Organic geochemistry of deep sea sediments from the Nankai Trough and the Southwest Japan forearc region

Earth's largest reactive carbon pool, marine sedimentary organic matter, becomes increasingly recalcitrant during burial, making it almost inaccessible as a substrate for microorganisms, and thereby limiting metabolic activity in the deep biosphere. Because elevated temperature acting over geological time leads to the massive thermal breakdown of the organic matter into volatiles, including petroleum, the question arises whether microorganisms can directly utilize these maturation products as a substrate. While migrated thermogenic fluids are known to sustain microbial consortia in shallow sediments, an in situ coupling of abiotic generation and microbial utilization has not been demonstrated. Here we show, using a combination of basin modelling, kinetic modelling, geomicrobiology and biogeochemistry, that microorganisms inhabit the active generation zone in the Nankai Trough, offshore Japan. Three sites from ODP Leg 190 have been evaluated, namely 1173, 1174 and 1177, drilled in nearly undeformed Quaternary and Tertiary sedimentary sequences seaward of the Nankai Trough itself. Paleotemperatures were reconstructed based on subsidence profiles, compaction modelling, present-day heat flow, downhole temperature measurements and organic maturity parameters. Today's heat flow distribution can be considered mainly conductive, and is extremely high in places, reaching 180 mW/m**2. The kinetic parameters describing total hydrocarbon generation, determined by laboratory pyrolysis experiments, were utilized by the model in order to predict the timing of generation in time and space. The model predicts that the onset of present day generation lies between 300 and 500 m below sea floor (5100-5300 m below mean sea level), depending on well location. In the case of Site 1174, 5-10% conversion has taken place by a present day temperature of ca. 85 °C. Predictions were largely validated by on-site hydrocarbon gas measurements. Viable organisms in the same depth range have been proven using 14C-radiolabelled substrates for methanogenesis, bacterial cell counts and intact phospholipids. Altogether, these results point to an overlap of abiotic thermal degradation reactions going on in the same part of the sedimentary column as where a deep biosphere exists. The organic matter preserved in Nankai Trough sediments is of the type that generates putative feedstocks for microbial activity, namely oxygenated compounds and hydrocarbons. Furthermore, the rates of thermal degradation calculated from the kinetic model closely resemble rates of respiration and electron donor consumption independently measured in other deep biosphere environments. We deduce that abiotically driven degradation reactions have provided substrates for microbial activity in deep sediments at this convergent continental margin.

Organic geochemistry of lower Cretaceous sediments at DSDP Hole 77-535

At Site 535, the four lithologic units of Cretaceous age are controlled by two types of sedimentologic facies: (1) the massive light-colored limestones or marly limestones in which the total organic carbon (TOC) content is low and the organic matter more or less oxidized and (2) laminated dark facies in which the TOC content is higher and associated with a well-preserved organic matter of Type II origin. Very little typical Type III organic matter occurs in the whole series from late Berriasian to Aptian and Cenomanian. Fluctuations from oxidizing to reducing environments of deposition are proposed to account for the variations in properties of the Type II organic matter between the different facies. Dark laminated layers are good but immature potential source rocks: petroleum potential is often higher than 2 kg HC/t of rock.

