Growing anthropogenic activity in the Arctic, especially near regional municipal and transportation hubs, threatens coastal environments with significant changes and contamination. A detailed study of a wide set of organic-geochemical proxies in surface and subsurface sediments and soils around the typical urbanized Arctic area (Tromsø, Norway) was performed to investigate natural and anthropogenic input of hydrocarbons. The sites were located close to main areas of human activity and differed in the level of anthropogenic pressure: oil terminal, boat harbor and recreation beach zone in the city center, and a remote, conditionally-clean area. The samples from each site were collected along four subtidal – intertidal – supratidal transects. GC–MS data on the distribution of more than 110 compounds were obtained including n-alkanes, isoprenoids, terpanes, parent polycyclic aromatic hydrocarbons (PAHs), and alkyl PAHs. Organic matter embedded in a mineral matrix was more thermally mature than its fresh non-bound fraction. Biomarker distribution and diagnostic ratios attested to the predominantly local origin of near-shore organic matter formation (phytoplankton, algae, high foliar plants, grass). PAH composition revealed a significant input of pyrogenic components from liquid and solid fuel combustion to the surface coarse-grained sediments. Background bacterial activity was evidenced by the high content of biohopanes and hopenes in less polluted sediments and soils. The presence of an unresolved complex mixture and even n-alkanes in sediment profiles from the most polluted sites attested to the active biodegradation that, together with the erosion of the upper layers by tidal currents, reduces the toxic compound penetration deeper into the sediments.
––The main factors controlling the bulk sedimentation in the Siberian segment of the Lomonosov Ridge (axial part and western slope) and the Laptev Sea continental margin during the late Cenozoic were studied using a complex of geomorphological, lithological, and organic geochemical data. Samples for the study were collected during the cruises of R/V Akademik Fedorov in 2005 and 2007 and nuclear icebreaker Rossiya in 2007. Analysis of the group and molecular composition of the dispersed organic matter (DOM) in bottom sediments has shown that the input of terrigenous sediments enriched in the products of abrasion of lithified rocks determines sedimentation process on the continental slope of the Laptev Sea and in the Amundsen Basin. The individual characteristics of the DOM of the late Cenozoic sediments from the Lomonosov Ridge reflect the wide diversity of sedimentary sources and depositional environments. Subaqueous erosion of edaphogenic products and pre-Holocene sediments plays an important part in sedimentation together with terrigenous flow and ice transport.
Summary The complex study of the organic matter (OM) and HC molecular markers in sediments and soils of the Arctic littoral is an important step to the environment protection. The study of polycyclic aromatic HCs (PAHs) is of particular interest due to their toxicity and high content in the main anthropogenic pollutants (oil, fuels, combustion products etc.).
Summary The main idea was to investigate the composition of hydrocarbon (HC) molecular markers, as indicators of the origin of sedimentary material. The object of the study is bottom sediments collected from latitudinal transects stretching along the outer edge of the shelf and the upper continental slope of the Laptev Sea. Sampling was made during the research cruise of FSBI VNIIOkeangeologia in 2018 (R/V Ivan Petrov). The molecular composition of the DOM indicates a significant input of terrigenous components of diagenetic maturity degree to the sediments of the region. Moreover, the input of molecular markers characteristic for the bacterial activity (possibly methanotrophic) is detected in some sediments (n-C16 and n-C18 predominate in composition of the lower molecular weight n-alkanes; the tricyclic terpanes ratio (2(C19+С20)/(C23+С24+C25+С26) < 1). The inflow of the reduced Atlantic waters with the along-slope currents and the processes of bottom and coastal abrasion determine the contribution of the transformed marine DOM to the sediments of continental margin.
Information about hydrocarbons (HCs) distribution in components of geological environment (including aromatic (Ar) compounds) allows to estimate relative amounts of both natural and anthropogenic components and reveal sources of contamination. HCs are widely spread in lithosphere and create stable geochemical background. Variations in their composition attest to the specificity of initial organic matter, conditions of its accumulation and transformation. The studied samples of soils and surface bottom sediments were collected during the research expedition in July, 2019 (supported by RFBR №18-54-20001 and NFR №280724). On the Norwegian coast of the Barents Sea the area of study included: salt marshes of Tana and Varanger fjords, littoral zone of rocky shores around Kiberg. In the Russian part of the Barents Sea samples were taken from the shallow water area of the Eastern coast of the Kola Bay. All samples were taken along the sublittoral – littoral – supralittoral transects appropriate for a detailed study of the organic matter (OM) spatial distribution. Study of the group composition of ArHCs in the extractable part of soil and sedimentary OM were performed using spectrofluorimetry. The method is based on the ability of ArHCs to fluoresce under the influence of ultraviolet emitting in narrow spectral ranges determined by their molecular structure. This allows us to characterize the nature of ArHCs and determine possible sources of their input. The spectrum characteristics of samples from intertidal zone of the Tana fjord salt marshes reflect the input of fresh unoxidized petroleum products such as diesel fuels and engine oils. The significant increase of ArHCs fluorescence intensity in surface sediments may testify to recent pollution accidents. The spectrum traditionally associated with the estuarine-delta and lacustrine and swampy facies and characteristic for the post-sedimentation and early diagenetic stage of OM transformation was detected in samples from the salt marshes of Varanger fjord. ArHCs of mixed origin (natural and anthropogenic) are identified in samples from the littoral zone of rocky shores of Kiberg. The spectral data of littoral sediments are typical for the polluted areas with high input of petroleum products. The specific maxima in the long wavelength region of spectrum that is characteristic for the high molecular weight aromatic compounds from the land plants is also detected in these samples. Spectral characteristics of ArHCs of bottom sediments and soils collected from the shallow water area of the Russian part of the Barents Sea point to the presence of both low molecular weight benzene HCs (high volatile components of flammable liquids) and high molecular weight compounds (oil fuel, gas oil). The detailed study of these anthropogenic HC components seems to be very important given the fact of their detection in all littoral samples. The further detailed study of the molecular markers and biomarkers (n-alkanes, isoprenoids, cyclanes, terpanes, PAHs) will increase our knowledge about HC sources, efficiency of their microbial and chemical degradation, allow to estimate human impacts on the environment of the region and draw up the regional “geochemical passport”.
