Hydrocarbons, sterols and alkenones at time series station KERFIX

Hydrocarbons, sterols and alkenones were analyzed in samples collected from a 10 month sediment trap time series deployed in the Indian Ocean sector of the Southern Ocean. Fluxes and within-class distributions varied seasonally. During higher mass and organic carbon (OC) flux periods, which occurred in austral summer and fall, fresh marine inputs were predominant. Vertical fluxes were most intense in January, but limited to one week in duration. They were, however, low compared with other oceanic regions. In contrast, low mass and OC flux periods were characterized by a strong unresolved complex mixture (UCM) in the hydrocarbon fraction and a high proportion of stanols as a result of zooplanktonic grazing. Terrigenous inputs were not detectable. The alkenone compositions were consistent with previous data on suspended particles from Antarctic waters. However, UK'37 values diverged from the linear and exponential fits established by Sikes et al. (1997, doi:10.1016/S0016-7037(97)00017-3) in the low temperature range. The seasonal pattern of alkenone production implied that IPT (integrated production temperature) is likely to be strongly imprinted by austral summer and fall SST (sea surface temperature).

Nature, origin, and petroleum source potential of organic matter at DSDP Leg 56-57 Holes

As part of a continuing program of organic-geochemistry studies of sediments recovered by the Deep Sea Drilling Project, we have analyzed the types, amounts, and thermal-alteration indices of organic matter in samples collected from the landward wall of the Japan Trench on Legs 56 and 57. The samples were canned aboard ship, enabling us to measure also their gas contents. In addition, we analyzed the heavy C15+ hydrocarbons, NSO compounds, and asphaltenes extracted from selected samples. Our samples form a transect down the trench wall, from Holes 438 and 438A (water depth 1558 m), through Holes 435 and 435A (water depth 3401 m), and 440 (water depth 4507 m), to Holes 434 and 434B (water depth 5986 m). The trench wall is the continental slope of Japan. Its sediments are Cenozoic hemipelagic diatomaceous muds that were deposited where they are found or have slumped from farther up the slope. Their terrigenous components probably were deposited from near-bottom nepheloid layers transported by bottom currents or in low density flows (Arthur et al., 1978). Our objective was to find out what types of organic matter exist in the sediment and to estimate their potential for generation of hydrocarbons.

(Table 1) Geochemical and geothermometry data from fibrous calcite vein fills in the Dabashan Fold Belt, China

Fibrous calcite veins with organic inclusions have been widely considered as indicators of oil and gas generation and migration under overpressure. Abundant fibrous calcite veins containing organic-bearing inclusions occur in faulted Lower Paleozoic through Triassic hydrocarbon source rocks in the Dabashan Foreland Belt (DBF). d13CPDB and d18OPDB values of the fibrous calcite range from - 4.8 to -1.9 to per mil and - 12.8 to - 8.4 per mil respectively, which is lighter than that of associated carbonate host rocks ranging from - 1.7 to + 3.1 per mil and - 8.7 to - 4.5 per mil. A linear relationship between d13CPDB and d18OPDB indicates that the calcite veins were precipitated from a mixture of basinal and surface fluids. The fibrous calcite contains a variety of inclusions, such as solid bitumen, methane bearing all-liquid inclusions, and vapor-liquid aqueous inclusions. Homogenization temperatures of aqueous inclusions range from 140 to 196° with an average of 179°. Salinities of aqueous inclusions average 9.7 wt% NaCl. Independent temperatures from bitumen reflectance and inclusion phase relationships of aqueous and methane inclusions were used to determine fluid pressures. Results indicate high pressures, elevated above typical lithostatic confining pressure, from 150 to 200 MPa. The elevated salinity and high temperature and pressure conditions of the fibrous calcite veins argue against an origin solely from burial overpressure resulting from clay transformation and dehydration reactions. Instead fluid inclusion P-T data and geochemistry results and regional geology indicate abnormally high pressures during fluid migration. These findings indicate that tectonic stress generated fracture and fault fluid pathways and caused migration of organic bearing fluids from the DBF during the Yanshan orogeny.

