Composition of organic matter in suspended matter and bottom sediments of the southeastern Baltic Sea

Data on contents and compositions of hydrocarbons (HCs)-aliphatic (AHCs) and polycyclic aromatic (PAHs) are provided in comparison with contents of total organic carbon (Corg), lipids in suspended matter, and Corg in bottom sediments. Particular attention is paid to distribution of HCs in the area of the Kravtsov oil field. It is established that concentrations of AHCs in water are governed by concentrations of suspended matter and elevated AHC concentrations are confined to coastal areas. In the area of D-6 platform sandy bottom sediments are notable for great variability of HC concentrations, both laterally and from year to year. In summer of 2010 average content of AHCs was 40 ppm (19% of Corg) and that of PAHs was 0.023 ppm. Natural seepage from sediment mass is considered to be a source of HCs along with oil contamination.

Biochemical, geochemical and sedimentological study of ODP Leg 112 samples

Organic-rich diatomaceous muds from Ocean Drilling Program Leg 112 (offshore Peru) are the subject of a comprehensive organic diagenetic study covering the burial interval, <1 to >100 m. The organic matter has been classified in terms of its elemental, biochemical, and geochemical compositions. About 60% of the organic carbon in sediments from <1 m can be attributed to hydrolyzable, biochemical constituents, while at 22 m this figure decreased to 20%. Pyrolysis-gas chromatography and gas chromatography-mass spectrometry chromatograms of these same sediments contain mainly hydrocarbons and nitrogenous compounds, with low amounts of other heteroatomic compounds, even though the total organic matter is rich in oxygen (about 35 atoms per 100 carbon atoms) and sulfur (1 to 5 atoms per 100 C atoms). Overall, the organic matter in these sediments, even at these shallow depths and young ages, has many of the geochemical features of far more deeply buried sediments, providing further strong evidence for the claim that "kerogen-formation" is a very early diagenetic process.

Geochemistry of Albian to Santonian black shale sequences on the Demerara Rise, South American margin

Ocean Drilling Program Leg 207 recovered thick sequences of Albian to Santonian organic-carbon-rich claystones at five drill-sites on the Demerara Rise in the western equatorial Atlantic Ocean. Dark-colored, finely laminated, Cenomanian-Santonian black shale sequences contain between 2% and 15% organic carbon and encompass Oceanic Anoxic Events 2 and 3. High Rock-Eval hydrogen indices signify that the bulk of the organic matter in these sequences is marine in origin. However, d13Corg values lie mostly between -30 per mil and -27 per mil, and TOC/TN ratios range from 15 to 42, which both mimic the source signatures of modern C3 land plants. The contradictions in organic matter source indicators provide important implications about the depositional conditions leading to the black shale accumulations. The low d13Corg values, which are actually common in mid-Cretaceous marine organic matter, are consequences of the greenhouse climate prevailing at that time and an associated accelerated hydrologic cycle. The elevated C/N ratios, which are also typical of black shales, indicate depressed organic matter degradation associated with low-oxygen conditions in the water column that favored preservation of carbon-rich forms of marine organic matter over nitrogen-rich components. Underlying the laminated Cenomanian-Santonian sequences are homogeneous, dark-colored, lower to middle Albian siltstones that contain between 0.2% and 9% organic carbon. The organic matter in these rocks is mostly marine in origin, but it occasionally includes large proportions of land-derived material.

Organic geochemistry of Lower Cretaceous sediments from the northwetsern Pacific guyits

Organic geochemical data of Lower Cretaceous shallow water sediments from two sites (865 and 866) drilled during ODP leg 143 are presented. The organic matter is mainly terrestrial at the bottom of the sedimentary column at site 865, whereas algal and/or bacterial organic matter is dominant at site 866. This is the first evidence of shallow water deposition of organic matter during the Early Cretaceous in the Northwestern Pacific. The lower Aptian organic carbon-rich layers from the shallow water sediments of site 866 are geochemically similar to coeval mid-water sediments of site 463.

Chemistry of organic matter of glacial and Cretaceous sediments from the Prydz Bay

Organic matter in Miocene glacial sediments in Hole 739C on the Antarctic Shelf represents erosional recycled continental material. Various indications of maturity in bulk organic matter, kerogens, and extracts imply that an exposed section of mature organic carbon-rich material was present during the Miocene. Based on biomarker, n-alkane, and kerogen analysis, a massive diamictite of early Eocene/Oligocene age at Hole 739C contains immature organic matter. Visual and pyrolysis analyses of the kerogens suggest a predominance of terrestrial organic matter in all samples from Hole 739C. A reversal of thermal maturities, i.e., more-mature overlying less-mature sections, may be related to redeposition generated from glacial erosion. Siliciclastic fluviatile sediments of Lower Cretaceous age from Hole 741A were analyzed. The organic matter from this hole contains immature aliphatic and aromatic biomarkers as well as a suite of odd carbon number-dominated nalkanes. Visual examination and pyrolysis analysis of the kerogen suggests that predominantly immature terrestrial organic matter is present at Hole 741A. The similarities between Hole 739C Unit V and Hole 741A suggest that the source of the organic matter in the glacial sediments in Unit V at Hole 739C could be Cretaceous in age and similar to sediments sampled at Hole 741A in Prydz Bay.

