Hydrocarbons in surface layer bottom sediments from the North Dvina Riverand the southern part of the Dvina Bay, White Sea

Analysis of molecular composition of alkanes in bottom sediments of the southern part of Dvina Bay (White Sea) in October 2001 revealed the following main peculiarities of hydrocarbon behavior in the estuary: dominating of high molecular C23-C45 compounds and irregular distribution of hydrocarbons in bottom sediments as a result of high sedimentation rate and active hydrodynamics in the studied area.

Hydrocarbon gases in ODP Leg 104 samples

Geochemical studies at three ODP Leg 104 sites on the Wring Plateau help define the distribution of hydrocarbon gases in sediment of this prominent feature of the Norwegian continental margin. Low levels of hydrocarbon gas were encountered in sediment of the outer part of the plateau, but sediment of the inner part of the plateau is very gassy. The molecular composition of inner plateau gases (>99.9% methane) and the carbon isotopic composition of the methane (avg. = -76 per mil relative to the PDB standard) clearly show that the gas is biogenic. Heavier hydrocarbon gases accompany this methane, and their presence is probably a result of both chemical and microbial low-temperature diagenesis. Although these heavier hydrocarbons were not detected in sediment of the outer part of the plateau during shipboard analyses, subsequent shore-based analyses showed that these compounds are present at very low concentrations. Methane in the gassy sediment of the inner part of the plateau may be present as gas hydrates, judging from sedimentological and inorganic geochemical considerations, but no discernible gas hydrates were recovered during drilling.

n-Alkanes and lignin in bottom sediments of the West European Basin (area of the battleship Bismark wreck site)

Three bottom sediment cores were collected from the top, slope, and foot of a small topographic high located near the West European continental rise within the Porcupine abyssal plain at the battleship Bismark wreck site. Using high-efficient gas chromatography technique we determined content and examined molecular composition of n-alkane fraction of hydrocarbons and phenol compounds of lignin. n-Alkane and phenol concentrations in bottom sediments of all three cores were low both in values per unit mass of sediments and in organic matter composition that is typical for pelagic deposits of the World Ocean. They vary from 0.07 to 2.01 µg/g of dry sediment and from 0.0001 to 0.01% of TOC; phenol ranges are from 1.43 to 11.1 µg/g and from 0.03 to 0.6%. Non-uniform supply of terrigenous matter to the bottom under conditions of changes in sedimentation environment in different geological epochs is the principal reason for significant variations in n-alkane and lignin concentrations with depth in the cores. Lignin and its derivatives make the main contribution to formation of organic matter composition of the region in study. With respect to n-alkane and lignin concentrations organic matter of deposits of the West European Basin is composed of remains of higher plants and of autochtonous organic matter of marine flora; they have mixed terrigenous-autochtonous (terrigenous-planktonogenic) origin.

Hydrocarbon gar in sediments of the Costa Rica ubduction zone

At the active continental margin off Costa Rica substantial amounts of hydrocarbon gases are encountered in sediments. The molecular composition (C1-C3) of free hydrocarbon gas as well as the isotopic composition (d13C of methane and ethane and D of methane) was analysed on core samples (ranging between 50 and 380 m depth) collected at sites 1040-1043 which was drilled during ODP Leg 170. In addition, the molecular composition of the C1-C3 hydrocarbons and the d13C composition of C1 and C2 hydrocarbons was determined on adsorbed gas from selected depth intervals at Site 1041 (50-380 mbsf). The molecular composition, and stable carbon and hydrogen isotope signature of low molecular weight hydrocarbons from core sediments and gas pockets indicate that most of the gas was generated by microbial CO2-reduction. Beside d13C values of about -80 per mil for methane (which is typical for microbially- generated methane) extremely light d13C values of -55 per mil were measured for ethane. The carbon isotope composition of methane and ethane, as well as the C1/(C2+C3) ratio display distinct trends with increasing depth. Gas mixing calculations indicate that the percentage of thermally-generated ethane increases from 10% at about 75 mbsf to almost 80% at 380 mbsf. The fraction of thermogenic methane in this depth interval is calculated to range from 0.03 to 1.8% of the total methane. The small contribution of thermogenic methane would increase the d13C value by <1 per mil. Therefore, the increase of d13C of methane (by about 12 per mil) with depth cannot be explained by gas mixing alone. Instead, the observed d13C trend is caused by successive isotope depletion of the methane precursor within the sedimentary organic matter due to progressing microbial gas generation.

n-Alkanes and phenols in bottom sediments and brown algae from the Blake-Bahama Abyssal Plain

Using gas chromatography technique we examined molecular composition of n-alkanes and lignin from bottom sediments of a core 385 cm long collected in the region of the Blake-Bahama Abyssal Plain. We determined C_org concentrations and lignin composition in soils, mangrove roots and leaves, in algae Sargassum and Ascophyllum, in corals and timber of a sunken ship; they were compared with data on lignin in bottom sediments. Mixed planktonogenic and terrigenous origin of organic matter in the core was proved with different proportions of terrigenous and planktonogenic components at different levels. Multiple changes in dominating sources of organic matter over a period required for accumulation of a four meter thick sedimentary sequence (about 4 m) are shown as obtained from changes in composition and contents of organic-chemical markers referring to classes of n-alkanes and phenols.

