface ocean turbulence, which may be enhanced or suppressed by the presence of sea ice. A lack of measurements means that air‐sea fluxes in polar regions, where the oceanic sink of CO₂ is poorly known, are generally estimated using open‐ocean transfer velocities scaled by ice fraction. Here, we describe direct determinations of CO₂ gas transfer velocity from eddy covariance flux measurements from a mast fixed to ice adjacent to a sea‐ice lead during the summer‐autumn transition in the central Arctic Ocean. Lead water CO₂ uptake is determined using flux footprint analysis of water‐atmosphere and ice‐atmosphere flux measurements made under conditions (low humidity and high CO₂ signal) that minimize errors due to humidity cross‐talk. The mean gas transfer velocity is found to have a quadratic dependence on wind speed: k₆₆₀ = 0.179 U₁₀², which is 30% lower than commonly used open‐ocean parameterizations. As such, current estimates of polar ocean carbon uptake likely overestimate gas exchange rates in typical summertime conditions of weak convective turbulence. Depending on the footprint model chosen, the gas transfer velocities also exhibit a dependence on the dimension of the lead, via its impact on fetch length and hence sea state. Scaling transfer velocity parameterizations for regional gas exchange estimates may therefore require incorporating lead width data.

Black carbon (BC) plays an important role in carbon burial in marine sediments globally. Yet the sequestration of BC in the Arctic Ocean is poorly understood. Here we assess the concentrations, fluxes, and sources of soot BC (SBC)—the most refractory component of BC—in sediments from the East Siberian Arctic Shelf (ESAS), the World’s largest shelf sea system. SBC concentrations in the contemporary shelf sediments range from 0.1 to 2.1 mg g−1 dw, corresponding to 2–12% of total organic carbon. The 210Pb-derived fluxes of SBC (0.42–11 g m−2 yr−1) are higher or in the same range as fluxes reported for marine surface sediments closer to anthropogenic emissions. The total burial flux of SBC in the ESAS ( 4,000 Gg yr−1) illustrates the great importance of this Arctic shelf in marine sequestration of SBC. The radiocarbon signal of the SBC shows more depleted yet also more uniform signatures (−721 to −896‰; average of −774 ± 62‰) than of the non-SBC pool (−304 to −728‰; average of −491 ± 163‰), suggesting that SBC is coming from an, on average, 5,900 ± 300 years older and more specific source than the non-SBC pool. We estimate that the atmospheric BC input to the ESAS is negligible ( 0.6% of the SBC burial flux). Statistical source apportionment modeling suggests that the ESAS sedimentary SBC is remobilized by thawing of two permafrost carbon (PF/C) systems: surface soil permafrost (topsoil/PF; 25 ± 8%) and Pleistocene ice complex deposits (ICD/PF; 75 ± 8%). The SBC contribution to the total mobilized permafrost carbon (PF/C) increases with increasing distance from the coast (from 5 to 14%), indicating that the SBC is more recalcitrant than other forms of translocated PF/C. These results elucidate for the first time the key role of permafrost thaw in the transport of SBC to the Arctic Ocean. With ongoing global warming, these findings have implications for the biogeochemical carbon cycle, increasing the size of this refractory carbon pool in the Arctic Ocean.

Fluvial and erosional release processes in permafrost-dominated Eurasian Arctic cause transport of large amounts of particulate organic carbon (POC) to coastal waters. The marine fate of this terrestrial POC (terr-POC), water column degradation, burial in shelf sediments, or export to depth, impacts the potential for climate-carbon feedback. As part of the International Siberian Shelf Study (ISSS-08; August-September 2008), the POC distribution, inventory, and fate in the water column of the extensive yet poorly studied Eurasian Arctic Shelf seas were investigated. The POC concentration spanned 1-152 mu M, with highest values in the SE Laptev Sea. The POC inventory was constrained for the Laptev (1.32 +/- 0.09 Tg) and East Siberian seas (2.85 +/- 0.20 Tg). A hydraulic residence time of 3.5 +/- 2 years for these Siberian shelf seas yielded a combined annual terr-POC removal flux of 3.9 +/- 1.4 Tg yr(-1). Accounting for sediment burial and shelf-break exchange, the terr-POC water column degradation was similar to 2.5 +/- 1.6 Tg yr(-1), corresponding to a first-order terr-POC degradation rate constant of 1.4 +/- 0.9 yr(-1), which is 5-10 times faster than reported for terr-DOC degradation in the Arctic Ocean. This terr-POC degradation flux thus contributes substantially to the dissolved inorganic carbon excess of 10 Tg C observed during ISSS-08 for these waters. This evaluation suggests that extensive decay of terr-POC occurs already in the water column and contributes to outgassing of CO2. This process should be considered as a geographically dislocated carbon-climate coupling where thawing of vulnerable permafrost carbon on land is eventually adding CO2 above the ocean.

Samples from two Greenland ice cores (NEEM and NGRIP) have been measured for methane carbon isotope ratios (delta C-13-CH4) to investigate the CH4 mixing ratio anomaly during Greenland Interstadial (GI) 21.2 (85,000 years before present). This extraordinarily rapid event occurred within 150 years, comprising a CH4 mixing ratio pulse of 150 ppb (similar to 25%). Our new measurements disclose a concomitant shift in delta C-13-CH4 of 1 parts per thousand. Keeling plot analyses reveal the delta C-13 of the additional CH4 source constituting the CH4 anomaly as -56.8 +/- 2.8 parts per thousand, which we confirm by means of a previously published box model. We propose tropical wetlands as the most probable additional CH4 source during GI-21.2 and present independent evidence that suggests that tropical wetlands in South America and Asia have played a key role. We find no evidence that boreal CH4 sources, such as permafrost degradation, contributed significantly to the atmospheric CH4 increase, despite the pronounced warming in the Northern Hemisphere during GI-21.2.

This study presents an assessment of benthic nutrient regeneration and its role for the nutrient budget of the outer Laptev and East Siberian shelf sea. Porewater profiles of the major nutrients dissolved silica (DSi), dissolved inorganic nitrogen (DIN), and dissolved inorganic phosphate (DIP) as well as total dissolved iron (DFe) were evaluated with a one-dimensional reaction transport model to derive net reaction rates and benthic nutrient fluxes from shelf and slope 16 stations. Integrated over the shelf area the benthic fluxes of DSi, DIN, and DIP were found to be 7.1, 1.2, and 0.5 Gmol/year in the Laptev Sea and 29.8, 9.5, and 2.8 Gmol/year in East Siberian Sea, respectively. A comparison of the ratios of the benthic nutrient fluxes with marine and riverine inputs and Arctic plankton stoichiometry indicate substantial benthic nitrogen loss likely due to denitrification relative to DIP and DSi. Our benthic flux estimation is likely a low estimate of benthic nutrient fluxes considering potentially higher regeneration rates of nutrients from more productive, bioturbated near-shore sediments. The estimate emphasizes the role of benthic nutrient fluxes by returning nutrients with a fundamentally different stoichiometry to bottom waters from that of Arctic marine phytoplankton, riverine sources, and open water inflow. With a simple box model, we provide a snapshot of today's nutrient budget in the two seas and estimate that about 10%-20% of nutrients required by primary production are derived from sediments. This proportion is expected to increase for a future warmer Arctic continental shelf in response to increasing primary production.