Pressure core barrel characteristics and composition of gases at DSDP Site 76-533

A pressure core barrel (PCB), developed by the Deep Sea Drilling Project, was used successfully to recover, at in situ pressure, sediments of the Blake Outer Ridge, offshore the southeastern United States. The PCB is a unique, wire-line tool, 10.4 m long, capable of recovering 5.8 m of core (5.8 cm in diameter), maintained at or below in situ pressures of 34.4 million Pascals (MPa), and 1.8 m of unpressurized core (5.8 cm in diameter). All excess internal pressure above the operating pressure of 34.4 MPa is automatically vented off as the barrel is retrieved. The PCB was deployed five times at DSDP Site 533 where geophysical evidence suggests the presence of gas hydrates in the upper 600 m of sediment. Three cores were obtained holding average in situ pressures of 30 MPa. Two other cores did not maintain in situ pressures. Three of the five cores were intermittently degassed at varying intervals of time, and portions of the vented gas were collected for analysis. Pressure decline followed paths indicative of gas hydrates and/or dissolved gas. The released gas was dominantly methane (usually greater than 90%), along with higher molecular-weight hydrocarbon gases and carbon dioxide. During degassing the ratio of methane to ethane did not vary significantly. On the other hand, concentrations of higher molecular-weight hydrocarbon gases increased, as did carbon dioxide concentrations. The results from the PCB experiments provide tentative but equivocal evidence for the presence of .gas hydrates at Site 533. The amount of gas hydrate indicated is small. Nevertheless, this work represents the first successful study of marine gas hydrates utilizing the PCB.

Geochemistry and mineralogy of selected carbonaceous claystones at DSDP Hole 76-534

Four dominant depositions of carbonaceous claystones are recognized to have occurred during the early Aptian to middle Albian at Site 534. There are correlations of stable isotope ratios with organic carbon content and of clay content with clay mineralogy of the samples. Almost all organic carbon in these sequences has very negative terrestrial isotope ratios, and the clay of that age indicates predominance of aluminous montmorillonite, which is thought to be of terrigenous origin. It is suggested that development of coastal vegetation belts and deltaic outbuilding with consequent outpouring of land-plant detritus and terrigenous elastics into the deep basins probably led to formation of the "black shale" facies.

Geochemistry at DSDP Site 76-533

Bulk X-ray mineralogy of 47 hemipelagic mud and clay samples from the Blake Outer Ridge has revealed that the sediments contain low magnesian calcite, calcian dolomite, ferroan dolomite, and magnesian siderite. Dolomite and siderite are authigenic and occur as rhombohedrons scattered through the sediments, whereas calcite is mostly biogenic. Pliocene dolomitic lenses are made up of interlocking polyhedral grains of ferroan dolomite. The contents of authigenic dolomite and siderite are 3 to 8% in carbonate sediments and 70 to 89% in dolomitic lenses. Dolomite occurs largely in the cores above 192 m sub-bottom depth, whereas siderite occurs in the cores below 87 m. The distribution and occurrence of dolomite and siderite have determined the diagenetic zonation of carbonates as Zone I (dolomitic zone, top-90 m), Zone II (transition zone, 90-180 m), and Zone III (sideritic zone, 180 m-bottom). Measurements of major and minor elements in the untreated total sediment samples and the insoluble residues after digestion in acid-reducing solution have revealed that the soluble fraction concentrates carbonates and ferromanganese associations (Ca, Mg, Sr, Fe, and Mn). Typical "hydrogenous elements" (Co, Cu, Ni, and V) are more concentrated in the insoluble residues rather than in the soluble fraction; the concentrations of these four elements are low and comparable to modern offshore mud, probably because the Site 533 sediments were deposited at a high rate of sedimentation. The contents of Fe2O3 and MnO are somewhat high for rapidly accumulated mud, particularly in the Pliocene sediments (8.09 and 0.26%, respectively, on a Carbonate-free basis). The high Fe and Mn contents are mainly due to the high contribution of the leacheable nonlithogenous fraction; leacheable Fe and Mn originate in the ferromanganese oxide accumulated on the seafloor. Only a small amount of ferric oxide was converted to iron sulfide in the surficial part of Zone I. Most ferromanganese oxide was reduced and precipitated as ferroan dolomite and magnesian siderite in Zones II and III under high alkalinity and high pH conditions in the organic-matter-rich sediments. Fe2+ and Mn2+ in the deeper sediments beneath Zone III possibly migrated upward and concentrated as siderite in Zone III, hence resulting in high contents of Fe and Mn in the Pliocene sediments. Analysis of carbonate zonation on the Blake Outer Ridge has revealed that the zonation is subparallel to the bedding plane rather than to the present seafloor. The sediments at Site 103 on the flank region of the Ridge are lacking Zone I and most of Zone II, probably the result of erosion of the most of the Pleistocene and Pliocene sediments by the enhanced bottom currents during the Pleistocene.