Diagenetic dolomite formation in Quaternary anoxic diatomaceous muds at DSDP Leg 64 Holes

During drilling in the Gulf of California, diagenetic carbonate rocks were recovered at 7 out of 8 sites. These are primarily dolomites which record 13C isotopic evidence of the incorporation of carbon derived from the decomposition of organic matter. In Hole 479, drilled to a sub-bottom depth of 440 meters on the Guaymas Slope, under a fertile upwelling belt, we recognized an excellent example of deep sea dolomitization in progress. This Quaternary section of organic-carbon- rich, low-carbonate, hemipelagic diatomaceous oozes contains numerous fine-grained, decimeter-thin, episodic beds of dolomite, which show sedimentologic, geochemical, and isotopic evidence of accretion by precipitation below 40 meters sub-bottom in zones of high alkalinity and low sulfate. The beds preserve original sedimentary structures. Carbon-13 varies from +3 to +14 per mil, indicating biogenic CO2 reservoirs related to active methanogenesis. In single beds, 18O values range outwardly from +5 to -7 per mil, reflecting increasing temperature with progressive accretion of dolomite with depth; the values parallel progressive trends in lithification, texture, mineralogy, and fossil preservation. We estimate slow accretion rates on the order of 0.1-0.7 mm/10**3 yr. with burial. Dolomitization does not proceed merely at the expense of nearby nannofossils. Ca and Mg ions must be derived from interstitial waters. The episodic appearance of beds in the sequence seems partly a reflection of latent climate signals. This process of deep sea dolomitization carries implications for hydrocarbon migration, as well as an interpretation of the presence of dolomite in other modern and ancient pelagic to hemipelagic sediment sequences.

Bitumen and n-alkanes in organic matter from sedimentary rocks sampled in DSDP Holes 47-397A and 47-398

A study of samples from DSDP Leg 47 shows that transformation of organic matter in deep sea sediments is completly analogous to evolution of organic matter in sedimentary sequences on continents and depends on the same factors. Crucial among these factors are: genesis of organic matter, nature of its diagenetic changes, and current stage of catagenesis.

Enzyme activity and liver tissue PCB concentrations of chicks of northern fulmars (F. glacialis) and black-legged kittiwakes (R. tridactyla) from Kongsfjorden

Arctic seabirds are exposed to a wide range of halogenated organic contaminants (HOCs). Exposure occurs mainly through food intake, and many pollutants accumulate in lipid-rich tissues. Little is known about how HOCs are biotransformed in arctic seabirds. In this study, we characterized biotransformation enzymes in chicks of northern fulmars (Fulmarus glacialis) and black-legged kittiwakes (Rissa tridactyla) from Kongsfjorden (Svalbard, Norway). Phase I and II enzymes were analyzed at the transcriptional, translational and activity levels. For gene expression patterns, quantitative polymerase chain reactions (qPCR), using gene-sequence primers, were performed. Protein levels were analyzed using immunochemical assays of western blot with commercially available antibodies. Liver samples were analyzed for phase I and II enzyme activities using a variety of substrates including ethoxyresorufin (cytochrome (CYP)1A1/1A2), pentoxyresorufin (CYP2B), methoxyresorufin (CYP1A), benzyloxyresorufin (CYP3A), testosterone (CYP3A/CYP2B), 1-chloro-2,4-nitrobenzene (CDNB) (glutathione S-transferase (GST)) and 4-nitrophenol (uridine diphosphate glucuronyltransferase (UDPGT)). In addition, the hydroxylated (OH-) polychlorinated biphenyls (PCBs) were analyzed in the blood, liver and brain tissue, whereas the methylsulfone (MeSO2-) PCBs were analyzed in liver tissue. Results indicated the presence of phase I (CYP1A4/CYP1A5, CYP2B, and CYP3A) and phase II (GST and UDPGT) enzymes at the activity, protein and/or mRNA level in both species. Northern fulmar chicks had higher enzyme activity than black-legged kittiwake chicks. This in combination with the higher XOH-PCB to parent PCB ratios suggests that northern fulmar chicks have a different biotransformation capacity than black-legged kittiwake chicks.

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.

