scholarly journals Macromolecular composition of terrestrial and marine organic matter in sediments across the East Siberian Arctic Shelf

2016 ◽  
Vol 10 (5) ◽  
pp. 2485-2500 ◽  
Author(s):  
Robert B. Sparkes ◽  
Ayça Doğrul Selver ◽  
Örjan Gustafsson ◽  
Igor P. Semiletov ◽  
Negar Haghipour ◽  
...  

Abstract. Mobilisation of terrestrial organic carbon (terrOC) from permafrost environments in eastern Siberia has the potential to deliver significant amounts of carbon to the Arctic Ocean, via both fluvial and coastal erosion. Eroded terrOC can be degraded during offshore transport or deposited across the wide East Siberian Arctic Shelf (ESAS). Most studies of terrOC on the ESAS have concentrated on solvent-extractable organic matter, but this represents only a small proportion of the total terrOC load. In this study we have used pyrolysis–gas chromatography–mass spectrometry (py-GCMS) to study all major groups of macromolecular components of the terrOC; this is the first time that this technique has been applied to the ESAS. This has shown that there is a strong offshore trend from terrestrial phenols, aromatics and cyclopentenones to marine pyridines. There is good agreement between proportion phenols measured using py-GCMS and independent quantification of lignin phenol concentrations (r2 = 0.67, p < 0.01, n = 24). Furfurals, thought to represent carbohydrates, show no offshore trend and are likely found in both marine and terrestrial organic matter. We have also collected new radiocarbon data for bulk OC (14COC) which, when coupled with previous measurements, allows us to produce the most comprehensive 14COC map of the ESAS to date. Combining the 14COC and py-GCMS data suggests that the aromatics group of compounds is likely sourced from old, aged terrOC, in contrast to the phenols group, which is likely sourced from modern woody material. We propose that an index of the relative proportions of phenols and pyridines can be used as a novel terrestrial vs. marine proxy measurement for macromolecular organic matter. Principal component analysis found that various terrestrial vs. marine proxies show different patterns across the ESAS, and it shows that multiple river–ocean transects of surface sediments transition from river-dominated to coastal-erosion-dominated to marine-dominated signatures.

2016 ◽  
Author(s):  
Robert B. Sparkes ◽  
Ayça Dogrul Selver ◽  
Örjan Gustafsson ◽  
Igor P. Semiletov ◽  
Negar Haghipour ◽  
...  

Abstract. Mobilisation of terrestrial organic carbon (terrOC) from permafrost environments in Eastern Siberia has the potential to deliver significant amounts of carbon to the Arctic Ocean, via both fluvial and coastal erosion. Eroded terrOC can be degraded during offshore transport, or deposited across the wide East Siberian Arctic Shelf (ESAS). Most studies of terrOC on the ESAS have concentrated on solvent-extractable organic matter, but this represents only a small proportion of the total terrOC load. In this study we have used pyrolysis gas chromatography mass spectrometry (py-GCMS) to study all major groups of macromolecular components of the terrOC; this is the first time that this technique has been applied to the ESAS. This has shown that there is a strong offshore trend from terrestrial Phenols, Aromatics, Cyclopentenones to marine Pyridines. There is good agreement between proportion Phenols measured using py-GCMS and independent quantification of lignin phenol concentrations (r2 = 0.67, p < 0.01, n = 24). Furfurals, thought to represent carbohydrates, show no offshore trend and are likely found in both marine and terrestrial organic matter. We have also collected new radiocarbon data for bulk OC (14COC) which, when coupled with previous measurements, allows us to produce the most comprehensive 14COC map of the ESAS to date. Combining the 14COC and py-GCMS data suggests that the Aromatics group of compounds is likely sourced from old, aged terrOC in contrast to the Phenols group, which is likely sourced from modern woody material. We propose that an index of the relative proportions of Phenols and Pyridines can be used as a novel terrestrial vs. marine proxy measurement for macromolecular organic matter. Principal component analysis found that various terrestrial vs. marine proxies show different patterns across the ESAS, and shows that multiple river-ocean transects of surface sediments transition from river-dominated to coastal erosion-dominated to marine-dominated signatures.


