Chemical and mineral compositions of sedimentary deposits and magmatic rocks from DSDP Legs 41, 45, 48, and 49

This collective monography by a group of lithologists from the Geological Institute of the USSR Academy of Sciences summarizes materials of the Deep-Sea Drilling Project from the Atlantic Ocean. It gives results of processing materials on the sequences drilled during DSDP Legs 41, 45, 48 and 49. These studies were based on lithological-facial analysis combined with detailed mineralogical-petrographic description. Its chapters give a number of ideas on formation of the Earth sedimentary cover, which can be used for compilation of regional and global schemes of ocean paleogeography, reconstruction of history of some structures in the World Ocean, correlation between sedimentary processes on continents and in oceans, estimation of perspectives for oil and gas fields and ore formation.

(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.

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.

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.

Lithology, stratigraphy, organic carbon content, extract and liquid chromatography yields, and Rock-Eval pyrolysis at DSDP Holes 75-530A and 75-532

Seventeen sediment samples of Albian-Cenomanian to early Pliocene age from DSDP Hole 530A in the Angola Basin and six sediment samples of early Pliocene to late Pleistocene age from the Walvis Ridge were 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. The organic matter in all samples is strongly influenced by a terrigenous component from the nearby continent. The amount of marine organic matter present usually increases with the total organic carbon content, which reaches an extreme value of more than 10% in a Cenomanian black shale from Hole 530A. At Site 530 the extent of preservation of organic matter in the deep sea sediments is related to mass transport down the continental slope, whereas the high organic carbon contents in the sediments from Site 532 reflect both high bioproductivity in the Benguela upwelling regime and considerable supply of terrigenous organic matter. The maturation level of the organic matter is low in all samples.

Electrical resistivity, formation factors, and sound velocity at DSDP Holes 75-530A and 75-530B

From 0 to 277 m at Site 530 are found Holocene to Miocene diatom ooze, nannofossil ooze, marl, clay, and debrisflow deposits; from 277 to 467 m are Miocene to Oligocene mud; from 467 to 1103 m are Eocene to late Albian Cenomanian interbedded mudstone, marlstone, chalk, clastic limestone, sandstone, and black shale in the lower portion; from 1103 to 1121 m are basalts. In the interval from 0 to 467 m, in Holocene to Oligocene pelagic oozes, marl, clay, debris flows, and mud, velocities are 1.5 to 1.8 km/s; below 200 m velocities increase irregularly with increasing depth. From 0 to 100 m, in Holocene to Pleistocene diatom and nannofossil oozes (excluding debris flows), velocities are approximately equivalent to that of the interstitial seawater, and thus acoustic reflections in the upper 100 m are primarily caused by variations in density and porosity. Below 100 or 200 m, acoustic reflections are caused by variations in both velocity and density. From 100 to 467 m, in Miocene-Oligocene nannofossil ooze, clay, marl, debris flows, and mud, acoustic anisotropy irregularly increases to 10%, with 2 to 5% being typical. From 467 to 1103 m in Paleocene to late Albian Cenomanian interbedded mudstone, marlstone, chalk, clastic limestone, and black shale in the lower portion of the hole, velocities range from 1.6 to 5.48 km/s, and acoustic anisotropies are as great as 47% (1.0 km/s) faster horizontally. Mudstone and uncemented sandstone have anisotropies which irregularly increase with increasing depth from 5 to 10% (0.2 km/s). Calcareous mudstones have the greatest anisotropies, typically 35% (0.6 km/s). Below 1103 m, basalt velocities ranged from 4.68 to 4.98 km/s. A typical value is about 4.8 km/s. In situ velocities are calculated from velocity data obtained in the laboratory. These are corrected for in situ temperature, hydrostatic pressure, and porosity rebound (expansion when the overburden pressure is released). These corrections do not include rigidity variations caused by overburden pressures. These corrections affect semiconsolidated sedimentary rocks the most (up to 0.25 km/s faster). These laboratory velocities appear to be greater than the velocities from the sonic log. Reflection coefficients derived from the laboratory data, in general, agree with the major features on the seismic profiles. These indicate more potential reflectors than indicated from the reflection coefficients derived using the Gearhart-Owen Sonic Log from 625 to 940 m, because the Sonic Log data average thin beds. Porosity-density data versus depth for mud, mudstone, and pelagic oozes agree with data for similar sediments as summarized in Hamilton (1976). At depths of about 400 m and about 850 m are zones of relatively higher porosity mudstones, which may suggest anomalously high pore pressure; however, they are more probably caused by variations in grain-size distribution and lithology. Electrical resistivity (horizontal) from 625 to 950 m ranged from about 1.0 to 4.0 ohm-m, in Maestrichtian to Santonian- Coniacian mudstone, marlstone, chalk, clastic limestone, and sandstone. An interstitial-water resistivity curve did not indicate any unexpected lithology or unusual fluid or gas in the pores of the rock. These logs were above the black shale beds. From 0 to 100 m at Sites 530 and 532, the vane shear strength on undisturbed samples of Holocene-Pleistocene diatom and nannofossil ooze uniformly increases from about 80 g/cm**2 to about 800 g/cm**2. From 100 to 300 m, vane shear strength of Pleistocene-Miocene nannofossil ooze, clay, and marl are irregular versus depth with a range of 500 to 2300 g/cm**2; and at Site 532 the vane shear strength appears to decrease irregularly and slightly with increasing depth (gassy zone). Vane shear strength values of gassy samples may not be valid, for the samples may be disturbed as gas evolves, and the sediments may not be gassy at in situ depths.

