Carbonaceous material export from Siberian permafrost tracked across the Arctic Shelf using Raman spectroscopy

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 slower 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

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

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

GDGT distributions in the East Siberian Sea: implications for organic carbon export, burial and degradation

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

Distributions of bacterial and archaeal membrane lipids in surface sediments reflect differences in input and loss of terrestrial organic carbon along a cross-shelf Arctic transect

Enhanced climate warming affecting the Arctic region could have a dramatic impact on the terrigenous organic carbon (terrOC) stored in the Eurasian permafrost and could increase the amount of OC remobilized to the Arctic shelves. An improved understanding of the fate of this remobilized soil OC is essential for better understanding of the consequences for the Arctic and global carbon cycle. In this study, glycerol dialkyl glycerol tetraethers (GDGTs) and bacteriohopanepolyols (BHPs) in surface sediments along a 500 km cross shelf transect from the mouth of the Kolyma River to the middle of the vast East Siberian Sea were analysed to assess their potential and that of the associated branched and isoprenoid tetraether (BIT) and R′soil indices for tracing terrOC in Arctic systems. Both BHP and GDGT contributions indicated the greatest contribution of terrOC close to the river mouth, while the associated indices showed declining trends in an offshore direction, supporting an increasing marine OC input and/or a decrease in terrOC. However, while the BHPs indicated a dominance of terrOC at the start of the transect, the GDGTs suggested a much larger, almost 50%, marine OC input at this point. In addition, the BIT index displayed an exponential decline, controlled mainly by a substantial contribution of marine GDGTs, while R′soil revealed a linear trend governed primarily by the removal of soil marker BHPs. These field results suggest that both biomarker approaches could be used to trace terrigenous derived OC in the Arctic environment. However, using a single proxy approach is not recommended and may lead to an under or over estimation of the relative importance of terrOC. Using a multi-proxy approach is valuable for fully understanding the fate of terrigenous derived OC along Arctic land-ocean transects

Source, transport and fate of soil organic matter inferred from microbial biomarker lipids on the East Siberian Arctic Shelf

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

Supplementary material to GDGT distributions in the East Siberian Sea: implications for organic carbon export, burial and degradation

This is supplimentary material to GDGT distributions in the East Siberian Sea: implications for organic carbon export, burial and degradatio

Distributions of bacterial and archaeal membrane lipids in surface sediments reflect differences in input and loss of terrestrial organic carbon along a cross-shelf Arctic transect

Tarjeta Postal de D. G. d´Aguanno, jurista italiano, a D. Pedro Dorado Montero, sobre un número de la "Rivista di Storia e Filosofia del Diritto