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

&lt;p&gt;&amp;#160; &amp;#160; 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&lt;sub&gt;2&lt;/sub&gt; and CH&lt;sub&gt;4&lt;/sub&gt; 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.&lt;/p&gt;&lt;p&gt;&amp;#160; &amp;#160; 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 &lt;strong&gt;1)&lt;/strong&gt; &lt;strong&gt;loss of functional groups&lt;/strong&gt;, thus the ratios of HMW n-alkanoic acids, HMW n-alkanols and sterols relative to HMW n-alkanes decrease; &lt;strong&gt;2)&lt;/strong&gt; &lt;strong&gt;reduction of unsaturated to saturated carbons&lt;/strong&gt;, so ratios of stanols relative to stenols increase; &lt;strong&gt;3) a higher formation of carboxylic acids in the lignin polymer&lt;/strong&gt; and hence&lt;strong&gt; &lt;/strong&gt;ratios of acids to aldehydes of vanillyl (Vd and Vl) and syringyl (Sd and Sl) increase.&lt;/p&gt;&lt;p&gt;&amp;#160; &amp;#160; 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 &amp;#8220;tannin-like&amp;#8221; compound 3,5-dihydrobenzoic acid to vanillyl (3,5-Bd/V), &amp;#946;-sitostanol/ &amp;#946;-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 &amp;#946;-sitostanol/&amp;#946;-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.&lt;/p&gt;


2021 ◽  
Author(s):  
Jens A. Hölemann ◽  
Bennet Juhls ◽  
Dorothea Bauch ◽  
Markus Janout ◽  
Boris P. Koch ◽  
...  

Abstract. Remobilization of soil carbon as a result of permafrost degradation in the drainage basin of the major Siberian rivers combined with higher precipitation in a warming climate potentially increase the flux of terrestrial derived dissolved organic matter (tDOM) into the Arctic Ocean. The Laptev (LS) and East Siberian Seas (ESS) receive enormous amounts of tDOM-rich river water, which undergoes at least one freeze-melt cycle in the Siberian Arctic shelf seas. To better understand how freezing and melting affect the tDOM dynamics in the LS and ESS, we sampled sea ice, river and seawater for their dissolved organic carbon (DOC) concentration and the colored fraction of dissolved organic matter. The sampling took place in different seasons over a period of 9 years (2010–2019). Our results suggest that the main factor regulating the tDOM distribution in the LS and ESS is the mixing of marine waters with freshwater sources carrying different tDOM concentrations. Of particular importance in this context are the 211 km3 of meltwater from land-fast ice from the LS, containing ~ 0.3 Tg DOC, which in spring mixes with 245 km3 of river water from the peak spring discharge of the Lena River, carrying ~ 2.4 Tg DOC into the LS. During the ice-free season, tDOM transport on the shelves takes place in the surface mixed layer, with the direction of transport depending on the prevailing wind direction. In winter, about 1.2 Tg of brine-related DOC, which was expelled from the growing land-fast ice in the LS, is transported in the near-surface water layer into the Transpolar Drift Stream that flows from the Siberian Shelf toward Greenland. The actual water depth in which the tDOM-rich brines are transported, depends mainly on the density stratification of the LS and ESS in the preceding summer and the amount of ice produced in winter. We suspect that climate change in the Arctic will fundamentally alter the dynamics of tDOM transport in the Arctic marginal seas, which will also have consequences for the Arctic carbon cycle.


2018 ◽  
Author(s):  
Birgit Wild ◽  
Natalia Shakhova ◽  
Oleg Dudarev ◽  
Alexey Ruban ◽  
Denis Kosmach ◽  
...  

