Carbon and deuterium isotopes and C ratios in gas hydrates of ODP Leg 204 sites

Sediments at the southern summit of Hydrate Ridge display two distinct modes of gas hydrate occurrence. The dominant mode is associated with active venting of gas exsolved from the accretionary prism and leads to high concentrations (15%-40% of pore space) of gas hydrate in seafloor or near-surface sediments at and around the topographic summit of southern Hydrate Ridge. These near-surface gas hydrates are mainly composed of previously buried microbial methane but also contain a significant (10%-15%) component of thermogenic hydrocarbons and are overprinted with microbial methane currently being generated in shallow sediments. Focused migration pathways with high gas saturation (>65%) abutting the base of gas hydrate stability create phase equilibrium conditions that permit the flow of a gas phase through the gas hydrate stability zone. Gas seepage at the summit supports rapid growth of gas hydrates and vigorous anaerobic methane oxidation. The other mode of gas hydrate occurs in slope basins and on the saddle north of the southern summit and consists of lower average concentrations (0.5%-5%) at greater depths (30-200 meters below seafloor [mbsf]) resulting from the buildup of in situ-generated dissolved microbial methane that reaches saturation levels with respect to gas hydrate stability at 30-50 mbsf. Net rates of sulfate reduction in the slope basin and ridge saddle sites estimated from curve fitting of concentration gradients are 2-4 mmol/m**3/yr, and integrated net rates are 20-50 mmol/m**2/yr. Modeled microbial methane production rates are initially 1.5 mmol/m**3/yr in sediments just beneath the sulfate reduction zone but rapidly decrease to rates of <0.1 mmol/m**3/yr at depths >100 mbsf. Integrated net rates of methane production in sediments away from the southern summit of Hydrate Ridge are 25-80 mmol/m**2/yr. Anaerobic methane oxidation is minor or absent in cored sediments away from the summit of southern Hydrate Ridge. Ethane-enriched Structure I gas hydrate solids are buried more rapidly than ethane-depleted dissolved gas in the pore water because of advection from compaction. With subsidence beneath the gas hydrate stability zone, the ethane (mainly of low-temperature thermogenic origin) is released back to the dissolved gas-free gas phases and produces a discontinuous decrease in the C1/C2 vs. depth trend. These ethane fractionation effects may be useful to recognize and estimate levels of gas hydrate occurrence in marine sediments.

Age model and elemental data of DSDP Holes 48-401 and 80-549

A growing body of geologic evidence suggests that emplacement of the North Atlantic Igneous Province (NAIP) played a major role in global warming during the early Paleogene as well as in the transient Paleocene-Eocene thermal maximum (PETM) event. A ~5 million year record of major and trace element abundances spanning 56 to 51 Ma at Deep Sea Drilling Project Sites 401 and 549 confirms that the majority of NAIP volcanism occurred as subaerial flows. Thus the trace element records provide constraints on the nature and scope of the environmental impact of the NAIP during the late Paleocene-early Eocene interval. Subaerial volcanism would have injected mantle CO2 directly into the atmosphere, resulting in a more immediate increase in atmospheric greenhouse gas abundances than CO2 input through submarine volcanism. The lack of significant hydrothermalism contradicts recently proposed mechanisms for thermally destabilizing methane hydrate reservoirs during the PETM. Any connection between NAIP volcanism and PETM warming had to occur through the atmosphere.

Chlorine concentration and isotopic data for sediments and serpentine seamount material from ODP Legs 125, 129, 185, and 195

Chlorine isotope ratios were determined for volcanic gas, geothermal well, ash, and lava samples along the Izu-Bonin-Mariana volcanic front, serpentinite clasts and muds from serpentine seamounts (Conical, South Chamorro, Torishima), basalts from the Guguan cross-chain, and sediments from Ocean Drilling Program (ODP) Sites 800, 801, 802, and 1149. There is no systematic variation in d37Cl values along the volcanic front in either gas or ash samples. In contrast, distinct variations occur across the arc, implying variations in the fluid source at different depths within the subduction zone. Serpentinite clasts and serpentine muds from the seamounts tap a source of ~30 km depth and have d37Cl values of structurally bound chloride of +0.4 per mil +/- 0.4 per mil (n = 24), identical to most seafloor serpentinites, suggesting a serpentinite (chrysotile and/or lizardite to antigorite transition) fluid source. Tapping deeper levels of the subduction zone (~115-130 km depth), volcanic gases and ashes have d37Cl values averaging -1.1 per mil +/- 1.0 per mil (n = 29), precisely overlapping the range measured in sediments from ODP cores (-1.1 per mil +/- +0.7 per mil, n = 11) and limited altered oceanic crust (AOC). Both sediments and AOC are possible Cl sources in the volcanic front. The Guguan cross-chain basalts come from the greatest depths and have an average d37Cl value of +0.2 per mil +/- 0.2 per mil (n = 3), suggesting a second serpentine-derived source, in this case from antigorite breakdown at ~200 km depth.

