Tracing terrestrial organic matter in surface sediments in Laptev Sea and East Siberian Sea: a Rock-Eval pyrolysis approach

Author(s):  
Elena Gershelis ◽  
Roman Kashapov ◽  
Alexey Ruban ◽  
Andrey Grin'ko ◽  
Oleg Dudarev ◽  
...  

<p>The East Siberian Arctic shelf (ESAS), the world’s largest continental shelf, receives substantial input of terrestrial organic carbon (TerrOC) both from increasing river discharge and from amplifying coastal erosion. Increasing TerrOC supply directly affects the Arctic marine carbon cycle, and, therefore, the fate of TerrOC upon its translocation to the Arctic continental margin has been the subject of growing interest in recent decades. Previous studies reported a strong decrease in sedimentary bulk TerrOC and terrestrial biomarkers with increasing distance from the coast during cross-shelf transport with much higher extent of degradation in the ESAS nearshore zone. Despite major progress has been made in estimating TerrOC inputs and quantifying its degradation rates in the Arctic land-shelf system, there are still important pieces insufficiently understood. Rock-Eval (RE) pyrolysis contributes to the traditional geochemical interpretations, based on elemental, isotopic and biomarker analyses and provides additional insight into the distribution, source and degradation state of organic carbon compounds of sedimentary organic matter.</p><p>In this study, the analytical approach included the characterization of marine and terrestrial carbon compounds using RE data coupled with organic carbon stable isotope composition. Rock-Eval analyses was performed on over 80 surface sediments samples from the Laptev Sea and western part of the East Siberian Sea collected during Arctic expeditions in 2011-2019. A track of rapidly degrading terrOC in shallow deposits may be traced using the ratios between hydrogen and oxygen indices and from the distribution of labile organic carbon fraction. Our results indicated high content of heavily degraded material with low hydrogen index, high oxygen index and a high content of residual carbon in sediments on the outer shelf of the western Laptev Sea and on the continental slope. Sharp decreasing of oxygen content in the eastern part of Laptev Sea and the western East Siberian Sea marked intensive dilution of degraded carbon with fresher material exported from New Siberian Islands. Furthermore, the RE data indicated a relatively high content of residual carbon (up to 87 %) stored in the studied surface sediments.</p><p>This research is supported by Russian Science Foundation, project # 19-77-00067.</p>

2020 ◽  
Author(s):  
Irina Oberemok ◽  
Elena Gershelis ◽  
Andrey Grin’ko ◽  
Alexey Ruban ◽  
Elizaveta Klevantseva ◽  
...  

<p>Accelerating coastal erosion and enhancing river sediment discharge are expected to greatly increase the delivery of terrestrial organic carbon (terrOC) to the Arctic Ocean. Remobilized terrOC may be buried in shallow or outer shelf sediments, degraded and translocated to the deeper basins, or remineralized in the water column causing a positive feedback to amplified global warming. The East Siberian Arctic Shelf (ESAS), represented by the Laptev Sea, the East Siberian Sea, and the Russian part of the Chukchi Sea, is the widest and shallowest continental shelf of the World Ocean. In the current study, we investigated surface sediment samples collected across the Laptev Sea shelf (from the coastline to the outer shelf) during the Arctic expedition onboard the Russian <em>R/V Academician M. Keldysh</em> during fall 2018.</p><p>We analyzed 16 samples for bulk (TOC, <em>δ</em>13C) and molecular (distribution and concentration of n-alkanes and PAHs) parameters. We also performed Rock-Eval (RE) analysis in order to compare its results with the signatures provided by traditional geochemical tracers and thereby to gain new insights into the sources of organic matter in modern surface sediments. In addition, a grain-size analysis was carried out to reveal hydrodynamic control on the organic carbon transport across the studied transect. Using a combination of traditional molecular interpretations (performed in this study and published earlier) and RE parameters (Hydrogen index, Oxygen index and T<sub>peak</sub>) we attempted to distinguish riverine input and coastal erosion and disentangle processes of terrOC degradation and its replacement with fresh/marine OC during cross-shelf transport. Overall, a strong decrease of terrigenous contribution to the sedimentary organic carbon was observed on molecular level with increasing distance from the coast. According to the RE data, intensive terrOC degradation takes place in the shallow and mid-shelf sediments which is traced by sharply increasing oxygen index. The clear correlation between OI and the clay content points toward the perception that mineral matrix do not seem to be such good protector as expected, and intensive microbial degradation of the sedimentary organic matter contained in fine particles occurs during repeated resuspension.</p><p>This research is supported by Russian Science Foundation, project # 19-77-00067.</p>