Abstract. Thaw of subsea permafrost across the Arctic Ocean shelves might promote the degradation of organic matter to CO2 and CH4, but also create conduits for transfer of deeper CH4 pools to the atmosphere and thereby amplify global warming. In this study, we describe sedimentary characteristics of three subsea permafrost cores of 21–56 m length drilled near the current delta of the Lena River in the Buor–Khaya Bay on the East Siberian Arctic Shelf, including content, origin and degradation state of organic matter around the current thaw front. Grain size distribution and optically stimulated luminescence dating suggest the alternating deposition of aeolian silt and fluvial sand over the past 160 000 years. Organic matter in 3 m sections across the current permafrost table was characterized by low organic carbon contents (average 0.7 ± 0.2 %) as well as enriched δ13C values and low concentrations of the terrestrial plant biomarker lignin compared to other recent and Pleistocene deposits in the study region. The lignin phenol composition further suggests contribution of both tundra and boreal forest vegetation, at least the latter likely deposited by rivers. Our findings indicate high variability in organic matter composition of subsea permafrost even within a small study area, reflecting its development in a heterogeneous and dynamic landscape. Even with this relatively low organic carbon content, the high rates of observed subsea permafrost thaw in this area yield a thaw-out of 1.6 kg OC m−2 year−1, emphasizing the need to constrain the fate of the poorly described and thawing subsea permafrost organic carbon pool.


2020 ◽  
Author(s):  
Felipe Matsubara ◽  
Birgit Wild ◽  
Jannik Martens ◽  
Rickard Wennström ◽  
Tommaso Tesi ◽  
...  

&lt;p&gt;Warming-induced permafrost thawing is expected to intensify the remobilization of terrigenous organic matter (terrOM) to the East Siberian Arctic Shelf (ESAS) via increasing river discharge and coastal erosion. Earlier studies have focused on source apportionment and transport of terrOM, with less emphasis on its degradation state during cross-shelf transport. Since degradation of terrOM is the link between permafrost thawing and release of GHGs such as CO&lt;sub&gt;2&lt;/sub&gt;, this study focuses on the degradation characteristics. Hence, the main objective of this study is to assess the patterns of terrOM degradation across the East Siberian Arctic Shelf using molecular proxies that are specific to terrOM.&lt;/p&gt;&lt;p&gt;Lignin phenols and high molecular weight (HMW) n-alkanes and n-alkanoic acids are only produced by terrestrial plants which make them suitable biomarkers to assess degradation of terrestrial material throughout the ESAS. The lignin-based proxies acid to aldehyde ratios of vanillyl (Vd/Vl) and syringyl (Sd/Sl) structural units, as well as the ratio of 3,5-dihydroxybenzoic acid over vanillin (3,5-Bd/V) are expected to increase during degradation under oxic conditions. Fresh terrestrial plant material is predominated by long odd-numbered (&gt;C&lt;sub&gt;25&lt;/sub&gt;) and even-numbered (&gt;C&lt;sub&gt;24&lt;/sub&gt;) carbon chain length of n-alkanes and n-alkanoic acids, respectively. This dominance is described in the Carbon Preference Index (CPI). When degradation takes place, CPI values decrease accordingly, describing how much of the original material was preserved. Ratios of HMW n-alkanoic acids to HMW n-alkanes are also expected to decrease during microbial degradation owing to preferential loss of functional groups.&lt;/p&gt;&lt;p&gt;The data show increasing Vd/Vl, Sd/Sl and 3,5-Bd/V ratios, and decreasing HMW n-alkanes CPI values toward the outer shelf, consistent with continuous degradation of terrOM across the ESAS. While Vd/Vl and HMW n-alkane CPI did not show strong differences between east and west, Sd/Sl ratios were highest in the outer western ESAS, and 3,5-Bd/V ratios were highest in the outer east. These differences may reflect different terrOM pools along the ESAS due to differences in vegetation zones releasing the input material through river discharge and coastal erosion. In contrast, HMW n-alkanoic acid to HMW n-alkane ratio and HMW n-alkanoic acid CPI showed inconsistent patterns across the ESAS; reasons for it are currently being investigated. These results will also be complemented by additional biomarkers to better understand the degradation of terrOM during cross-shelf transport.&lt;/p&gt;


2016 ◽  
Vol 13 (17) ◽  
pp. 4899-4914 ◽  
Author(s):  
Juliane Bischoff ◽  
Robert B. Sparkes ◽  
Ayça Doğrul Selver ◽  
Robert G. M. Spencer ◽  
Örjan Gustafsson ◽  
...  