Analysis of organic matter from DSDP Leg 81 Holes

Organic geochemical and visual kerogen analyses were carried out on approximately 50 samples from Leg 81 (Rockall Plateau, North Atlantic). The sediments are from four sites (Sites 552-555), Pleistocene to Paleocene in age, and represent significantly different depositional environments and sources of organic matter. The Pleistocene glacial-interglacial cycles show differences in sedimentary organic matter based on Rock-Eval pyrolysis, organic phosphorus, and pyrolysis/mass-spectrometry analyses. Glacial samples contain more organic carbon, with a larger proportion of reworked organic matter. This probably reflects increased erosion of continental and shelf areas as a result of low sea level stands. Inter glacial samples contain a larger proportion of marine organic matter as determined by organic phosphorus and pyrolysis analyses. This immature, highly oxidized marine organic matter may be associated with the skeletal organic matrix of calcareous organisms. In addition, Rock-Eval data indicate no significant inorganic-carbonate contribution to the S3 pyrolysis peak. The Pliocene-Miocene sediments consist of pelagic, biogenic carbonates. The organic matter is similar to that of the Pleistocene interglacial periods; a mixture of oxidized marine organic matter and reworked, terrestrial detritus. The Paleocene-Oligocene organic matter reflects variations in source and depositional factors associated with the isolation of Rockall from Greenland. Paleocene sediments contain primarily terrestrial organic matter with evidence of in situ thermal stress resulting from interbedded lava flows. Late Paleocene and early Eocene organic matter suggests a highly oxidized marine environment, with major periods of deposition of terrestrially derived organic matter. These fluctuations in organic-matter type are probably the result of episodic shallowing and deepening of Rockall Basins. The final stage of Eocene/Oligocene sedimentation records the accelerating subsidence of Rockall and its isolation from terrestrial sources (Rockall and Greenland). This is shown by the increasingly marine character of the organic matter. The petroleum potential of sediments containing more than 0.5% organic carbon is poor because of their thermal immaturity and their highly oxidized and terrestrial organic-matter composition.

Chemical and isotopic analysis of bulk organic matter and hydrocarbon biomarkers from IODP Holes 311-U1327C, 311-U1328B and 311-U1328C

The chemical and isotopic compositions of sedimentary organic matter (SOM) from two mid-slope sites of the northern Cascadia margin were investigated during Integrated Ocean Drilling Program (IODP) Expedition 311 to elucidate the organic matter origins and identify potential microbial contributions to SOM. Gas hydrate is present at both locations (IODP Sites U1327 and U1328), with distinct patterns of near-seafloor structural accumulations at the cold seep Site U1328 and deeper stratigraphic accumulations at the slope-basin Site U1327. Source characterization and evidence that some components of the organic matter have been diagenetically altered are determined from the concentrations and isotopic compositions of hydrocarbon biomarkers, total organic carbon (TOC), total nitrogen (TN) and total sulfur (TS). The carbon isotopic compositions of TOC (d13C TOC = -26 to -22 per mil) and long-chain n-alkanes (C27, C29 and C31, d13C = -34 to -29 per mil) suggest the organic matter at both sites is a mixture of 1) terrestrial plants that employ the C3 photosynthetic pathway and 2) marine algae. In contrast, the d15N TN values of the bulk sediment (+4 to +8 per mil) are consistent with a predominantly marine source, but these values most likely have been modified during microbial organic matter degradation. The d13C values of archaeal biomarker pentamethylicosane (PMI) (-46.4 per mil) and bacterial-sourced hopenes, diploptene and hop-21-ene (-40.9 to -34.7 per mil) indicate a partial contribution from methane carbon or a chemoautotrophic pathway. Our multi-isotope and biomarker-based conclusions are consistent with previous studies, based only on the elemental composition of bulk sediments, that suggested a mixed marine-terrestrial organic matter origin for these mid-slope sites of the northern Cascadia margin.