2021 ◽  
Author(s):  
Felipe Matsubara ◽  
Birgit Wild ◽  
Jannik Martens ◽  
Rickard Wennström ◽  
Oleg Dudarev ◽  
...  

<p>    Ongoing global warming is expected to accelerate the thaw of permafrost on land and to increase the input of terrigenous organic matter (terrOM) into the Arctic Ocean through coastal erosion and river discharge. Large remobilization of terrOM into the East Siberian Arctic Shelf (ESAS) dominates the organic matter in surface sediments over large parts of the shelf and its degradation contributes to ocean acidification. Previous studies have focused on the source apportionment of terrOM and the releases of CO<sub>2</sub> and CH<sub>4</sub> to the atmosphere from terrOM degradation; this study focuses on its diagenetic state during cross-shelf transport, since degradation is the link between permafrost thawing and greenhouse gases emissions. This study probes the degradation status of different terrOM components across the ESAS using various molecular and isotopic proxies and hence evaluates their differences to infer degradation.</p><p>    High-molecular weight (HMW) lipid compounds and lignin phenols are exclusively produced by terrestrial plants, providing protection, strength and rigidity to the plant structure. Owing to diagenesis, microbial degradation leads to <strong>1)</strong> <strong>loss of functional groups</strong>, thus the ratios of HMW n-alkanoic acids, HMW n-alkanols and sterols relative to HMW n-alkanes decrease; <strong>2)</strong> <strong>reduction of unsaturated to saturated carbons</strong>, so ratios of stanols relative to stenols increase; <strong>3) a higher formation of carboxylic acids in the lignin polymer</strong> and hence<strong> </strong>ratios of acids to aldehydes of vanillyl (Vd and Vl) and syringyl (Sd and Sl) increase.</p><p>    The concentrations of lipid- and lignin-derived products per sediment specific surface area decreased with offshore distance of the samples. During cross-shelf transport, the biomarker degradation proxies showed an increasing degradation for Sd/Sl, Vd/Vl, the “tannin-like” compound 3,5-dihydrobenzoic acid to vanillyl (3,5-Bd/V), β-sitostanol/ β-sitostenol and Carbon Preference Index (CPI) of HMW n-alkanes. Some other proxies showed no clear trend from inner to outer shelf and such inconsistent patterns are currently being investigated to better understand both the usefulness/response of different proxies and of the lability of terrOM in the ESAS. While β-sitostanol/β-sitostenol and CPI HMW n-alkane did not show strong differences between the East Siberian Sea and the Laptev Sea, Vd/Vl and Sd/Sl ratios indicated stronger degradation on the outer Laptev Sea and 3,5-Bd/V ratios indicated stronger degradation in the outer eastern East Siberian Sea. Such differences could reflect source properties of terrOM entering the ESAS, such as differences in source vegetation or transport pathway, i.e. coastal erosion or river discharge.</p>


Water ◽  
2020 ◽  
Vol 12 (12) ◽  
pp. 3511
Author(s):  
Elena Gershelis ◽  
Andrey Grinko ◽  
Irina Oberemok ◽  
Elizaveta Klevantseva ◽  
Natalina Poltavskaya ◽  
...  