Study of the molecular composition of the dispersed organic matter (OM) in bottom sediments of Lake Baikal was conducted (supported by RSF #19-17-00226). Sediments (11 gravity cores - 28 samples) were collected during research expeditions of the R/V “G.U. Vereschagin” (LIN SB RAS, Irkutsk) in 2016-2018. Variations in composition and ratios of aliphatic and aromatic components reflect changes of OM sources. Most n-alkane profiles show the distinguishable predominance of terrigenous components C27-C31. The highest biodegradation degree and increased content of isoprenoids is detected near the Gorevoy cliff where the active oil discharge was observed. Biogenic hopanes (ββ-hopanes and hopenes) predominate in most samples and diagenetic type of distribution is identified only in sediments with oil inclusions. Steranes are the minor components with ethylcholestanes as the main peaks attesting to the input of land plants. Increased values of perylene and phenanthrene in polycyclic aromatic HCs composition indicate the mixed biogenic-petrogenic nature of OM of the studied Lake Baikal sediments, while the oily samples contain only trace amounts of perylene. The branched 2,7-dimethyl alkanes (m/z 127) have been identified in mudstone samples from the Vendian Marna Formation from the Sayan-adjacent Biryusa area and in Permian and Upper Carboniferous coal-bearing rocks from superdeep well SV-27 (Vilui syneclise) [1]. Their precursors most likely are the analogues of branched methylenated acids detected in lipids of modern bacteria (9,10-methylene hexadecane, 9,10-methylene octadecane, and 11,12-methylene octadecane acids). Decarboxylation of the methylenated acids branched at the second and seventh carbon atoms during diagenesis and catagenesis should have resulted in 2,7-dimethyl alkanes that were detected in all immersed sediments of the southern, central and northern parts of Lake Baikal. Trace amounts of the other poorly studied group of compounds – monoaromatic steroids (MAS) were identified in bottom sediments near the mud volcano Kedr in the southern part of the lake. These structures can be formed during diagenetic transformations of sediments at the contacts of OM with clays (catalyzers) together with the formation of regular steranes and diasteranes (C27-C29). They have been previously detected in apocatagenetic rocks of the East Siberian sedimentary basin (ultradeep hole SV-27 from the Middle Vilyui area of the Vilyui syneclise) [2]. The absence of the main fragmental ion m/z 253 in the analyzed samples points to the migration of methyl alternate from C-17 to C-23 alkyl-chain position and agrees with distribution of the similar structures (m/z 281, 309, 366) in rocks of the hole SV-27. The detected 17-desmethyl-23-methylmonoaromatic steroids appear and exist at high temperatures and pressures and are very thermodynamically stable. Thus, the input of the OM of catagenetic maturity degree to the bottom sediments of Lake Baikal is likely associated with the deep fluid migration and mud volcanic breccia uplift to the surface. References [1] Kashirtsev V.A. et al., 2009. New homologous series of biomarker molecules from Vendian deposits of the Sayan-adjacent Biryusa area. Russian Geology and Geophysics 50, 541–545. [2] Kashirtsev V.A. et al., 2016. New monoaromatic steroids in organic matter of the apocatagenesis zone. Doklady Earth Sciences 469, 815–818.
—The main factors controlling the bulk sedimentation in the region of the Mendeleev Rise and the adjacent part of the Arctic Ocean during the late Cenozoic were studied using a complex of geomorphological, lithological, and organic geochemical data. Samples for the study were collected during the cruises of the R/V Akademik Fedorov in 2000, 2005, and 2007 and icebreaker Kapitan Dranitsyn in 2012. Analysis of the group and molecular compositions of the dispersed organic matter (DOM) in bottom sediments has shown that the input of terrigenous sediments enriched with abrasion products of lithified rocks from the eastern source province determines the Holocene–Pleistocene sedimentation on the continental slope of the East Siberian Sea and in the Podvodnikov Basin. The individual characteristics of DOM of the late Cenozoic deposits from the underwater mountains of the Mendeleev Rise reflect the wide diversity of sedimentary sources and depositional conditions. Subaqueous erosion and redeposition of denudation products of source rocks and pre-Holocene sediments play an important part in sedimentation together with a terrigenous flow and ice transport.