Noble gases sampled from three cruises in the eastern tropical Atlantic in September 2005 and June/July 2006

Upwelling velocities w in the equatorial band are too small to be directly observed. Here, we apply a recently proposed indirect method, using the observed helium isotope (3He or 4He) disequilibria in the mixed layer. The helium data were sampled from three cruises in the eastern tropical Atlantic in September 2005 and June/July 2006. A one-dimensional two-box model was applied, where the helium air-sea gas exchange is balanced by upwelling from 3He-rich water below the mixed layer and by vertical mixing. The mixing coefficients Kv were estimated from microstructure measurements, and on two of the cruises, Kv exceeded 1 x 10**-4 m**2/s, making the vertical mixing term of the same order of magnitude as the gas exchange and the upwelling term. In total, helium disequilibrium was observed on 54 stations. Of the calculated upwelling velocities, 48% were smaller than 1.0 x 10**-5 m/s, 19% were between 1.0 and 2.0 x 10**-5 m/s, 22% were between 2.0 and 4.0 x 10**-5 m/s, and on 11% of upwelling velocities exceeded this limit. The highest upwelling velocities were found in late June 2006. Meridional upwelling distribution indicated an equatorial asymmetry with higher vertical velocities between the equator and 1° to 2° south compared to north of the equator, particularly at 10°W. Associated heat flux into the mixed layer could be as high as 138 W/m**2, but this depends strongly on the chosen depths where the upwelled water comes from. By combining upwelling velocities with sea surface temperature and productivity distributions, a mean monthly equatorial upwelling rate of 19 Sv was estimated for June 2006 and a biweekly mean of 24 Sv was estimated for September 2005.

Gridded bathymetry from multibeam echosounder EM120 data of the cruise M72/3a and M72/3b (2007)

Bathymetry based on data recorded during M72-3 between 17.03.2007 and 23.04.2007 in the Black Sea. This cruise concentrated on interdisciplinary work on gas hydrates with a main focus on the gas hydrate transition zone in and below 750 m water depth. Gas hydrate environments have been studied in various geological settings, mainly of the eastern Black Sea. Origins, distributions and dynamics of methane and gas hydrates in sediments and also methane fluxes from the sediment to the water column have been the focus. Main working areas were the Sorokin Trough, an area south of the Kerch Strait and the Andrusov Ridge in Ukrainian waters and the Gudauta Ridge and Gurian Trough in Georgian waters.

