Gas hydrate structures and C1-C5 hydrocarbons at individual sites in the Gulf of Mexico

Gas hydrate samples from various locations in the Gulf of Mexico (GOM) differ considerably in their microstructure. Distinct microstructure characteristics coincide with discrete crystallographic structures, gas compositions and calculated thermodynamic stabilities. The crystallographic structures were established by X-ray diffraction, using both conventional X-ray sources and high-energy synchrotron radiation. The microstructures were examined by cryo-stage Field-Emission Scanning Electron Microscopy (FE-SEM). Good sample preservation was warranted by the low ice fractions shown from quantitative phase analyses. Gas hydrate structure II samples from the Green Canyon in the northern GOM had methane concentrations of 70-80% and up to 30% of C2-C5 of measured hydrocarbons. Hydrocarbons in the crystallographic structure I hydrate from the Chapopote asphalt volcano in the southern GOM was comprised of more than 98% methane. Fairly different microstructures were identified for those different hydrates: Pores measuring 200-400 nm in diameter were present in structure I gas hydrate samples; no such pores but dense crystal surfaces instead were discovered in structure II gas hydrate. The stability of the hydrate samples is discussed regarding gas composition, crystallographic structure and microstructure. Electron microscopic observations showed evidence of gas hydrate and liquid oil co-occurrence on a micrometer scale. That demonstrates that oil has direct contact to gas hydrates when it diffuses through a hydrate matrix.

Physical properties, grain size distribution and clay mineralogy of ODP Leg 117 sites

The fabric of sediments recovered at sites drilled on the Indus Fan, Owen Ridge, and Oman margin during Ocean Drilling Program Leg 117 was examined by scanning electron microscopy to document changes that accompany sediment burial. Two sediment types were studied: (1) biogenic sediments consisting of a variety of marly nannofossil and nannofossil oozes and chalks and (2) terrigenous sediments consisting of fine-grained turbidites deposited in association with the Indus Fan. Biogenic sediments were examined with samples from the seafloor to depths of 306 m below seafloor (mbsf) on the Owen Ridge (Site 722) and 368 mbsf on the Oman margin (Sites 723 and 728). Over these depth ranges the biogenic sediments are characterized by a random arrangement of microfossils and display little chemical diagenetic alteration. The microfossils are dispersed within a fine-grained matrix that is predominantly microcrystalline carbonate particles on the Owen Ridge and clay and organic matter on the Oman margin. Sediments with abundant siliceous microfossils display distinct, open fabrics with high porosity. Porosity reduction resulting from gravitational compaction appears to be the primary process affecting fabric change in the biogenic sediment sections. Fabric of illite-rich clayey silts and silty claystones from the Indus Fan (Site 720) and Owen Ridge (Sites 722 and 731) was examined for a composite section extending from 45 to 985 mbsf. In this section fabric of the fine-grained turbidites changes from one with small flocculated clay domains, random particle arrangement, and high porosity to a fabric with larger domains, strong preferred particle orientation roughly parallel to bedding, and lower porosity. These changes are accomplished by a growth in domain size, primarily through increasing face-to-face contacts, and by particle reorientation which is characterized by a sharp increase in alignment with bedding between 200 and 400 mbsf. Despite extensive particle reorientation, flocculated clay fabric persists in the deepest samples examined, particularly adjacent to silt grains, and the sediments lack fissility. Fabric changes over the 45-985 mbsf interval occur in response to gravitational compaction. Porosity reduction and development of preferred particle orientation in the Indus Fan and Owen Ridge sections occur at greater depths than outlined in previous fabric models for terrigenous sediments as a consequence of a greater abundance of silt and a greater abundance of illite and chlorite clays.

Paleomagnetic of ODP Leg 125 sites

During Leg 125, scientists drilled Sites 782, 783, 784, and 786 across a transect of the Izu-Bonin forearc near 31°N. Magnetostratigraphy for whole-core and discrete specimens has been integrated with biostratigraphic data and correlated to the geomagnetic polarity time scale. These correlations are good back to the middle Miocene at Sites 783, 784, and 786 and to the late Oligocene at Site 782, but become more tentative in older sediments because of poor recovery and complex magnetizations.