Abstract. The Siberian Arctic contains a globally significant pool of organic carbon (OC) vulnerable to enhanced warming and subsequent release by both fluvial and coastal erosion processes. However, the rate of release, its behaviour in the Arctic Ocean and vulnerability to remineralisation is poorly understood. Here we combine new measurements of microbial biohopanoids including adenosylhopane, a lipid associated with soil microbial communities, with published glycerol dialkyl glycerol tetraethers (GDGTs) and bulk δ13C measurements to improve knowledge of the fate of OC transported to the East Siberian Arctic Shelf (ESAS). The microbial hopanoid-based soil OC proxy R′soil ranges from 0.0 to 0.8 across the ESAS, with highest values nearshore and decreases offshore. Across the shelf R′soil displays a negative linear correlation with bulk δ13C measurements (r2 = −0.73, p =  < 0.001). When compared to the GDGT-based OC proxy, the branched and isoprenoid tetraether (BIT) index, a decoupled (non-linear) behaviour on the shelf was observed, particularly in the Buor-Khaya Bay, where the R′soil shows limited variation, whereas the BIT index shows a rapid decline moving away from the Lena River outflow channels. This reflects a balance between delivery and removal of OC from different sources. The good correlation between the hopanoid and bulk terrestrial signal suggests a broad range of hopanoid sources, both fluvial and via coastal erosion, whilst GDGTs appear to be primarily sourced via fluvial transport. Analysis of ice complex deposits (ICDs) revealed an average R′soil of 0.5 for the Lena Delta, equivalent to that of the Buor-Khaya Bay sediments, whilst ICDs from further east showed higher values (0.6–0.85). Although R′soil correlates more closely with bulk OC than the BIT, our understanding of the endmembers of this system is clearly still incomplete, with variations between the different East Siberian Arctic regions potentially reflecting differences in environmental conditions (e.g. temperature, pH), but other physiological controls on microbial bacteriohopanepolyol (BHP) production under psychrophilic conditions are as yet unknown.


2016 ◽  
Author(s):  
Juliane Bischoff ◽  
Robert B. Sparkes ◽  
Ayça Doğrul Selver ◽  
Robert G. M. Spencer ◽  
Örjan Gustafsson ◽  
...  

Abstract. The Siberian Arctic contains a globally significant pool of organic carbon (OC) vulnerable to enhanced warming and subsequent release by both fluvial and coastal erosion processes. However, the rate of release, its behaviour in the Arctic Ocean and vulnerability to remineralisation is poorly understood. Here we combine new measurements of microbial biohopanoids including adenosylhopane, a lipid associated with soil microbial communities, with published glycerol dialkyl glycerol tetraether (GDGTs) and bulk δ13C 5 measurements to improve knowledge of the fate of OC transported to the East Siberian Arctic Shelf (ESAS). The microbial hopanoid-based soil OC proxy R'soil ranges from 0.0 to 0.8 across the ESAS, with highest values near shore and decreases offshore. Across the shelf R'soil displays a negative linear correlation with bulk δ13C measurements (r2 = −0.73, p = < 0.001). When compared to the GDGT based OC proxy, the Branched and Isoprenoid tetraether (BIT) index, a decoupled (non-linear) behaviour on the shelf was observed, particularly in the Buor-Khaya Bay where the R'soil shows limited 10 variation, whereas the BIT index shows a rapid decline moving away from the Lena River outflow channels. This reflects a balance between delivery and removal of OC from different sources. The good correlation between the hopanoid and bulk terrestrial signal suggests a broad range of hopanoid sources, both fluvial and via coastal erosion whilst GDGTs appear to be primarily sourced via fluvial transport. Analysis of ice complex deposits (ICDs) revealed an average R'soil of 0.5 for the Lena delta, equivalent to that of the Buor-Khaya Bay sediments, whilst ICDs from further East showed higher values (0.6–0.85). Al15 though R'soil correlates more closely with bulk OC than the BIT, our understanding of the endmembers of this system is clearly still incomplete with east-west variations potentially reflecting differences in environmental conditions (e.g. temperature, pH) but other physiological controls on microbial BHP production under psychrophilic conditions are as yet unknown.