Heavy metal and petroleum product concentrations in waters at the Obskaya 1 drill site

During recent years, the basins of the Kara Sea (Kamennomysskaya, Obskaya, and Chugor'yakhinskaya structures) in the Russian Federation have been considered as promising regions for oil and gas exploration and, simultaneously, as possible paths of relatively cheap pipeline and tanker transportation of hydrocarbons projected for recovery. On the other hand, exploration operations, recovery, and transportation of gas pose a considerable risk of accidents and environmental pollution, which causes a justified concern about the future state of the ecological system of the Gulf of Ob and the adjoining parts of the Kara Sea. Therefore, regular combined environmental investigations (monitoring) are the most important factor for estimating the current state and forecasting the dynamics of the development of estuary systems. The program of investigations (schedule, station network, and measured parameters) is standardized in accordance with the international practice of such work and accounts for the experience of monitoring studies of Russian and foreign researchers. Two measurement sessions were performed during ecological investigations in the region of exploration drilling: at the beginning at final stage of drilling operations and borehole testing; in addition, natural parameters were determined in various parts of the Ob estuary before the beginning of investigations. Hydrophysical and hydrochemical characteristics of the water medium were determined and bottom sediments and water were analyzed for various pollutants (petroleum products, heavy metals, and radionuclides). The forms of heavy-metal occurrence in river and sea waters were determined by the method of continuous multistep filtration, which is based on water component fractionation on membrane filters of various pore sizes. These investigations revealed environmental pollution by chemical substances during the initial stage of drilling operations, when remains of fuels, oils, and solutions could be spilled, and part of the chemical pollutants could enter the environment. Owing to horizontal and vertical turbulent diffusion, wave mixing, and the effect of the general direction of currents in the Ob estuary from south to north, areas are formed with elevated concentrations of the analyzed elements and compounds. However, the concentration levels of chemical pollutants are practically no higher than the maximum admissible concentrations, and their substantial dissipation to the average regional background contents can be expected in the near future. Our investigations allowed us to determine in detail the parameters of anthropogenic pollution in the regions affected by hydrocarbon exploration drilling in the Obskii and Kamennomysskii prospects in the Gulf of Ob and estimate their influence on the ecological state of the basin of the Ob River and the Kara Sea on the whole.

Geochemistry and petrography of organic matter at DSDP Site 93-603

A series of 22 sediment samples of Cretaceous and Cenozoic age from DSDP Holes 603, 603B, and 603C at the continental rise off the northeastern American coast near Cape Hatteras was investigated by organic geochemical methods including organic carbon determination, Rock-Eval pyrolysis, gas chromatography and combined gas chromatography/mass spectrometry of extractable hydrocarbons, and kerogen microscopy. An abundance of terrigenous organic matter, including larger coal particles (almost exclusively consisting of huminite/vitrinite macerals), is the dominant characteristic of the organofacies types at Site 603. Marine organic matter, mostly structurally degraded and in the form of fecal pellets, was preserved in the Valanginian laminated marls and in Cenomanian black claystone turbidites. Long-chain nalkanes reflect the terrigenous imprint in the nonaromatic hydrocarbon fractions, whereas a second maximum at lower carbon numbers in most cases is caused by the presence of more mature recycled organic matter. Abundant isoprenoid and steroid hydrocarbons were found in sediments containing mainly marine organic matter, whereas hopanoids reflect the ubiquitous microbial activity. The organic matter in the Site 603 sediments, in so far as it is not recycled, is thermally immature.

Organic compounds and bitumen in surface sediments from the Pechora Bay

Detailed geochemical investigations of bottom sediments in the Pechora Bay were carried out under a monitoring regime. The regional geochemical background is characterized. Organic matter of sediments is found to be clastic, formed under the influence of Pechora River run-off, and determined by genetic and lithofacial factors. An application of geochemical methodology is suggested for estimating hydrocarbon contamination of bottom sediments. As an example consequences of the accidental Usinsky oil spill are studied. They are based on analysis of composition of molecular markers. It is shown that increasing technogenic impact on Pechora Bay sediments is fixed only at molecular level and is not disastrous.