Compilation of sedimentation rates and smear slide analysis of DSDP sites

A history of Mesozoie and Cenozoic palaeoenvironments of the North Atlantie Oeean has been developed based on a detailed analysis of the temporal and spatial distribution of major pelagie sediment facies, of hiatuses. of bulk sediment accumulation rates, and of concentrations and fluxes of the main deep-sea sediment components. The depositional history of the North Atlantic can be subdivided into three major phase: (a) Late Jurassie and Early Cretaceous phase: clastic terrigenous and biogenic pelagic sediment components accumulated rapidly under highly productive surface water masses over the entire occan basin; (b) Late Cretaceous to Early Miocene phase: relatively little terrigenous and pelagic biogenic sediment reached the North Atlantic Ocean floor, intensive hiatus formation occurred at variable rates, and wide stretches of the deep-ocean floor were covered by slowly accumulating terrigenous muds: (c) Middle Miocene to Recent phase: accumulation rates of biogenic and terrigenous deep-sea sediment components increased dramatically up to Quaternary times, rates of hiatus formation and the intensity of deep-water circulation inferred from them seem to have decreased. However, accumulation rate patterns of calcareous pelagic sediment components suggest that large scale reworking and di splacement of deep-sea sediments occurred at a variable rate over wide areas of the North Atlantic during this period.

Index properties, consolidation characteristics and sediment rebound of ODP Sites 167-1020 and 167-1021 sediments

Drilling during Leg 167 at the California margin was scheduled to recover continuous sedimentary sections. Multiple advanced piston core (APC) holes drilled at different depth offsets provided core overlap in successive APCs. Correlation of high-resolution laboratory physical properties data from adjacent APC holes was used to compile composite depth sections for each site. The composite depth sections were used to confirm continuous recovery and enable high-resolution sampling. The meters composite depth (mcd) scale differs from the shipboard meters below seafloor (mbsf) scale because of (1) core expansion following recovery (MacKillop et al., 1995, doi:10.2973/odp.proc.sr.138.118.1995), (2) coring gaps, and (3) stretching/compression of sediment during coring (Lyle, Koizumi, Richter, et al., 1997, doi:10.2973/odp.proc.ir.167.1997). Moran (1997, doi:10.2973/odp.proc.sr.154.132.1997) calculated that sediment expansion accounted for 90%-95% of the Leg 154 depth offset between shipboard mbsf and the mcd scales. Terzaghi's one-dimensional theory of consolidation (Terzaghi, 1943) describes the response of sediments to stress loading and release. Mechanical loading in marine environments is provided by the buoyant weight of the overlying sediments. The load increases with depth below seabed, resulting in sediment volume reduction as water is "squeezed" out of the voids in the sediment. Stress release during core recovery results in expansion of the sediment and volume increase as water returns to the sediment. The sediment expansion or rebound defines the elastic properties of the sediment. In this study we examine the elastic deformation properties of sediments recovered from Sites 1020 and 1021. These results are used to (1) correct the laboratory index properties measurements to in situ values and (2) determine the contribution of sediment rebound to the depth offset between the mbsf and mcd scales.

Silicoflagellates, actiniscidians, and ebridians of ODP Leg 105 sites

Neogene and Quaternary silicoflagellates, actiniscidians, and ebridians are described from Sites 679 through 688 in the eastern Pacific off Peru. Five silicoflagellate zones and one horizon can be distinguished in the Neogene and Quaternary sequences. The encountered Eocene and Oligocene sequences are barren in silicoflagellates. Several hiatuses were noted in the Neogene and early Pleistocene sequences. Displaced silicoflagellates and ebridians from older strata were found occasionally, with a distinct increase in the Quaternary at Site 688. Distribution lists for species found are presented for Sites 682, 683, 685 and 688. Systematic discussion centers on the Distephanus bioctonarius group, with special reference to Hole 681A. Two new forms (Distephanus bioctonarius f. decimarius and Distephanus speculum subsp. speculum f. pseudoseptenarius) are described from the eastern Pacific Quaternary sequence.

