The burial of terrestrial organic carbon (terrOC) in marine sediments contributes to the regulation of atmospheric CO2 on geological timescales and may mitigate positive feedback to present-day climate warming. However, the fate of terrOC in marine settings is debated, with uncertainties regarding its degradation during transport. Here, we employ compound-specific radiocarbon analyses of terrestrial biomarkers to determine cross-shelf transport times. For the World's largest marginal sea, the East Siberian Arctic shelf, transport requires 3600 +/- 300 years for the 600 km from the Lena River to the Laptev Sea shelf edge. TerrOC was reduced by similar to 85% during transit resulting in a degradation rate constant of 2.4 +/- 0.6 kyr(-1). Hence, terrOC degradation during cross-shelf transport constitutes a carbon source to the atmosphere over millennial time. For the contemporary carbon cycle on the other hand, slow terrOC degradation brings considerable attenuation of the decadal-centennial permafrost carbon-climate feedback caused by global warming.

The Siberian Arctic Sea shelf and slope is a key region for the degradation of terrestrial organic material transported from the organic carbon-rich permafrost regions of Siberia. We report on sediment carbon mineralization rates based on O2 microelectrode profiling, intact sediment core incubations, 35 S-sulfate tracer experiments, porewater dissolved inorganic carbon (DIC), δ13 CDIC, and iron, manganese, and ammonium concentrations from 20 shelf and slope stations. This data set provides a spatial overview of sediment carbon mineralization rates and pathways over large parts of the outer Laptev and East Siberian Arctic shelf and slope, and allowed us to assess degradation rates and efficiency of carbon burial in these sediments. Rates of oxygen uptake and iron and manganese reduction were comparable to temperate shelf and slope environments, but bacterial sulfate reduction rates were comparatively low. In the topmost 20 to 50 cm of sediment, aerobic carbon mineralization dominated degradation and comprised on average 82% of the depthintegrated carbon mineralization. Oxygen uptake rates and 35 S-sulfate reduction rates were higher in the eastern East Siberian Sea shelf compared to the Laptev Sea shelf. DIC/NH4 + ratios in porewaters and the stable carbon isotope composition of remineralized DIC indicated that the degraded organic matter on the Siberian shelf and slope was a mixture of marine and terrestrial organic matter. Based on dual end member calculations, the terrestrial organic carbon contribution varied between 32% and 36%, with a higher contribution in the Laptev Sea than in the East Siberian Sea. Extrapolation of the measured degradation rates using  isotope end member apportionment over the outer shelf of the Laptev and East Siberian Sea suggests that about 16 Tg C per year are respired in the outer shelf sea floor sediment. Of the organic matter buried below the oxygen penetration depth, between 0.6 and 1.3 Tg C per year are degraded by anaerobic processes, with a terrestrial organic carbon contribution ranging between 0.3 and 0.5 Tg per year.

Recent Arctic studies suggest that sea ice decline and permafrost thawing will affect phytoplankton dynamics and stimulate heterotrophic communities. However, in what way the plankton composition will change as the warming proceeds remains elusive. Here we investigate the chemical signature of the plankton-dominated fraction of particulate organic matter (POM) collected along the Siberian Shelf. POM (>10 mu m) samples were analysed using molecular biomarkers (CuO oxidation and IP25 ) and dual-carbon isotopes (delta C-13 and Delta C-14). In addition, surface water chemical properties were integrated with the POM (>10 mu m) dataset to understand the link between plankton composition and environmental conditions. delta C-13 and Delta C-14 exhibited a large variability in the POM (> 10 mu m) distribution while the content of terrestrial biomarkers in the POM was negligible. In the Laptev Sea (LS), delta C-13 and Delta C-14 of POM (> 10 mu m) suggested a heterotrophic environment in which dissolved organic carbon (DOC) from the Lena River was the primary source of metabolisable carbon. Within the Lena plume, terrestrial DOC probably became part of the food web via bacteria uptake and subsequently transferred to relatively other heterotrophic communities (e.g. dinoflagellates). Moving eastwards toward the sea-ice-dominated East Siberian Sea (ESS), the system became progressively more autotrophic. Comparison between delta C-13 of POM (> 10 mu m) samples and CO(2)aq concentrations revealed that the carbon isotope fractionation increased moving towards the easternmost and most productive stations. In a warming scenario characterised by enhanced terrestrial DOC release (thawing permafrost) and progressive sea ice decline, heterotrophic conditions might persist in the LS while the nutrient-rich Pacific inflow will likely stimulate greater primary productivity in the ESS. The contrasting trophic conditions will result in a sharp gradient in delta C-13 between the LS and ESS, similar to what is documented in our semi-synoptic study.