Environmental characteristics and gas composition of Lost Hammer, Canadian Arctic

We report the first microbiological characterization of a terrestrial methane seep in a cryo-environment in the form of an Arctic hypersaline (~24% salinity), subzero (-5 C), perennial spring, arising through thick permafrost in an area with an average annual air temperature of -15 C. Bacterial and archaeal 16S rRNA gene clone libraries indicated a relatively low diversity of phylotypes within the spring sediment (Shannon index values of 1.65 and 1.39, respectively). Bacterial phylotypes were related to microorganisms such as Loktanella, Gillisia, Halomonas and Marinobacter spp. previously recovered from cold, saline habitats. A proportion of the bacterial phylotypes were cultured, including Marinobacter and Halomonas, with all isolates capable of growth at the in situ temperature (-5 C). Archaeal phylotypes were related to signatures from hypersaline deep-sea methane-seep sediments and were dominated by the anaerobic methane group 1a (ANME-1a) clade of anaerobic methane oxidizing archaea. CARD-FISH analyses indicated that cells within the spring sediment consisted of ~84.0% bacterial and 3.8% archaeal cells with ANME-1 cells accounting for most of the archaeal cells. The major gas discharging from the spring was methane (~50%) with the low CH4/C2 + ratio and hydrogen and carbon isotope signatures consistent with a thermogenic origin of the methane. Overall, this hypersaline, subzero environment supports a viable microbial community capable of activity at in situ temperature and where methane may behave as an energy and carbon source for sustaining anaerobic oxidation of methane-based microbial metabolism. This site also provides a model of how a methane seep can form in a cryo-environment as well as a mechanism for the hypothesized Martian methane plumes.

Volume of natural gas within gas-hydrate and free-gas occurrences in ODP Leg 164 sites

Leg 164 of the Ocean Drilling Program was designed to investigate the occurrence of gas hydrate in the sedimentary section beneath the Blake Ridge on the southeastern continental margin of North America. Sites 994, 995, and 997 were drilled on the Blake Ridge to refine our understanding of the in situ characteristics of natural gas hydrate. Because gas hydrate is unstable at surface pressure and temperature conditions, a major emphasis was placed on the downhole logging program to determine the in situ physical properties of the gas hydrate-bearing sediments. Downhole logging tool strings deployed on Leg 164 included the Schlumberger quad-combination tool (NGT, LSS/SDT, DIT, CNT-G, HLDT), the Formation MicroScanner (FMS), and the Geochemical Combination Tool (GST). Electrical resistivity (DIT) and acoustic transit-time (LSS/SDT) downhole logs from Sites 994, 995, and 997 indicate the presence of gas hydrate in the depth interval between 185 and 450 mbsf on the Blake Ridge. Electrical resistivity log calculations suggest that the gas hydrate-bearing sedimentary section on the Blake Ridge may contain between 2 and 11 percent bulk volume (vol%) gas hydrate. We have determined that the log-inferred gas hydrates and underlying free-gas accumulations on the Blake Ridge may contain as much as 57 trillion m**3 of gas.