Oxygen and hydrogen isotope ratios of pore waters from ODP sites in the Mediterranean Sea

Pore fluids from two ODP sites at Eastern Mediterranean mud volcanoes have been analyzed for their Cl concentration and their delta18O and deltaD isotopic composition. The Cl data span a wide range of concentrations, from extremely depleted with respect to seawater (as low as 60 mM) at the crest of Milano dome (site 970) to strongly enriched (up to 5.4 M) at Napoli dome (site 971). Chloride enrichment is known to be due to dissolving Messinian evaporites, whereas the source of the low-Cl fluid is deduced from stable isotope data presented here. The isotopic composition of the endmember fluid is found to be +10? for delta18O and -32? for deltaD for low- as well as for high-Cl waters. From this signature it can be concluded that neither gas hydrates nor meteoric water play a significant role in the freshening of the pore water. Several other processes altering the delta18O/deltaD composition of pore waters are discussed and considered to be of only negligible influence. The process characterizing the isotopic composition of the fluid is found to be clay mineral dehydration (mainly smectite-illite transformation), corresponding to a depth range of 3.5-7 km and an elevated temperature of about 120-165°C. A quantitative estimate shows that this reaction is capable of producing the observed extreme Cl depletion.

Mineral composition of mid-ocean-ridge basalts from ODP Leg 187 sites

The chemical compositions of olivine, plagioclase, pyroxene, and spinel in lavas collected during Ocean Drilling Program Leg 187 in the Australian Antarctic Discordance, Southeast Indian Ridge (41°-46°S, 126°-135°E) were analyzed, and modeling of the theoretical equilibrium petrogenetic conditions between olivine and melt was conducted. The cores of larger olivine phenocrysts, particularly in the isotopic Indian-type mid-ocean-ridge basalt (MORB), are not equilibrated with melt compositions and are considered to be xenocrystic. Larger plagioclase phenocrysts with compositionally reversed zonation are also xenocrystic. The compositions of primary magma were calculated using a "maximum olivine fractionation" model for primitive MORB that should fractionate only olivine. Olivine compositions equilibrated with calculated primary magma and compositions of calculated primary magma suggest that (1) isotopic Pacific-type MORB is more fractionated than Indian-type MORB, (2) Pacific-type MORB was produced by higher degrees of partial melting than Indian-type MORB, and (3) primary magma for Indian-type MORB was segregated from mantle at 10 kbar (~30 km depth), whereas that for Pacific-type MORB was segregated at 15 kbar (~45 km depth).

Minerals, geochemistry and x-ray power characteristics at DSDP Sites 54-424, 60-458 and 60-459

Secondary minerals filling veins and vesicles in volcanic basement at Deep Sea Drilling Project Sites 458 and 459 indicate that there were two stages of alteration at each site: an early oxidative, probably hydrothermal, stage and a later, low-temperature, less oxidative stage, probably contemporaneous with faulting in the tectonically active Mariana forearc region. The initial stage is most evident in Hole 459B, where low-Al, high Fe smectites and iron hydroxides formed in vesicles in pillow basalts and low-Al palygorskite formed in fractures. Iron hydroxides and celadonite formed in massive basalts next to quartz-oligoclase micrographic intergrowths. Palygorskite was found in only one sample near the top of basement in Hole 458, but it too is associated with iron hydroxides. Palygorskite has previously been reported only in marine sediments in DSDP and other occurrences. It evidently formed here as a precipitate from fluids in which Si, Mg, Fe, and even some Al were concentrated. Experimental data suggest that the solutions probably had high pH and somewhat elevated temperatures. The compositions of associated smectites resemble those in hydrothermal sediments and in basalts at the Galapagos mounds geothermal field. The second stage of alteration was large-scale replacement of basalt by dioctahedral, trioctahedral, or mixed-layer clays and phillipsite along zones of intense fracturing, especially near the bottom of Holes 458 and 459B. The basalts are commonly slickensided, and there are recemented microfault offsets in overlying sediments. Native copper occurs in one core of Hole 458, but associated smectites are dominantly dioctahedral, unlike Hole 459B, where they are mainly trioctahedral, indicating nonoxidative alteration. The alteration in both holes is more intense than at most DSDP ocean crust sites and may have been augmented by water derived from subducting ocean crust beneath the fore-arc region.