Global warming in high latitudes causes destabilization of vulnerable permafrost deposits followed by massive thaw-release of organic carbon. Permafrost-derived carbon may be buried in the nearshore sediments, transported towards the deeper basins or degraded into the greenhouse gases, potentially initiating a positive feedback to climate change. In the present study, we aim to identify the sources, distribution and degradation state of organic matter (OM) stored in the surface sediments of the Laptev Sea (LS), which receives a large input of terrestrial carbon from both Lena River discharge and intense coastal erosion. We applied a suite of geochemical indicators including the Rock Eval parameters, traditionally used for the matured OM characterization, and terrestrial lipid biomarkers. In addition, we analyzed a comprehensive grain size data in order to assess hydrodynamic sedimentation regime across the LS shelf. Rock-Eval (RE) data characterize LS sedimentary OM with generally low hydrogen index (100–200 mg HC/g TOC) and oxygen index (200 and 300 CO2/g TOC) both increasing off to the continental slope. According to Tpeak values, there is a clear regional distinction between two groups (369–401 °C for the inner and mid shelf; 451–464 °C for the outer shelf). We suggest that permafrost-derived OM is traced across the shallow and mid depths with high Tpeak and slightly elevated HI values if compared to other Arctic continental margins. Molecular-based degradation indicators show a trend to more degraded terrestrial OC with increasing distance from the coast corroborating with RE results. However, we observed much less variation of the degradation markers down to the deeper sampling horizons, which supports the notion that the most active OM degradation in LS land-shelf system takes part during the cross-shelf transport, not while getting buried deeper.


2010 ◽  
Vol 7 (2) ◽  
pp. 2889-2926 ◽  
Author(s):  
B. He ◽  
M. Dai ◽  
W. Huang ◽  
Q. Liu ◽  
H. Chen ◽  
...  

Abstract. Organic matter in surface sediments from the upper reach of the Pearl River Estuary and Lingdingyang Bay, as well as the adjacent northern South China Sea shelf was characterized by a variety of techniques, including elemental (C and N), stable carbon isotopic (δ 13C) composition, as well as molecular-level analyses. Total organic carbon (TOC) content was 1.61±1.20% in the upper reach down to 1.00±0.22% in Lingdingyang Bay and to 0.80±0.10% on the inner shelf and 0.58±0.06% on the outer shelf. δ13C values ranged from −25.11‰ to −21.28‰ across the studied area, with a trend of enrichment seaward. The spatial trend in C/N ratios mirrored that of δ13C, with a substantial decrease in C/N ratio from 10.9±1.3 in the Lingdingyang Bay surface sediments to 6.5±0.09 in the outer shelf surface sediments. Total carbohydrate yields ranged from 22.1 to 26.7 mg (100 mg OC)−1, and typically followed TOC concentrations in the estuarine and shelf sediments, suggesting that the relative abundance of total carbohydrate was fairly constant in TOC. Total neutral sugars as detected by the nine major monosaccharides (lyxose, rhamnose, ribose, arabinose, fucose, xylose, galactose, mannose, and glucose) yielded between 4.0 and 18.6 mg (100 mg OC)−1 in the same sediments, suggesting that a significant amount of carbohydrates were not neutral aldoses. The bulk organic matter properties, isotopic composition and C/N ratios, combined with molecular-level carbohydrate compositions were used to assess the sources and accumulation of terrestrial organic matter in the Pearl River Estuary and the adjacent northern South China Sea shelf. Results showed a mixture of terrestrial riverine organic carbon with in situ phytoplankton organic carbon in the areas studied. Using a two end-member mixing model based on δ13C values and C/N ratios, we estimated that the terrestrial organic carbon contribution to the surface sediment TOC was ca. 57±13% for Lingdingyang Bay, 19±2% for the inner shelf, which decreased further to 4.3±0.5% on the outer shelf. The molecular composition of the carbohydrate in surface sediments also suggested that the inner estuary was rich in terrestrial-derived carbohydrates but that the contribution of terrestrial-derived carbohydrates decreased offshore. Terrestrial organic carbon accumulation flux was estimated as 1.37±0.92×1011 g yr−1 in Lingdingyang Bay, which accounted for 37±25% of the terrestrial organic carbon transported to the Bay. The burial efficiency of terrestrial organic matter was markedly lower than that of suspended particulate substance (~71%) suggesting that the riverine POC undergoes significant degradation and replacement during transportation through the estuary.