Pleistocene ice complex permafrost deposits contain roughly a quarter of the organic carbon (OC) stored in permafrost (PF) terrain. When permafrost thaws, its OC is remobilized into the (aquatic) environment where it is available for degradation, transport or burial. Aquatic or coastal environments contain sedimentary reservoirs that can serve as archives of past climatic change. As permafrost thaw is increasing throughout the Arctic, these reservoirs are important locations to assess the fate of remobilized permafrost OC. We here present compound-specific deuterium (delta H-2) analysis on leaf waxes as a tool to distinguish between OC released from thawing Pleistocene permafrost (ice complex deposits; ICD) and from thawing Holocene permafrost (from near-surface soils). Bulk geochemistry (%OC; delta C-13; % total nitrogen, TN) was analyzed as well as the concentrations and delta H-2 signatures of long-chain n-alkanes (C-21 to C-33) and midto long-chain n-alkanoic acids (C-16 to C-30) extracted from both ICD-PF samples (n = 9) and modern vegetation and Ohorizon (topsoil-PF) samples (n = 9) from across the northeast Siberian Arctic. Results show that these topsoil-PF samples have higher %OC, higher OC/TN values and more depleted delta(COC)-C-13 values than ICD-PF samples, suggesting that these former samples trace a fresher soil and/or vegetation source. Whereas the two investigated sources differ on the bulk geochemical level, they are, however, virtually indistinguishable when using leaf wax concentrations and ratios. However, on the molecular isotope level, leaf wax biomarker delta H-2 values are statistically different between topsoil PF and ICD PF. For example, the mean delta H-2 value of C-29 n-alkane was -246 +/- 13% (mean +/- SD) for topsoil PF and -280 +/- 12 parts per thousand for ICD PF. With a dynamic isotopic range (difference between two sources) of 34 to 50 parts per thousand; the isotopic fingerprints of individual, abundant, biomarker molecules from leaf waxes can thus serve as endmembers to distinguish between these two sources. We tested this molecular delta H-2 tracer along with another source-distinguishing approach, dual-carbon (delta C-13-Delta C-14) isotope composition of bulk OC, for a surface sediment transect in the Laptev Sea. Results show that general offshore patterns along the shelfslope transect are similar, but the source apportionment between the approaches vary, which may highlight the advan-tages of either. This study indicates that the application of delta H-2 leaf wax values has potential to serve as a complementary quantitative measure of the source and differential fate of OC thawed out from different permafrost compartments.

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 Pb-210-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 (similar to 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 (similar to 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.

Thawing of permafrost carbon (PF-C) due to climate warming can remobilise considerable amounts of terrestrial carbon from its long-term storage to the marine environment. PF-C can be then be buried in sediments or remineralised to CO2 with implications for the carbon-climate feedback. Studying historical sediment records during past natural climate changes can help us to understand the response of permafrost to current climate warming. In this study, two sediment cores collected from the East Siberian Sea were used to study terrestrial organic carbon sources, composition and degradation during the past similar to 9500 cal yrs BP. CuO-derived lignin and cutin products (i.e., compounds solely biosynthesised in terrestrial plants) combined with delta C-13 suggest that there was a higher input of terrestrial organic carbon to the East Siberian Sea between similar to 9500 and 8200 cal yrs BP than in all later periods. This high input was likely caused by marine transgression and permafrost destabilisation in the early Holocene climatic optimum. Based on source apportionment modelling using dual-carbon isotope (Delta C-14, Delta C-13) data, coastal erosion releasing old Pleistocene permafrost carbon was identified as a significant source of organic matter translocated to the East Siberian Sea during the Holocene.

Ocean acidification affects marine ecosystems and carbon cycling, and is considered a direct effect of anthropogenic carbon dioxide uptake from the atmosphere(1-3). Accumulation of atmospheric CO2 in ocean surface waters is predicted to make the ocean twice as acidic by the end of this century(4). The Arctic Ocean is particularly sensitive to ocean acidification because more CO2 can dissolve in cold water(5,6). Here we present observations of the chemical and physical characteristics of East Siberian Arctic Shelf waters from 1999,2000-2005,2008 and 2011, and find extreme aragonite undersaturation that reflects acidity levels in excess of those projected in this region for 2100. Dissolved inorganic carbon isotopic data and Markov chain Monte Carlo simulations of water sources using salinity and delta O-18 data suggest that the persistent acidification is driven by the degradation of terrestrial organic matter and discharge of Arctic river water with elevated CO2 concentrations, rather than by uptake of atmospheric CO2. We suggest that East Siberian Arctic Shelf waters may become more acidic if thawing permafrost leads to enhanced terrestrial organic carbon inputs and if freshwater additions continue to increase, which may affect their effciency as a source of CO2.