Petrology of ODP Leg 210 and Leg 173, and DSDP Leg 47 sites

Sand detrital modes of Albian-Eocene clastic gravity-flow deposits cored and recovered at Ocean Drilling Program Site 1276 reflect the postrift geologic evolution of the Newfoundland passive continental margin. Cretaceous sandstone compositions (average: Q57F23L20; Ls%Lsc = 35; total%bioclasts = 3) are consistent with a source on Grand Banks such as Avalon Uplift. Their relatively low potassium feldspar (Qm71K8P21) contents distinguish them from Iberian sandstones and appear to preclude an easterly source during the early history of the ocean basin. Isolated volcaniclastic input near the Paleocene/Eocene boundary (~60 Ma) at Site 1276 is also present in Iberian samples of this age, suggesting that magmatism was widespread across the North Atlantic during this time frame; the source(s) of this volcanic debris remains equivocal. In the Eocene, the development of carbonate bank facies on the shelf marks a profound compositional change to calcareous grainstones (average: Q27F11L62; Ls%Lsc = 82; total%bioclasts = 55) in basinal gravity-flow deposits at Site 1276. This calcareous petrofacies is present on the Iberian margin and in the Pyrenees, suggesting that it was a regional event. The production and downslope redistribution of carbonate debris, including bioclastic and lithic fragments, was likely eustatically controlled. The Newfoundland (Site 1276 and Jeanne d'Arc Basin) sandstones are mainly quartzolithic. Their composition and the contrast in composition between them and more quartzofeldspathic sandstones from the Iberian margin are likely a product of rifting along a Paleozoic suture zone separating distinct basement terranes. This prerift geologic setting contrasts with that of rifts developed within other cratonic settings with variable amounts of synrift volcanism. When synthesized, the spectrum of synrift and postrift sand compositions produces a general model of passive margin (rift-to-drift) sandstone provenance.

Late Cretaceous planktonic foraminiferal assemblages from the Exmouth Plateau, ODP Sites 122-762 and 122-763, eastern Indian Ocean