2015 ◽  
Vol 12 (12) ◽  
pp. 3753-3768 ◽  
Author(s):  
R. B. Sparkes ◽  
A. Doğrul Selver ◽  
J. Bischoff ◽  
H. M. Talbot ◽  
Ö. Gustafsson ◽  
...  

Abstract. Siberian permafrost contains a globally significant pool of organic carbon (OC) that is vulnerable to enhanced warming and subsequent release into the contemporary carbon cycle. OC release by both fluvial and coastal erosion has been reported in the region, but the behaviour of this material in the Arctic Ocean is insufficiently understood. The balance between OC deposition and degradation on the East Siberian Arctic Shelf (ESAS) influences the climate–carbon cycle feedback in this area. In this study we couple measurements of glycerol dialkyl glycerol tetraethers (GDGTs) with bulk geochemical observations to improve knowledge of the sources of OC to the ESAS, the behaviour of specific biomarkers on the shelf and the balance between delivery and removal of different carbon pools. Branched GDGT (brGDGT) concentrations were highest close to river mouths, yet low in "ice complex" permafrost deposits, supporting recent observations that brGDGTs are mostly delivered by fluvial erosion, and may be a tracer for this in complex sedimentary environments. BrGDGT concentrations and the branched and isoprenoidal tetraether (BIT) index reduced quickly offshore, demonstrating a rapid reduction in river influence. Stable carbon isotope ratios changed at a different rate to the BIT index, suggesting not only that OC on the shelf is sourced from fluvial erosion but also that erosion of coastal sediments delivers substantial quantities of OC to the Arctic Ocean. A model of OC export from fluvial, coastal and marine sources is able to recreate the biomarker and bulk observations and provide estimates for the influence of fluvial and coastal OC across the whole shelf. The model shows that coastal erosion delivers 43 % of the OC and 87 % of the mineral sediment to the ESAS, but that rivers deliver 72 % of brGDGTs, indicating that brGDGTs can be used as a proxy for river-derived sediment.


2018 ◽  
Vol 12 (10) ◽  
pp. 3293-3309 ◽  
Author(s):  
Robert B. Sparkes ◽  
Melissa Maher ◽  
Jerome Blewett ◽  
Ayça Doğrul Selver ◽  
Örjan Gustafsson ◽  
...  

Abstract. Warming-induced erosion of permafrost from Eastern Siberia mobilises large amounts of organic carbon and delivers it to the East Siberian Arctic Shelf (ESAS). In this study Raman spectroscopy of carbonaceous material (CM) was used to characterise, identify and track the most recalcitrant fraction of the organic load: 1463 spectra were obtained from surface sediments collected across the ESAS and automatically analysed for their Raman peaks. Spectra were classified by their peak areas and widths into disordered, intermediate, mildly graphitised and highly graphitised groups and the distribution of these classes was investigated across the shelf. Disordered CM was most prevalent in a permafrost core from Kurungnakh Island and from areas known to have high rates of coastal erosion. Sediments from outflows of the Indigirka and Kolyma rivers were generally enriched in intermediate CM. These different sediment sources were identified and distinguished along an E–W transect using their Raman spectra, showing that sediment is not homogenised on the ESAS. Distal samples, from the ESAS slope, contained greater amounts of highly graphitised CM compared to the rest of the shelf, attributable to degradation or, more likely, winnowing processes offshore. The presence of all four spectral classes in distal sediments demonstrates that CM degrades much more slowly than lipid biomarkers and other traditional tracers of terrestrial organic matter and shows that alongside degradation of the more labile organic matter component there is also conservative transport of carbon across the shelf toward the deep ocean. Thus, carbon cycle calculations must consider the nature as well as the amount of carbon liberated from thawing permafrost and other erosional settings.


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