Ongoing global warming in high latitudes may cause an increasing supply of permafrost-derived organic carbon through both river discharge and coastal erosion to the Arctic shelves. Mobilized permafrost carbon can be either buried in sediments, transported to the deep sea or degraded to CO2 and outgassed, potentially constituting a positive feedback to climate change. This study aims to assess the fate of terrigenous organic carbon (TerrOC) in the Arctic marine environment by exploring how it changes in concentration, composition and degradation status across the wide Laptev Sea shelf. We analyzed a suite of terrestrial biomarkers as well as source-diagnostic bulk carbon isotopes (delta C-13, Delta C-14) in surface sediments from a Laptev Sea transect spanning more than 800 km from the Lena River mouth (< 10m water depth) across the shelf to the slope and rise (2000-3000m water depth). These data provide a broad view on different TerrOC pools and their behavior during cross-shelf transport. The concentrations of lignin phenols, cutin acids and high-molecular-weight (HMW) wax lipids (tracers of vascular plants) decrease by 89-99% along the transect. Molecular-based degradation proxies for TerrOC (e.g., the carbon preference index of HMW lipids, the HMW acids / alkanes ratio and the acid / aldehyde ratio of lignin phenols) display a trend to more degraded TerrOC with increasing distance from the coast. We infer that the degree of degradation of permafrost-derived TerrOC is a function of the time spent under oxic conditions during protracted cross-shelf transport. Future work should therefore seek to constrain cross-shelf transport times in order to compute a TerrOC degradation rate and thereby help to quantify potential carbon-climate feedbacks.

Destabilization and degradation of permafrost carbon in the Arctic regions could constitute a positive feedback to climate change. A better understanding of its fate upon discharge to the Arctic shelf is therefore needed. In this study, bulk carbon isotopes as well as terrigenous and marine biomarkers were used to construct two centennial records in the East Siberian Sea. Differences in topsoil and Pleistocene Ice Complex Deposit permafrost concentrations, modeled using delta C-13 and Delta C-14, were larger between inner and outer shelf than the changes over time. Similarly, lignin-derived phenol and cutin acid concentrations differed by a factor of ten between the two stations, but did not change significantly over time, consistent with the dual-carbon isotope model. High molecular weight (HMW) n-alkane and n-alkanoic acid concentrations displayed a smaller difference between the two stations (factor of 3-6). By contrast, the fraction for marine OC drastically decreased during burial with a half-life of 19-27 years. Vegetation and degradation proxies suggested supply of highly degraded gymnosperm wood tissues. Lipid Carbon Preference Index (CPI) values indicated more extensively degraded HMW n-alkanes on the outer shelf with no change over time, whereas n-alkanoic acids appeared to be less degraded toward the core top with no large differences between the stations. Taken together, our results show larger across-shelf changes than down-core trends. Further investigation is required to establish whether the observed spatial differences are due to different sources for the two depositional settings or, alternatively, a consequence of hydrodynamic sorting combined with selective degradation during cross-shelf transport.

Permafrost soils in the Arctic store large quantities of organic matter, roughly twice the amount of carbon that was present in the atmosphere before the industrial revolution. This freeze-locked carbon pool is susceptible to thawing caused by amplified global warming at high latitudes. The remobilization of old permafrost carbon facilitates its degradation to carbon dioxide and methane, thereby providing a positive feedback to climate change.

Accelerating coastal erosion in addition to projected rising river discharge with enhancing sediment loads are anticipated to transport increasing amounts of land-derived organic carbon (OC) to the Arctic Ocean. On its shallow continental shelves, this material may be remineralized in the water column or in the sediments, transported without being altered off shelf towards the deep sea of the Arctic Interior or buried in marine sediments and hence sequestered from the contemporary carbon cycle. The fate of terrigenous material in the marine environment, though offering potentially important mechanisms to either strengthen or attenuate the permafrost-carbon climate feedback, is so far insufficiently understood.

In this doctoral thesis, sediments from the wide East Siberian Arctic Shelf, the world’s largest shelf-sea system, were used to investigate some of the key processes for OC cycling. A range of bulk sediment properties, carbon isotopes and molecular markers were employed to elucidate the relative importance of different organic matter sources, the role of cross-shelf transport and the relevance of degradation during transport and after burial.

Overall, OC released from thawing permafrost constitutes a significant proportion of the sedimentary organic matter on the East Siberian Arctic Shelf. Two sediment cores from the inner and outer East Siberian Sea recorded no substantial changes in source material or clear trends in degradation status for the last century. With increasing distance from the coast, however, strong gradients were detected towards lower concentrations of increasingly reworked land-derived OC. The time spent during cross-shelf transport was consequently found to exert first-order control on degradation. Compound-specific radiocarbon dating on terrigenous biomarkers revealed a net transport time of ~4 000 years across the 600 km wide Laptev Sea shelf, yielding degradation rate constants for bulk terrigenous OC and specific biomarkers on the order of 2-4 kyr^-1.

From these results, the carbon flux released by degradation of terrigenous OC in surface sediments was estimated to be ~1.7 Gg yr^-1, several orders of magnitude lower than what had been quantified earlier for dissolved and particulate OC in the water column. Lower oxygen availability and close associations with the mineral matrix may protect sedimentary OC from remineralization and thereby weaken the permafrost-carbon feedback to present climate change.