Light hydrocarbons in sediments of ODP Site 124-768

Geochemical investigations on gases and interstitial waters from ODP Site 768 (Sulu Trench/Philippines) demonstrate the application of molecular gas composition in combination with stable isotope analyses to the genetic classification of light hydrocarbons. 13C/12C and D/H ratios of methane from gas pockets in cores and gases desorbed from frozen sediments by a vacuum/acid treatment suggest a microbial generation of methane by a CO2 reducing process in sediments with low sulfate concentrations. Isotope data and molecular composition of sediment gases liberated by the vacuum/acid treatment seem to be affected by a secondary desorption process during sampling. A comparison between the D/H ratios of methane from gas pockets and interstitial H2O points to an in-situ generation of methane down to a sub-bottom depth of approx. 720 m. Below this depth hydrogen isotope data indicate a migration of light hydrocarbons into pyroclastic sediments at this site. The occurrence of higher hydrocarbons (propane to pentane) in gases from gas pockets coincides with the vertical distribution of mature organic matter. Gases within the zone of mature organic matter are gases of a mixed microbial and thermal origin.

Dissolved organic matter in the Lena Delta in 2009

Large Arctic rivers discharge significant amounts of dissolved organic matter (DOM) into the Arctic Ocean. We sampled natural waters of the Lena River, the Buor-Khaya Bay (Laptev Sea), permafrost melt water creeks, ice complex melt water creeks and a lake. The goal of this study was to characterize the molecular DOM composition with respect to different water bodies within the Lena Delta. We aimed at an identification of source-specific DOM molecular markers and their relative contribution to DOM of different origin. The molecular characterization was performed for solid-phase extracted DOM by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Average dissolved organic carbon concentrations in the original samples were 490±75 µmol C/L for riverine and bay samples and 399±115 µmol C/L for permafrost melt water creeks. Average TDN concentrations were elevated in the permafrost melt waters (19.7±7.1 µmol N/L) in comparison to the river and the bay (both 13.2±2.6 µmol N/L). FT-ICR MS and statistical tools demonstrated that the origin of DOM in the Lena Delta was systematically reflected in its molecular composition. Magnitude weighted parameters calculated from MS data (O/Cwa, H/Cwa, C/Nwa) highlighted preliminary sample discrimination. The highest H/Cwa of 1.315 was found for DOM in melt water creeks in comparison to 1.281 for river and 1.230 for the bay samples. In the bay samples we observed a higher fraction of oxygen-rich components which was reflected in an O/Cwa ratio of 0.445 in comparison to 0.425 and 0.427 in the river and creeks, respectively. From the southernmost location to the bay a relative depletion of nitrogenous molecular markers and an enrichment of oxidized DOM components occurred. The highest contribution of nitrogenous components was indicative for creeks reflected in a C/Nwa of 104 in comparison to 143 and 176 in the river and bay, respectively. These observations were studied on a molecular formula level using principal component and indicator value analyses. The results showed systematic differences with respect to water origin and constitute an important basis for a better mechanistic understanding of DOM transformations in the changing Arctic rivers.

Lignin and chemical elements in the surface layer of bottom sediments from the Kandalaksha Bay of the White Sea

Chemical composition of the upper layer of sediments (0-1 cm) in the Kolvits and Knazhaya inlets, and also in the deep-water part of the Kandalaksha Bay is considered. It is shown that silts are richer in Fe, TOC, and heavy metals, than sands. The highest concentration of these elements is found in sediments under mixing zones of riverine and sea waters. Correlations of P, Zn, Cd, and Cu with iron are high, and correlations of Pb and Cu with organic carbon are also high. Very high concentration of Pb in the Kandalaksha Bay indicate technogenic pollution of sediments. Lignin makes significant contribution to formation of organic matter in the sediments. Composition of lignin in bottom sediments of the Kandalaksha Bay is defined by composition of lignin in soils and aerosols. Vanillin and syringyl structures prevail in molecular composition of lignin in bottom sediments. Their sources are coniferous vegetations, soils, and mosses. Ratios of certain types of phenol compounds indicate pollution of the upper layer of sediments by technogenic lignin. Lead and copper correlate well with this technogenic lignin.