Geochemistry and isotopes at DSDP Site 76-533

Concentrations and d34S and d13C values were determined on SO4, HCO3, CO2, and CH4 in interstitial water and gas samples from the uppermost 400 m of sediment on the Blake Outer Ridge. These measurements provide the basis for detailed interpretation of diagenetic processes associated with anaerobic respiration of electrons generated by organic- matter decomposition. The sediments are anaerobic at very shallow depths (<1 m) below the seafloor. Sulfate reduction is confined to the uppermost 15 m of sediment and results in a significant outflux of oxidized carbon from the sediments. At the base of the sulfate reduction zone, upward-diffusing CH4 is being oxidized, apparently in conjunction with SO4 reduction. CH4 generation by CO2 reduction is the most important metabolic process below the 15-m depth. CO2 removal is more rapid than CO2 input over the depth interval from 15 to 100 m, and results in a slight decrease in HCO3 concentration accompanied by a 40 per mil positive shift in d13C. The differences among coexisting CH4, CO2, and HCO3 are consistent with kinetic fractionation between CH4 and dissolved CO2, and equilibrium fractionation between CO2 and HCO3. At depths greater than 100 m, the rate of input of CO2 (d13C = -25 per mil) exceeds by 2 times the rate of removal of CO2 by conversion to CH4 (d13C of -60 to -65 per mil). This results in an increase of dissolved HCO3 concentration while maintaining d13C of HCO3 relatively constant at +10 per mil. Non-steady-state deposition has resulted in significantly higher organic carbon contents and unusually high (70 meq/l) pore-water alkalinities below 150 m. These high alkalinities are believed to be related more to spontaneous decarboxylation reactions than to biological processes. The general decrease in HCO3 concentration with constant d13C over the depth interval of 200 to 400 m probably reflects increased precipitation of authigenic carbonate. Input-output carbon isotope-mass balance calculations, and carbonate system equilibria in conjunction with observed CO2-CH4 ratios in the gas phase, independently suggest that CH4 concentrations on the order of 100 mmol/kg are present in the pore waters of Blake Outer Ridge sediments. This quantity of CH4 is believed to be insufficient to saturate pore waters and stabilize the CH4*6H2O gas hydrate. Results of these calculations are in conflict with the physical recovery of gas hydrate from 238 m, and with the indirect evidence (seismic reflectors, sediment frothing, slightly decreasing salinity and chlorinity with depth, and pressure core barrel observations) of gas-hydrate occurrence in these sediments. Resolution of this apparent conflict would be possible if CH4 generation were restricted to relatively thin (1-10 m) depth intervals, and did not occur uniformly at all depths throughout the sediment column, or if another methanogenic process (e.g., acetate fermentation) were a major contributor of gas.

Lithology and organic geochemistry at DSDP Hole 76-534

The organic facies of Early and middle Cretaceous sediments drilled at DSDP Site 534 is dominated by terrestrially derived plant remains and charcoal. Marine organic matter is mixed with the terrestrial components, but through much of this period was diluted by the terrestrial material. The supply of terrestrial organic matter was high here because of the nearness of the shore and high runoff promoted by a humid temperate coastal climate. Reducing conditions favored preservation of both marine and terrestrial organic matter, the terrestrial materials having reached the site mostly in turbidity currents or in the slow-moving, near-bottom nepheloid layer. An increase in the abundance of terrestrial organic matter occurred when the sea level dropped in the Valanginian and again in the Aptian-Albian, because rivers dumped more terrigenous elastics into the Basin and marine productivity was lower at these times than when sea level was high. A model is proposed to explain the predominance of reducing conditions in the Valanginian-Aptian, of oxidizing conditions in the late Aptian, and of reducing conditions in the Albian-Cenomanian. The model involves influx of oxygen-poor subsurface waters from the Pacific at times of high or rising sea level (Valanginian-Aptian, and Albian- Cenomanian) and restriction of that influx at times of low sea level (late Aptian). In the absence of a supply of oxygenpoor deep water, the bottom waters of the North Atlantic became oxidizing in the late Aptian, probably in response to development of a Mediterranean type of circulation. The influx of nutrients from the Pacific led to an increase in productivity through time, accounting for an increase in the proportion of marine organic matter from the Valanginian into the Aptian and from the Albian to the Cenomanian. Conditions were dominantly oxidizing through the Middle Jurassic into the Berriasian, with temporary exceptions when bottom waters became reducing, as in the Callovian. Mostly terrestrial and some marine organic matter accumulated during the Callovian reducing episode. When Jurassic bottom waters were oxidizing, only terrestrial organic matter was buried in the sediments, in very small amounts.

Calcareous nannofossil zonation, ages and sedimentation rates at DSDP Hole 76-534

A zonation is presented for the oceanic late Middle Jurassic to Late Jurassic of the Atlantic Ocean. The oldest zone, the Stephenolithion bigotii Zone (subdivided into a Stephanolithion hexum Subzone and a Cyclagelosphaera margerelii Subzone), is middle Callovian to early Oxfordian. The Vagalapilla stradneri Zone is middle Oxfordian to Kimmeridgian. The Conusphaera mexicana Zone, subdivided into a lower Hexapodorhabdus cuvillieri Subzone and a Polycostella beckmannii Subzone, is the latest Kimmeridgian to Tithonian. Direct correlation of this zonation with the boreal zonation established for Britain and northern France (Barnard and Hay, 1974; Medd, 1982; Hamilton, 1982) is difficult because of poor preservation resulting in low diversity for the cored section at Site 534 and a lack of Tithonian marker species in the boreal realm. Correlations based on dinoflagellates and on nannofossils with stratotype sections (or regions) give somewhat different results. Dinoflagellates give generally younger ages, especially for the Oxfordian to Kimmeridgian part of the recovered section, than do nannofossils.