The evolution of planktonic foraminifera during the Late Cretaceous is marked in the Santonian by the disappearance of complex morphotypes (the marginotruncanids), and the contemporary increasing importance and diversification of another group of complex taxa, the globotruncanids. Upper Turonian to lower Campanian planktonic foraminiferal assemblages from Holes 762C and 763B (Ocean Drilling Program, Leg 122, Exmouth Plateau, 47°S palaeolatitude) were studied in detail to evaluate the compositional variations at the genus and species level based on the assumption that, in the Cretaceous oceans as in the modern, any faunal change was associated with changes in the characteristics and the degree of stability of the oceanic surface waters. Three major groups were recognised based on gross morphology, and following the assumption that Cretaceous planktonic foraminifera, although extinct, had life-history strategies comparable to those of modern planktonics: 1 - r-selected opportunists; 2 - k-selected specialists; 3 - r/k intermediate morphotypes which include all genera that display a range of trophic strategies in-between opportunist and specialist taxa. Although planktonic foraminiferal assemblages are characterised by a progressive appearance of complex taxa, this trend is discontinuous. Variation in number of species and specimens within genera has allowed recognition of five discrete intervals each of them reflecting different oceanic conditions based on fluctuations in diversity and abundance of the major morphotypes. Planktonic forms show cyclical fluctuations in diversity and abundance of cold (r-strategists) and warm taxa (k-strategists), perhaps representing alternating phases of unstable conditions (suggesting a weakly stratified upper water column in a mesotrophic environment), and well-stratified surface and near-surface waters (indicating a more oligotrophic environment). Interval 1, middle Turonian to early Coniacian in age, is dominated by the r/k intermediate morphotypes which alternate with r-strategists. These cyclical alternations are used to identify three additional subintervals. Interval 2, aged middle to late Coniacian, is characterised by the increasing number of species and relative abundance of k-strategists. After this maximum diversification the k-strategists show a progressive decrease reaching a minimum value in Interval 3 (early to late Santonian), which corresponds to the extinction of the genus Marginotruncana. In the Interval 4, latest Santonian in age, the k-strategists, represented mainly by the genera Globotruncana, increase again in diversity and abundance. The last Interval 5 (early Campanian) is dominated by juvenile globotruncanids and r-strategists which fluctuate in opposite phase. The positive peak (Interval 2) related to the maximum diversification of warm taxa (k-strategists) in the Coniacian seems to correspond to a warmer episode. It is followed by a marked decrease in the relative abundance of warm taxa (k-strategists crisis) with a minimum in the late Santonian (Interval 3), reflecting a decrease in temperature. Detailed analysis of faunal variations allows the Santonian faunal turnover to be ascribed to a cooling event strong enough to cause the extinction of the marginotruncanids.

Barium in sediments and pore waters of several ODP Leg 170 and Leg 205 sites

Barium concentrations were measured on 17 pore fluid and 13 sediment samples from Sites 1253 and 1254 drilled offshore Costa Rica during Ocean Drilling Program (ODP) Leg 205. An additional 83 pore fluid and 29 sediment samples were analyzed for Ba concentrations from Sites 1039 and 1040 drilled during ODP Leg 170 offshore Costa Rica. Sites 1039/1253 and 1040/1254 are part of a transect across the Middle America Trench offshore Nicoya Peninsula. The entire incoming sediment section is being underthrust beneath the margin, providing an ideal setting to examine Ba cycling in the shallow levels of the subduction zone. Results from these analyses indicate that a significant amount of Ba is liberated from the mineral barite (BaSO4) in the uppermost hemipelagic sediments arcward of the trench. The shallow distillation of Ba may impact the amount of sedimentary Ba reaching the deeper subduction zone.

Consolidation properties and permeability values of sediments from three ODP Leg 205 sites

Vertical permeability and sediment consolidation measurements were taken on seven whole-round drill cores from Sites 1253 (three samples), 1254 (one sample), and 1255 (three samples) drilled during Ocean Drilling Program Leg 205 in the Middle America Trench off of Costa Rica's Pacific Coast. Consolidation behavior including slopes of elastic rebound and virgin compression curves (Cc) was measured by constant rate of strain tests. Permeabilities were determined from flow-through experiments during stepped-load tests and by using coefficient of consolidation (Cv) values continuously while loading. Consolidation curves and the Casagrande method were used to determine maximum preconsolidation stress. Elastic slopes of consolidation curves ranged from 0.097 to 0.158 in pelagic sediments and 0.0075 to 0.018 in hemipelagic sediments. Cc values ranged from 1.225 to 1.427 for pelagic carbonates and 0.504 to 0.826 for hemipelagic clay-rich sediments. In samples consolidated to an axial stress of ~20 MPa, permeabilities determined by flow-through experiments ranged from a low value of 7.66 x 10**-20 m**2 in hemipelagic sediments to a maximum value of 1.03 x 10**-16 m**2 in pelagic sediments. Permeabilities calculated from Cv values in the hemipelagic sediments ranged from 4.81 x 10**-16 to 7.66 x 10**-20 m**2 for porosities 49.9%-26.1%.