Specific microbial biomarker signatures from Congo fan sediments of ODP site 175-1075, Congo soils, wetland and estuary sediments

Methane (CH4) is a strong greenhouse gas known to have perturbed global climate in the past, especially when released in large quantities over short time periods from continental or marine sources. It is therefore crucial to understand and, if possible, quantify the individual and combined response of these variable methane sources to natural climate variability. However, past changes in the stability of greenhouse gas reservoirs remain uncertain and poorly constrained by geological evidence. Here, we present a record from the Congo fan of a highly specific bacteriohopanepolyol (BHP) biomarker for aerobic methane oxidation (AMO), 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol), that identifies discrete periods of increased AMO as far back as 1.2 Ma. Fluctuations in the concentration of aminopentol, and other 35-aminoBHPs, follow a pattern that correlates with late Quaternary glacial-interglacial climate cycles, with highest concentrations during warm periods. We discuss possible sources of aminopentol, and the methane consumed by the precursor methanotrophs, within the context of the Congo River setting, including supply of methane oxidation markers from terrestrial watersheds and/or marine sources (gas hydrate and/or deep subsurface gas reservoir). Compound-specific carbon isotope values of -30 per mil to -40 per mil for BHPs in ODP 1075 and strong similarities between the BHP signature of the core and surface sediments from the Congo estuary and floodplain wetlands from the interior of the Congo River Basin, support a methanotrophic and likely terrigenous origin of the 35-aminoBHPs found in the fan sediments. This new evidence supports a causal connection between marine sediment BHP records of tropical deep sea fans and wetland settings in the feeding river catchments, and thus tropical continental hydrology. Further research is needed to better constrain the different sources and pathways of methane emission. However, this study identifies the large potential of aminoBHPs, in particular aminopentol, to trace and, once better calibrated and understood, quantify past methane sources and fluxes from terrestrial and potentially also marine sources.

Stable carbon isotopic composition of biomarker lipids of DSDP Hole 31-302

The middle Paleocene through early Eocene long-term gradual warming was superimposed by several transient warming events, such as the Paleocene-Eocene Thermal Maximum (PETM) and Eocene Thermal Maximum 2 (ETM2). Both events show evidence for extreme global warming associated with a major injection of carbon into the ocean-atmosphere system, but the mechanisms of carbon injection and many aspects of the environmental response are still poorly understood. In this study, we analyzed the concentration and stable carbon isotopic (d13C) composition of several sulfur-bound biomarkers derived from marine photoautotrophs, deposited in the Arctic Ocean at ~85°N, during ETM2. The presence of sulfur-bound biomarkers across this event points toward high primary productivity and anoxic bottom water conditions. The previously reported presence of isorenieratene derivatives indicates euxinic conditions in the photic zone, likely caused by a combination of enhanced primary productivity and salinity stratification. The negative carbon isotope excursion measured at the onset of ETM2 for several biomarkers, ranges between 3 per mil and 4.5 per mil, much larger than the ~1.4 per mil recorded in marine carbonates elsewhere, suggesting substantial enhanced isotopic fractionation by the primary producers likely due to a significant rise in pCO2. In the absence of biogenic carbonates in the ETM2 section of our core we use coeval planktonic d13C from elsewhere to estimate surface water d13C in the Arctic Ocean and then apply the relation between isotopic fractionation and pCO2, originally calibrated for haptophyte alkenones, to three selected organic biomarkers (i.e., S-bound phytane, C35 hopane, and a C25 highly branched isoprenoid). This yields pCO2 values potentially in the range of four times preindustrial levels. However, these estimates are uncertain because of a lack of knowledge on the importance of pCO2 on photosynthetic isotopic fractionation.

Proto-kerogens in Holocene sediments of ODP Hole 165-1002C

Proto-kerogens were isolated, by extraction and HF/HC1 treatment, from core samples of Holocene sediments of the Cariaco Trench, with interpolated ages of 900, 2850 and 6000 years, and examined via a combination of microscopic, spectroscopic and pyrolytic methods. It appears that these proto-kerogens were chiefly formed from phytoplanktonic components via the degradation-recondensation pathway. The natural sulfurisation pathway only afforded a minor contribution, in spite of the conditions prevailing in the water column and sediments that correspond to those generally considered as especially favourable for the formation of sulfurised organic matter. Proto-kerogen formation via sulfurisation, i.e. the endpoint of the continuum leading to insoluble high molecular weight structures cross-linked by sulfur and resistant to acid hydrolysis, is therefore a rather slow process under these conditions. However, the contribution of sulfurised moieties to the total proto-kerogen substantially increased with depth due to continuous sulfurisation in the time/depth interval, whereas formation through degradation-recondensation is almost complete for the 900 years old sample onwards. Proto-kerogen formation via carbohydrate sulfurisation is faster than lipid sulfurisation and only sulfurised carbohydrates were detected in the shallowest sample. In contrast, sulfurised lipids occur in the other two proto-kerogens. Moreover, their contribution relative to sulfurised carbohydrates increases with depth, probably due to the higher resistance of lipids to mineralisation compared to carbohydrates.