2020 ◽  
Author(s):  
Van Liem Nguyen ◽  
Birgit Wild ◽  
Örjan Gustafsson ◽  
Igor Semiletov ◽  
Oleg Dudarev ◽  
...  

<p>Widespread accelerated permafrost thawing is predicted for this century and beyond. This threatens to remobilize the large amounts of Mercury (Hg) currently ‘locked’ in Arctic permafrost soils to the Arctic Ocean and thus potentially lead to severe consequences for human and wildlife health. Future risks of Arctic Hg in a warmer climate are, however, poorly understood. One crucial knowledge gap to fill is the fate of Hg once it enters the marine environment on the continental shelves. Arctic rivers are already today suggested to be the main source of Hg into the Arctic Ocean, with dissolved and particulate organic matter (DOM and POM, respectively) identified as important vectors for the land to sea transport.</p><p>In this study, we have investigated total Hg (HgT) and monomethylmercury (MeHg) concentrations in surface sediments from the East Siberian Arctic Shelf (ESAS) along a transect from the Lena river delta to the Laptev Sea continental slope. The ESAS is the world’s largest continental shelf and receives large amounts of organic carbon by the great Arctic Russian rivers (e.g., Lena, Indigirka and Kolyma), remobilized from continuous and discontinuous permafrost regions in the river catchments, and from coastal erosion. Data on HgT and MeHg levels in ESAS sediments is however limited. Here, we observed concentrations of Hg ranging from 30 to 96 ng Hg g<sup>-1</sup> d.w. of HgT, and 0.03 to 9.5 ng Hg g<sup>-1</sup> d.w. of MeHg. Similar concentrations of HgT were observed close to the river delta (54 ± 19 ng Hg g<sup>-1</sup> d.w.), where >95 % of the organic matter is of terrestrial origin, and the other section of the transect (42 ± 7 ng Hg g<sup>-1</sup> d.w.) where the terrestrial organic matter is diluted with carbon from marine sources. In contrast, we observed higher concentrations of MeHg close to the river delta (0.72 ± 0.71 ng Hg g<sup>-1</sup> d.w. as MeHg) than further out on the continental shelf (0.031 ± 0.71 ng Hg g<sup>-1</sup> d.w. as MeHg). We also observed a positive correlation between the MeHg:Hg ratio and previously characterized molecular markers of terrestrial organic matter (Bröder et al. Biogeosciences (2016) & Nature Com. (2018)). We thus suggest riverine inputs, rather than in situ MeHg formation, to explain observed MeHg trends.</p>


2018 ◽  
Vol 15 (2) ◽  
pp. 471-490 ◽  
Author(s):  
Volker Brüchert ◽  
Lisa Bröder ◽  
Joanna E. Sawicka ◽  
Tommaso Tesi ◽  
Samantha P. Joye ◽  
...  

Abstract. 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; 35S-sulfate tracer experiments; pore-water dissolved inorganic carbon (DIC); δ13CDIC; 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 allows 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 50 cm of sediment, aerobic carbon mineralization dominated degradation and comprised on average 84 % of the depth-integrated carbon mineralization. Oxygen uptake rates and anaerobic carbon mineralization rates were higher in the eastern East Siberian Sea shelf compared to the Laptev Sea shelf. DIC ∕ NH4+ ratios in pore waters 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 seas suggests that about 16 Tg C yr−1 is respired in the outer shelf seafloor sediment. Of the organic matter buried below the oxygen penetration depth, between 0.6 and 1.3 Tg C yr−1 is degraded by anaerobic processes, with a terrestrial organic carbon contribution ranging between 0.3 and 0.5 Tg yr−1.