Geochemistry, lithology and maceral analysis at DSDP Hole 71-511

The quantity, type, and maturity of the organic matter in Recent through Upper Jurassic sediments from the Falkland Plateau, DSDP Site 511, have been determined. Sediments were investigated for their hydrocarbon potential by organic carbon and Rock-Eval pyrolysis. Kerogen concentrates were prepared and analyzed in reflected and transmitted light to determine vitrinite reflectance and maceral content. Total extractable organic compounds were analyzed for their elemental composition, and the fraction of the nonaromatic hydrocarbons was determined by capillary column gas chromatography and combined gas chromatography/mass spectrometry. Three main classes of organic matter can be determined at DSDP Site 511 by a qualitative and quantitative evaluation of microscopic and geochemical results. The Upper Jurassic to lower Albian black shales contain high amounts of organic matter of dominantly marine origin. The content of terrigenous organic matter increases at the base of the black shales, whereas the shallowest black shales near the Aptian/Albian boundary are transitional in composition, with increasing amounts of inert, partly oxidized organic matter which is the dominant component in all Albian through Tertiary sediments investigated. The organic matter in the black shales has a low level of maturity and has not yet reached the onset of thermal hydrocarbon generation. This is demonstrated by the low amounts of total extractable organic compounds, low percentages of hydrocarbons, and the pattern and composition of nonaromatic hydrocarbons. The observed reflectance of huminite and vitrinite particles (between 0.4% and 0.5% Ro at bottom-hole depth of 632 m) is consistent with this interpretation. Several geochemical parameters indicate, however, a rapid increase in the maturation of organic matter with depth of burial. This appears to result from the relatively high heat flow observed at Site 511. If we relate the level of maturation of the black shales at the bottom of Hole 511 to their present shallow depth of burial, they appear rather mature. On the basis of comparisons with other sedimentary basins of a known geothermal history, a somewhat higher paleotemperature gradient and/or additional overburden are required to give the observed maturity at shallow depth. A comparison with contemporaneous sediments of DSDP Site 361, Cape Basin, which was the basin adjacent and to the north of the Falkland Plateau during the early stages of the South Atlantic Ocean, demonstrates differences in sedimentological features and in the nature of sedimentary organic matter. We interpret these differences to be the result of the different geological settings for Sites 361 and 511.

Common depth points and associated geographic coordinates

Fluids in subduction zones can influence seismogenic behaviour and prism morphology. The Eastern Makran subduction zone, offshore Pakistan, has a very thick incoming sediment section of up to 7.5 km, providing a large potential fluid source to the accretionary prism. A hydrate-related bottom simulating reflector (BSR), zones of high amplitude reflectivity, seafloor seep sites and reflective thrust faults are present across the accretionary prism, indicating the presence of fluids and suggesting active fluid migration. High amplitude free gas zones and seep sites are primarily associated with anticlinal hinge traps, and fluids here appear to be sourced from shallow biogenic sources and migrate to the seafloor along minor normal faults. There are no observed seep sites associated with the surface expression of the wedge thrust faults, potentially due to burial of the surface trace by failure of the steep thrust ridge slopes. Thrust fault reflectivity is restricted to the upper 3 km of sediment and the deeper décollement is non-reflective. We interpret that fluids and overpressure are not common in the deeper stratigraphic section. Thermal modelling of sediments at the deformation front suggests that the deeper sediment section is relatively dewatered and not currently contributing to fluid expulsion in the Makran accretionary prism.

Epoch, organic carbon and compounds at DSDP Holes 93-605 and 95-613

Twenty-four sediment samples from DSDP Holes 605 (Leg 93) and 613 (Leg 95) on the New Jersey continental rise were analyzed by pyrolysis-gas chromatography. Twelve of these samples were also analyzed by pyrolysis-gas chromatography/mass spectrometry. The degree of preservation of sediment organic matter, as determined by these techniques, helped to distinguish slumped sediments from sediments that have not moved from their original place of deposition. Total levels of pyrolyzable organic material, as determined from pyrolysis-gas chromatography, were low in sediments that were not slumped, indicating that the organic material is highly degraded. Nitrogen- and oxygen-containing compounds were the primary compounds detected by gas chromatography/mass spectrometry (GCMS) analysis of the pyrolyzate of non-slumped sediments. Smaller amounts of aromatic compounds and branched alkanes were also present in some of these samples. In contrast, slumped sediments showed larger amounts of pyrolyzable organic matter, as determined from pyrolysis-gas chromatography, and better preservation of alkyl chains in the sediment organic matter, as suggested by the presence of n-alkanes in GCMS analysis of the pyrolyzate. Better preservation of the organic matter in slumped sediments can be attributed to more moderate bioturbation by bottom-dwelling organisms at the original deposition site.