Hydrous and anhydrous pyrolysis of DSDP Leg 75 kerogens

The aliphatic hydrocarbon distributions obtained from the natural bitumens of three Leg 75 sediments were compared using computerised gas chromatography-mass spectrometry (C-GC-MS). The kerogens isolated from these sediments were heated in sealed tubes at 330°C using the techniques of hydrous (i.e. heating kerogen in the presence of water) and anhydrous pyrolysis (i.e. heating dry kerogen alone). These experiments were then repeated at a lower temperature (280°C). At 330°C, under anhydrous conditions, considerable destruction of biomarkers in the ancient kerogens (i.e. pre-Tertiary) occurred, whereas with water present significant amounts of hopanes were obtained. However, with more recent kerogens (which contain larger amounts of chemically bound water), both anhydrous and hydrous pyrolysis gave a similar suite of biological markers, in which long chain acyclic isoprenoids (C40) are significant components. Lowering the temperature of pyrolysis to 280°C yielded biological markers under both hydrous and anhydrous conditions for all kerogens. n-Alkenes were not detected in any of the pyrolysates; however, a single unknown triterpene was discovered in several of the hydrous and anhydrous pyrolysates. The results tentatively indicate that the chief value to petroleum research of kerogen hydrous pyrolysis lies in its ability to increase the yield of pyrolysate. High temperature hydrous pyrolysis (280-330°C), under high pressure (2000 psi), does not appear to mimic natural conditions of oil generation. However, this study does not take into account whole rock pyrolysis.

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.

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.

Pyrolyzable carbon, temperature maximum, production index and lithology for DSDP Leg 96 holes

Sediments from Deep Sea Drilling Project Sites 615, 617, 618, 619, and 620-623 were subjected to pyrolysis. The sediments are immature with respect to petroleum generation as determined by production index values of less than 0.1 and Tmax values of 460-480°C. The amount of pyrolyzable organic matter was moderately low as compared to typical petroleum source rocks. The immature organic matter present does not appear to contain a significant proportion of woody material as shown by the low gas-generating potential. Typical overbank sediments from Sites 617 and 620 generally show higher P2 values (500-800 µg hydrocarbon per g dry weight sediment) than typical channel-fill sediments from Sites 621 and 622 (P2 = 450-560 µg/g). Tmax for both types of sediment remained very constant (462-468 °C) with a slight elevation (+ 15°C) occurring in samples containing lignite. The highest P2 values occurred in sections described as turbidites. Very low P2 values (about 50 µg/g) occurred in sands. P2 values for shallower sections of basin Sites 618 and 619 tended to be higher (900-1000 µg/g) and decreased in deeper, more terrigenous sections of Site 619. Preliminary experiments indicate that microbiological degradation of sediment organic matter causes a decrease in P2. Pyrolyzable organic matter from lower fan Site 623 appears to increase with depth in two different sediment sequences (40-85 and 95-125 m sub-bottom). Organic matter type, as shown by pyrolysis capillary gas chromatography (GC) patterns, was generally the same throughout the well, with much more scatter occurring in the deepest sections (130-155 m sub-bottom). One major and two minor organic matter types could be recognized in both fan and basin sites drilled on Leg 96.

Hydrocarbon concentrations from pressurized cores in the northern Gulf of Mexico

Two newly developed coring devices, the Multi-Autoclave-Corer and the Dynamic Autoclave Piston Corer were deployed in shallow gas hydrate-bearing sediments in the northern Gulf of Mexico during research cruise SO174 (Oct-Nov 2003). For the first time, they enable the retrieval of near-surface sediment cores under ambient pressure. This enables the determination of in situ methane concentrations and amounts of gas hydrate in sediment depths where bottom water temperature and pressure changes most strongly influence gas/hydrate relationships. At seep sites of GC185 (Bush Hill) and the newly discovered sites at GC415, we determined the volume of low-weight hydrocarbons (C1 through C5) from nine pressurized cores via controlled degassing. The resulting in situ methane concentrations vary by two orders of magnitudes between 0.031 and 0.985 mol kg**-1 pore water below the zone of sulfate depletion. This includes dissolved, free, and hydrate-bound CH4. Combined with results from conventional cores, this establishes a variability of methane concentrations in close proximity to seep sites of five orders of magnitude. In total four out of nine pressure cores had CH4 concentrations above equilibrium with gas hydrates. Two of them contain gas hydrate volumes of 15% (GC185) and 18% (GC415) of pore space. The measurements prove that the highest methane concentrations are not necessarily related to the highest advection rates. Brine advection inhibits gas hydrate stability a few centimeters below the sediment surface at the depth of anaerobic oxidation of methane and thus inhibits the storage of enhanced methane volumes. Here, computerized tomography (CT) of the pressure cores detected small amounts of free gas. This finding has major implications for methane distribution, possible consumption, and escape into the bottom water in fluid flow systems related to halokinesis.