Determination of hydrocarbon gases in mud volcanoes in the Sorokin Trough

Hydrocarbon gases were determined in sediments from three mud volcanoes in the Sorokin Trough. In comparison to a reference station outside the mud volcano area, the deposits are characterized by an enrichment of high-molecular hydrocarbons (C2-C4), an absence of unsaturated homologues, a predominance of iso-butane in comparison with n-butane, and the presence of gas hydrate. The molecular composition of the hydrocarbon gases suggests their deep sources and thermogenic origin. In the pelagic sediments at the reference station, the methane concentration is relatively low (up to 49 ml/l); maximum concentrations are reached in deposits of the Dvurechenskii mud volcano (up to 400 ml/l). It was the first time that gas hydrate was sampled at the Dvurechenskii mud volcano. The gas extracted by dissociation of hydrate samples was dominated by methane (99.5%) with low amounts of ethane and propane (less than 0.5%). The isotopic composition of the methane varies between -62 and -66 per mill PDB in d13C, and between -185 and -209 per mill SMOW in dD, indicating a mainly biogenic origin with an admixture of thermogenic gas.

Organic matter and sediment properties of samples from site GeoB15105 from the Black Sea

Dissolved organic matter (DOM) in marine sediments is a complex mixture of thousands of individual constituents that participate in biogeochemical reactions and serve as substrates for benthic microbes. Knowledge of the molecular composition of DOM is a prerequisite for a comprehensive understanding of the biogeochemical processes in sediments. In this study, interstitial water DOM was extracted with Rhizon samplers from a sediment core from the Black Sea and compared to the corresponding water-extractable organic matter fraction (<0.4 µm) obtained by Soxhlet extraction, which mobilizes labile particulate organic matter and DOM. After solid phase extraction (SPE) of DOM, samples were analyzed for the molecular composition by Fourier Transform Ion-Cyclotron Resonance Mass Spectrometry (FT-ICR MS) with electrospray ionization in negative ion mode. The average SPE extraction yield of the dissolved organic carbon (DOC) in interstitial water was 63%, whereas less than 30% of the DOC in Soxhlet-extracted organic matter was recovered. Nevertheless, Soxhlet extraction yielded up to 4.35% of the total sedimentary organic carbon, which is more than 30-times the organic carbon content of the interstitial water. While interstitial water DOM consisted primarily of carbon-, hydrogen- and oxygen-bearing compounds, Soxhlet extracts yielded more complex FT-ICR mass spectra with more peaks and higher abundances of nitrogen- and sulfur-bearing compounds. The molecular composition of both sample types was affected by the geochemical conditions in the sediment; elevated concentrations of HS- promoted the early diagenetic sulfurization of organic matter. The Soxhlet extracts from shallow sediment contained specific three- and four-nitrogen-bearing molecular formulas that were also detected in bacterial cell extracts and presumably represent proteinaceous molecules. These compounds decreased with increasing sediment depth while one- and two-nitrogen-bearing molecules increased, resulting in a higher similarity of both sample types in the deep sediment. In summary, Soxhlet extraction of sediments accessed a larger and more complex pool of organic matter than present in interstitial water DOM.

n-Alkanes and lignin in bottom sediments of the Norwegian Sea

Investigations of bottom sediments from the central and northern parts of the Norwegian Sea including study regions at the Storegga landslide, the Haakon Mosby mud volcano, and Knipovich Ridge were carried out. Concentration of n-alkanes in bottom sediments from these regions ranges from 0.53 to 22.1 µg/g of dry sediments that corresponds to 0.02-1.97% of Corg. Molecular composition of hydrocarbons indicates mixed allochtonous-authochtonous genesis of total organic matter (TOC) formed by hydrobiota and residuals of terrestrial plants. Terrigenous organic mater dominates in bottom sediments. Active redox, microbial and thermolytic processes of organic matter transformation take place in the sedimentary mass. Special character of chromatographic spectra of n-alkane distribution in both low and high-molecular ranges, as well as increased naphtene contents can be interpreted as a sign of oil hydrocarbon generation from maternal organic matter as a result of thermocatalytic reactions within sedimentary mass and their displacement into the upper sedimentary layers. Molecular compositions and concentrations of phenols and lignin were determined in core samples from the Norwegian Sea. Total concentration of phenols in the cores ranges from 8.1 to 101.8 (µg/g of dry sediments that corresponds to 0.15-1.15% of TOC. Lignin concentration was estimated at 21.0-459.0 µg/g of dry sediments (0.59-7.9% of ?org. Phenol compounds of p-hydroxybenzoic, vanillin, syringyl and cinnamyl families as basic components of lignin macromolecules were identified. It was found that sea currents and aerosols are the main contributors of lignin into the abyssal part of the Norwegian Sea.

Porosity in sediment cores from the central Arctic Ocean during POLARSTERN cruise ARK-XXVII/3 from August-September 2012

During the RV Polarstern cruise ARK-XXVII/3 to the Arctic Ocean in summer 2012, when sea ice declined to a record minimum bottom, sediment cores were collected with a TV-guided multicorer at stations in the Nansen and Amundsen basin. For porosity measurements cores were subsampled and samples were stored at 4°C until analyzes in the home laboratory.