Carbon/oxygen ratios, clay composition and gas-hydrate saturation of ODP Leg 164 sites

The analyses of downhole log data from Ocean Drilling Program (ODP) boreholes on the Blake Ridge at Sites 994, 995, and 997 indicate that the Schlumberger geochemical logging tool (GLT) may yield useful gas hydrate reservoir data. In neutron spectroscopy downhole logging, each element has a characteristic gamma ray that is emitted from a given neutron-element interaction. Specific elements can be identified by their characteristic gamma-ray signature, with the intensity of emission related to the atomic elemental concentration. By combining elemental yields from neutron spectroscopy logs, reservoir parameters including porosities, lithologies, formation fluid salinities, and hydrocarbon saturations (including gas hydrate) can be calculated. Carbon and oxygen elemental data from the GLT was used to determine gas hydrate saturations at all three sites (Sites 994, 995, and 997) drilled on the Blake Ridge during Leg 164. Detailed analyses of the carbon and oxygen content of various sediments and formation fluids were used to construct specialized carbon/oxygen ratio (COR) fan charts for a series of hypothetical gas hydrate accumulations. For more complex geologic systems, a modified version of the standard three-component COR hydrocarbon saturation equation was developed and used to calculate gas hydrate saturations on the Blake Ridge. The COR-calculated gas hydrate saturations (ranging from about 2% to 14% bulk volume gas hydrate) from the Blake Ridge compare favorably to the gas hydrate saturations derived from electrical resistivity log measurements.

Sea surface temperture reconstruction for ODP Site 189-1172

Relative to the present day, meridional temperature gradients in the Early Eocene age (~56-53 Myr ago) were unusually low, with slightly warmer equatorial regions (Pearson et al., 2007, doi:10.1130/G23175A.1 ) but with much warmer subtropical Arctic (Sluijs et al., 2008, doi:10.1029/2007PA001495) and mid-latitude (Sluijs et al., 2007, doi:10.1038/nature06400) climates. By the end of the Eocene epoch (~34 Myr ago), the first major Antarctic ice sheets had appeared (Zachos et al., 1992, doi:10.1130/0091-7613(1992)020<0569:EOISEO>2.3.CO;2; Barker et al., 2007, doi:10.1016/j.dsr2.2007.07.027), suggesting that major cooling had taken place. Yet the global transition into this icehouse climate remains poorly constrained, as only a few temperature records are available portraying the Cenozoic climatic evolution of the high southern latitudes. Here we present a uniquely continuous and chronostratigraphically well-calibrated TEX86 record of sea surface temperature (SST) from an ocean sediment core in the East Tasman Plateau (palaeolatitude ~65° S). We show that southwest Pacific SSTs rose above present-day tropical values (to ~34° C) during the Early Eocene age (~53 Myr ago) and had gradually decreased to about 21° C by the early Late Eocene age (~36 Myr ago). Our results imply that there was almost no latitudinal SST gradient between subequatorial and subpolar regions during the Early Eocene age (55-50 Myr ago). Thereafter, the latitudinal gradient markedly increased. In theory, if Eocene cooling was largely driven by a decrease in atmospheric greenhouse gas concentration Zachos et al. (2008, doi:10.1038/nature06588), additional processes are required to explain the relative stability of tropical SSTs given that there was more significant cooling at higher latitudes.

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.

Diatom biostratigraphy, Argon ages and chronology of ODP Hole 183-1138A

A thick Neogene section was recovered in the upper ~300 m of Ocean Drilling Program Hole 1138A, drilled on the Central Kerguelen Plateau in the Indian sector of the Southern Ocean. Sediment lithologies consist primarily of mixed carbonate and biosiliceous clays and oozes, with several thin (1-3 cm) tephra horizons. The tephras are glass rich, well sorted, and dominantly trachytic to rhyolitic in composition. Volcaniclastic material in these horizons is interpreted to have originated from Heard Island, 180 km northwest of Site 1138, and was likely emplaced through both primary ash fall and turbiditic, submarine flows. A Neogene age-depth model for Hole 1138A is constructed primarily from 36 diatom biostratigraphic datums. Nannofossil and planktonic foraminifer biostratigraphy provides supporting age information. Additionally, four high-precision 40Ar-39Ar ages are derived from ash and tephra horizons, and these radiometric ages are in close agreement with the biostratigraphic ages. The integrated age-depth model reveals a reasonably complete lower Miocene to upper Pleistocene section in Hole 1138A, with the exception of a ~1-m.y. hiatus at the Miocene/Pliocene boundary. Another possible hiatus is also identified at the Oligocene/Miocene boundary. High Neogene sedimentation rates and the presence of both calcareous and siliceous microfossils, combined with datable tephra horizons, establish Site 1138 as a suitable target for future drilling legs with paleoceanographic objectives. This report also proposes two new diatom species, Fragilariopsis heardensis and Azpeitia harwoodii, from Pliocene strata of Hole 1138A.