Organic carbon chemistry of late Tertiary to Quaternary sediments ODP Leg 107

We analyzed samples from ODP Holes 652A and 654A (Leg 107, Tyrrhenian Sea) for the amount, type, and thermal maturity of organic matter. The sediments encompass clastic and biogenic lithologies, which were deposited on the passive margin east of Sardinia since the late Miocene to the Pleistocene. Marine, hypersaline/evaporitic, lacustrine/riverine, and finally hemipelagic marine conditions with occasional anoxic(?) interludes gave rise to very diverse sedimentary facies. The majority of samples is lean in organic matter (<0.2% TOC). Notable exceptions are Tortonian sediments (TOC average 0.3%), Messinian oil shales from Core 107-652A-64R (up to 11% TOC), Messinian lacustrine/fluvial sediments from Hole 652A (TOC average 0.42%,), and Pleistocene sapropel samples (>2% TOC). The Messinian oil shale in Hole 652A appears to be the only mature hydrocarbon source rock. In general, Pliocene sediments are the leanest and least mature samples. Pleistocene and Pliocene samples derive organic matter from a marine source. In spite of obvious facies differences in the Messinian between the two sites, pyrolysis results are not conclusive in separating hypersaline facies of Site 654 from the fresh water facies of Site 652, because both appear to have received terrestrial organic tissue as the main component of TOC. It is apparent from the distribution of maximum pyrolysis temperatures that heat flow must have been considerably higher at Site 652 on the lower margin in the Messinian. Molecular maturity indices in lipid extracts substantiate the finding that the organic matter in Tortonian and Messinian samples from Hole 654A is immature, while thermal maturation is more advanced in coeval samples from Hole 652A. Analyses of lipid biomarkers showed that original odd-even predominance was preserved in alkanes and alkylcyclohexanes from Messinian samples in Hole 654A, while thermal maturation had removed any odd-even predominance in Hole 652A. Isomerization data of hopanes and steranes support these differences in thermal history for the two sites. Hopanoid distribution further suggests that petroleum impregnation from a deeper, more mature source resulted in the co-occurrence of immature and mature groups of pentacyclic biomarkers. Even though the presence of 4-methylsteranes may imply that dinoflagellates were a major source for organic matter in the oil shale interval of Hole 652, we did not find intact dinoflagellates or related nonskeletal algae during microscopic investigation of the organic matter in the fine laminations. Morphologically, the laminations resemble bacterial mats.

Geochemical characterizations of the Cretaceous formations at DSDP Holes 93-603B and 11-105

Geochemical characterizations of the Cretaceous formations at Site 603 are quite comparable with those at Site 105. In the Blake-Bahama and the Hatteras formations, the petroleum potential is medium (<5 kg HC/t of rock) to very low (<0.5 kg HC/t of rock), and the organic matter is mainly of type III origin, that is, terrestrial. At the top of the Hatteras Formation, there is a condensed series, which chiefly contains organic matter of type II origin, with up to 20 wt.% total organic carbon content in Core 603B-34 and 25 wt.% in Core 105-9. This accumulation corresponds to the Cenomanian/Turonian boundary event. An examination of dinoflagellates in the kerogen concentration assigns dates to the samples studied by organic geochemistry. The Cenomanian and Turonian age of the organic-matter-rich black claystones indicates a low rate of sedimentation, about 1 m/Ma. Furthermore, the occurrence of type II organic matter indicates an anoxic environment with insufficient oxygen renewal to oxidize the sinking hemipelagic organic matter. This organic enrichment is not related to local phenomena but to sedimentation over an extended area, because deposits are well known in various areas with different paleodepths in the North Atlantic.