2014 ◽  
Vol 11 (10) ◽  
pp. 14359-14411 ◽  
Author(s):  
M. Winterfeld ◽  
M. A. Goñi ◽  
J. Just ◽  
J. Hefter ◽  
G. Mollenhauer

Abstract. The Lena River in central Siberia is one of the major pathways translocating terrestrial organic matter (OM) from its vast catchment area to the coastal zone of the Laptev Sea and the Arctic Ocean. The permafrost soils of its far south stretching catchment, which store huge amounts of OM, will most likely respond differently to climate warming and remobilize previously frozen OM with distinct properties specific for the source vegetation and soil. To characterize the material discharged by the Lena River, we analyzed the lignin phenol composition in total suspended matter (TSM) from surface water collected in spring and summer, surface sediments from the Buor Khaya Bay along with soils from the Lena Delta's first (Holocene) and third terraces (Pleistocene ice complex), and plant samples. Our results show that lignin-derived cinnamyl:vanillyl (C/V) and syringyl:vanillyl (S/V) ratios are >0.14 and 0.25, respectively, in TSM and surface sediments, whereas in delta soils they are >0.16 and >0.51, respectively. These lignin compositions are consistent with significant inputs of organic matter from non-woody angiosperm sources mixed with organic matter derived from woody gymnosperm sources. We applied a simple linear mixing model based on the C/V and S/V ratios and the results indicate the organic matter in delta TSM samples and Buor Khaya Bay surface sediments contain comparable contributions from gymnosperm material, which is primarily derived from the taiga forests south of the delta, and angiosperm material typical for tundra vegetation. Considering the small catchment area covered by tundra (∼12%), the input is substantial and tundra-derived OM input is likely to increase in a warming Arctic. The similar and high acid to aldehyde ratios of vanillyl and syringyl (Ad/AlV, S) in Lena Delta summer TSM (>0.7 and >0.5, respectively) and Buor Khaya Bay surface sediments (>1.0 and >0.9, respectively) suggest that the OM is highly degraded and Lena River summer TSM could be a possible source for the surface sediments. The Ad/AlV, S ratios of the first and third delta terraces were generally lower (mean ratios >0.4 and >0.4, respectively) than summer TSM and surface sediments. This implies that TSM contains additional contributions from a more degraded OM source (southern catchment and/or finer more degraded particle size). Alternatively, OM degradation on land after permafrost thawing and subaqueously during transport and sedimentation could be considerable. Despite the high natural heterogeneity of OM stored in delta soils and exported by the Lena River, the catchment characteristic vegetation is reflected by the lignin biomarker composition. Climate warming related changes in the Lena River catchment may be detectable in changing lignin biomarker composition and diagenetic alteration.


2015 ◽  
Vol 12 (7) ◽  
pp. 2261-2283 ◽  
Author(s):  
M. Winterfeld ◽  
M. A. Goñi ◽  
J. Just ◽  
J. Hefter ◽  
G. Mollenhauer