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The composition of bottom sediments of the western arctic shelf is mainly determined by the geological structure and lithologic-petrographic characteristics of rocks that form the coast, bottom and islands of the basin (Romankevich et al., 2001; Levitan et al., 2007). The presence of deep-sea troughs, shallow underwater plains and a complex hydrological regime is typical for the Kara Sea. Furthermore the maximum value of river discharge (about 41%), the inflow of cold waters from the Arctic basin and the Laptev Sea, and warm Atlantic waters from the Barents Sea create variety of sedimentation regimes.
The recent intensification of energy resource exploration and human activities in the Barents Sea (BS) requires a more thorough assessment of the natural and anthropogenic impact of hydrocarbons on the environment. We analyzed a wide set of sensitive indicators, including hydrocarbon molecular markers and organic matter (OM) maturity parameters in the Holocene sediments from three regions of the BS: the Kola-Kanin Monocline (KKM), the Svalbard shelf, and the Shtokman gas-condensate field (GCF). An increase in pyrogenic polycyclic aromatic hydrocarbons toward the core surface traces the intensification of anthropogenic contamination in the KKM region during last century. An input of highly mature OM from the eroded coal rocks of Barentsburg were confirmed by comparison of biomarker distribution in sediments and coals. An increase in biogenic hopanes and hopenes content down-core, and a crude-oil stage of OM maturity in surface sediments of the Shtokman GCF attests to hydrocarbons migration from subsurface strata.
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Variability in levels and sources of polycyclic aromatic hydrocarbons (PAH) in sediments from one large sea area off the coast of northern Norway (“North area”, NA) have been compared to similar data from another large area off the coast of southern Norway (“South area”, SA). Samples from NA were collected at the Norwegian continental shelf in south-western Barents Sea and north-eastern Norwegian Sea. Samples from SA were from the Norwegian Trench and the Skagerrak. Sediment cores have been dated, characterised by grain size distribution (GS) and organic carbon content (TOC), and the composition of PAH and geochemical biomarkers (alkanes and triterpanes) studied to provide an insight into the different sources of PAH. Generally, PAH levels are higher in sediments from SA compared to NA. A mixture of pyrogenic and petrogenic sources contribute to PAH levels in SA, while the contents of petrogenic PAH is negligible in surface sediments in NA. At some locations in NA, petrogenic PAH levels are elevated in the deepest sediment layers from pre-industrial times, indicating a natural input of petroleum through seepage. Occurrence of elevated levels of microbial hopanoids (hopenes) in the deepest sediment layers at some locations both in the north and the south indicate the presence of petroleum.
Subsurface sediments from a pockmark area in South-Western Barents Sea have been earlier found to contain elevated levels of petroleum-related polycyclic aromatic hydrocarbons. This work describes a comprehensive analysis of various biomarkers, including the highly source-specific hopanes, in a 4.5 m long gravity core from the same area, together with subsurface sediment samples from other areas in the region without pockmarks present ("background samples"). A clear difference between the pockmark gravity core and the background sediment cores was found, both with regard to genesis and the level of transformation of organic matter. A number of indicator parameters, such as methylphenanthrene index (MPI-1), point towards a significantly higher maturity of hydrocarbons in the pockmark core throughout its length as compared to the other sampled locations. Higher contents of microbial hopanoids (hopenes) may indicate the former presence of petroleum. These findings confirm the hypothesis of a natural hydrocarbon source in the deeper strata present in the studied location with pockmarks.
Abstract In order to reveal possible multi-year dynamics in sediment PAH concentrations and composition, data sets from the years 2001–2005 have been compared with data sets obtained during the years 1992–1998. K-means-clustering of the 2001–2005 data sets suggests dividing the sampling area into five geographical areas based upon levels and compositions of PAHs. The five areas are Svalbard offshore, Bear Island Trough, SW Barents Sea, NE Barents Sea and SE Barents Sea. Comparison of the two groups of data sets revealed no significant differences between geometric means of PAH concentrations and PAH ratios for sediments from Svalbard offshore, Bear Island Trough and NE Barents Sea. These results are supported by down core analyses of PAH distributions. In the SW Barents Sea area, mean total PAH concentrations found in the 2000s and 1990s did not differ significantly. However, the sum of two- to three-ring PAH compounds and Fossil Fuel Pollution Index in samples of 2000s were significantly higher than in data sets from the 1990s. In the SE Barents Sea area, both total concentrations of pyrogenic PAHs and PAH ratios in the data sets from the 2000s were significantly higher than the 1990s data sets, which suggest higher input of combustion and/or anthropogenic PAHs.