Abstract. The Lena River in central Siberia is one of the major pathways translocating terrestrial organic matter (OM) from its vast catchment area to the coastal zone of the Laptev Sea and the Arctic Ocean. The permafrost soils of its far south-stretching catchment, which store huge amounts of OM, will most likely respond differently to climate warming and remobilize previously frozen OM with distinct properties specific for the source vegetation and soil. To characterize the material discharged by the Lena River, we analyzed the lignin phenol composition in total suspended matter (TSM) from surface water collected in spring and summer, surface sediments from Buor Khaya Bay along with soils from the Lena Delta's first (Holocene) and third terraces (Pleistocene ice complex), and plant samples. Our results show that lignin-derived cinnamyl : vanillyl (C / V) and syringyl : vanillyl (S / V) ratios are > 0.14 and 0.25, respectively, in TSM and surface sediments, whereas in delta soils they are > 0.16 and > 0.51, respectively. These lignin compositions are consistent with significant inputs of organic matter from non-woody angiosperm sources mixed with organic matter derived from woody gymnosperm sources. We applied a simple linear mixing model based on the C / V and S / V ratios, and the results indicate the organic matter in delta TSM samples and Buor Khaya Bay surface sediments contain comparable contributions from gymnosperm material, which is primarily derived from the taiga forests south of the delta, and angiosperm material typical for tundra vegetation. Considering the small catchment area covered by tundra (~ 12%), the input is substantial and tundra-derived OM input is likely to increase in a warming Arctic. The similar and high acid to aldehyde ratios of vanillyl and syringyl (Ad / AlV, S) in Lena Delta summer TSM (> 0.7 and > 0.5, respectively) and Buor Khaya Bay surface sediments (> 1.0 and > 0.9, respectively) suggest that the OM is highly degraded and Lena River summer TSM could be a possible source of the surface sediments. The Ad / AlV, S ratios of the first and third delta terraces were generally lower (mean ratios > 0.4 and > 0.4, respectively) than summer TSM and surface sediments. This implies that TSM contains additional contributions from a more degraded OM source (southern catchment and/or finer more degraded particle size). Alternatively, OM degradation on land after permafrost thawing and subaqueously during transport and sedimentation could be considerable. Despite the high natural heterogeneity of OM stored in delta soils and exported by the Lena River, the catchment-characteristic vegetation is reflected by the lignin biomarker composition. Climate-warming-related changes in the Lena River catchment may be detectable in changing lignin biomarker composition and diagenetic alteration.


2021 ◽  
Author(s):  
Alexander Ulyantsev ◽  
Svetlana Bratskaya ◽  
Nikolay Belyaev ◽  
Oleg Dudarev ◽  
Igor Semiletov

<p>The modern East Siberian Arctic shelf represents a fascinating area with a vast expansion of subsea permafrost that holds a large pool of frozen immobilised organic carbon (OC). Amplified climate change at high latitudes has raised growing concerns about potential positive carbon–climate feedbacks. Degradation of permafrost in the Arctic could constitute a positive feedback to climate change due to activation of this OC stock, while recognizing the origin and peculiarities of organic matter (OM) is useful for predicting the potential for involving the ancient OC in modern carbon cycling. This paper emphasises the molecular composition of lignin-derived phenols (LDP) in bottom sediments and subsea permafrost from the Laptev Sea shelf as a proxy to describe the main sources, distribution, and preservation of terrestrial OM. The compositional pattern and concentration of LDP revealed irregular dynamics of terrigenous OM supply in the study area, that were governed primarily by continental flows. The OC concentration in the studied sediments varied from 0.04% to 23.1% (mean 1.74%, median 1.07%). The concentration of LDP in the studied 126 samples from five sediment cores obtained from Buor-Khaya Bay varied from 0.7 to 13191 (mean 539, median 63.5) µg/g of dry sediment as the sum of vanillyl, syringyl, and cinnamyl (VSC) compounds and from 0.03 to 27.6 (mean 1.61, median 0.76) mg/100 mg of OC content. All OC-rich samples showed higher concentrations of LDP and virtually non-oxidized lignin. Vegetation proxies suggested that vascular plant tissues account for a significant fraction of the lignin in the examined samples, with a strong share of gymnosperms. The concentration of LDP correlates to OC content, indicating a strong supply of terrestrial OC to the study area. Degradation proxies indicate a predominant supply of wood-rich non-oxidized terrestrial OM. The well-preserved lignin revealed in the studied deposits represents a specific feature of Quaternary lithodynamics of the Laptev Sea and is not typical for the majority of bottom sediments of the World Ocean. Good correlation between OC and lignin concentration suggests that terrigenous fluxes were the main contributor to OM supply. Distribution of specific lignin phenols and related ratios coupled with lithology and grain size revealed that fluvial processes have been leading here.</p><p>This research was supported through the Russian Scientific Foundation (grant no. 19-77-10044) within the framework of the state assignment of the Shirshov Institute of Oceanology RAS (grant no. 0149-2019-0006).</p>


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