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.

Diatom datums and abundance in ODP Hole 188-1165B and 188-1166A sediments

The biostratigraphic distribution and qualitative relative abundance of Quaternary-Pliocene diatoms from Ocean Drilling Program Leg 188, Sites 1165 (64.380°S, 67.219°E) and 1166 (67.696°S, 74.787°E) offshore from East Antarctica, are documented in this report. The upper ~50 meters below seafloor (mbsf) of Hole 1165B consists of brown diatom-bearing silty clay spanning the upper Pleistocene to lower Pliocene. The diatom stratigraphy indicates a disconformity at ~17.1 mbsf of 0.5- to 0.6-m.y. duration. The integration of biostratigraphic and magnetostratigraphic data identified other disconformities at ~6.0, 14.4, 15.6, and 16.0 mbsf, but the duration of these hiatuses cannot be resolved through diatom biostratigraphy. In Hole 1166A, a narrow interval of diatomaceous Quaternary sediment is identified in the upper 2.92 mbsf and dated biostratigraphically at <0.38 Ma. The remaining Quaternary-Pliocene section is dominated by diamicton, except at ~114 mbsf, where two thin diatomaceous beds are present. The lower bed is ~65 cm thick, 2.5-2.7 to 2.7-3.2 Ma in age, and possibly disconformably overlain by the upper bed, which is ~15 cm thick and 1.8-2.0 to 2.1-2.5 Ma in age. The Pliocene assemblages in Hole 1166A contain components of both Southern Ocean and Antarctic continental shelf (Ross Sea) diatom floras.

Sulphate and d34S in pore waters and d13C, d18O and mineral composition of carbonate nodules from ODP Leg 188 sites

Carbon and oxygen isotopic compositions of authigenic carbonate nodules or layers reflect the diagenetic conditions at the time of nodule growth. The shallowest samples of carbonate nodules and dissolved inorganic carbon of pore water samples beneath the sulfate reduction zone (0-160 meters below seafloor [mbsf]) at Site 1165 have extremely negative d13C values (-50 per mil and -62 per mil, respectively). These negative d13C values indicate nodule formation in association with anaerobic methane oxidation coupled with sulfate reduction. The 34S of residual sulfate at Site 1165 shows only minor 34S enrichment (+6 per mil), even with complete sulfate reduction. This small degree of apparent 34S enrichment is due to extreme "open-system" sulfate reduction, with sulfate abundantly resupplied by diffusion from overlying seawater. Ten calcite nodules from Site 1165 contain minor quartz and feldspar and have d13C values ranging from -49.7 per mil to -8.2 per mil. The nodules with the most negative d13C values currently are at depths of 273 to 350 mbsf and must have precipitated from carbonate largely derived from subsurface anaerobic methane oxidation. The processes of sulfate reduction coupled with methane oxidation in sediments of Hole 1165B are indicated by characteristic concentration and isotopic (d34S and d13C) profiles of dissolved sulfate and bicarbonate. Three siderite nodules from Site 1166 contain feldspar and mica and one has significant carbonate-apatite. The siderite has d13C values ranging from -15.3 per mil to -7.6 per mil. These siderite nodules probably represent early diagenetic carbonate precipitation during microbial methanogenesis.

Conglomerate and sandstone petrography at DSDP Hole 58-445

Conglomerates and sandstones in lithologic unit V at DSDP Site 445 comprise lithic clasts, detrital minerals, bioclasts, and authigenic minerals. The lithic clasts are dominantly plagioclase-phyric basalt and microdolerite, followed by plagioclase-clinopyroxene-phyric basalt, aphyric basalt, chert, and limestone. A small amount of hornblende schist occurs. Detrital minerals are dominantly plagioclase, augite, titaniferous augite, olivine, green to pale-brown hornblende, and dark-brown hornblende, with subordinate chromian spinel, epidote, ilmenite, and magnetite, and minor amounts of diopside, enstatite, actinolite, and aegirine-augite. Bioclasts are Nummulites boninensis, Asterocyclina sp. cf. A. penuria, and some other larger foraminifers. Correlation of cored and dredged samples indicates that the Daito Ridge is mainly composed of igneous, metamorphic, ultramafic, and sedimentary rocks. The igneous rocks are mafic (probably tholeiitic) and alkalic. The metamorphic rocks are hornblende schist, tremolite schist, and diopside-chlorite schist. The ultramafic rocks are alpinetype peridotites. Mineralogical data suggest that there were two metamorphic events in the Daito Ridge. The older one was intermediate- to high-pressure metamorphism. The younger one was contact metamorphism caused by a Paleocene volcanic event, possibly related to the beginning of spreading of the west Philippine Basin. The ultramafic rocks suffered from the same contact metamorphism. During the Eocene, exposed volcanic and metamorphic rocks on the uplifted Daito Ridge may have supplied pebble clasts to the surrounding coast and shallow sea bottom. The steep slope offshore may have caused frequent slumping and transportation of the pebble clasts and shallow-water benthic organisms into deeper water, forming the conglomerates and sandstones treated here.

Composition of drilled sediments and pore waters from the continental slope of the Northern Gulf of Mexico

Pore waters were analyzed from 6 holes drilled from M.V. "Eureka" as a part of the Shell Oil Co. deeper offshore study. The holes were drilled in water depths of 600-3000 ft. (approximately 180-550 m) and penetrated up to 1000 ft. (300 m) of Pliocene-Recent clayey sediments. Salt and anhydrite caprock was encountered in one diapiric structure on the continental slope. Samples from holes drilled near diapiric structures showed systematic increases of pore-water salinity with depth, suggestive of salt diffusion from underlying salt plugs. Anomalous concentrations of K and Br indicate that at least one plug contains late-stage evaporite minerals. Salinities approaching halite saturation were observed. Samples from holes away from diapiric structures showed little change in pore-water chemistry, except for loss of SO4 and other variations attributable to early-stage diagenetic reactions with enclosing sediments. Thus, increased salt concentrations in even shallow sediments from this part of the Gulf appear to provide an indicator of salt masses at depth.

Inorganic major, minor, and trace element geochemistry and clay mineralogy of sediments from the Deep Sea Drilling Project Leg 96, Gulf of Mexico

Sediment samples collected at DSDP Leg 96 Mississippi Fan Sites 615, 616, 620, 621, and 623, Orca Basin Site 618, and Pigmy Basin Site 619 were analyzed for 22 major, minor, and trace elements. This study was undertaken to document the downhole variability in inorganic geochemistry between sites. The mineralogy of the clays, including those from Sites 614, 617, and 622 on the fan, was determined by X-ray diffraction to define the principal clay minerals present at the sites, examine any downhole trends in clay mineralogy, and aid in the interpretation of the geochemical signature of the sediments. Clay mineral composition at all the sites is smectite:illite:chlorite:kaolinite in the approximate percentage ratio 50:20:20:10. Geochemical results indicate only slight variation between and within the sites, with the exception of a discrete unit of carbonates that occurs near the bottom of Site 615. Variation in the major, minor, and trace element composition can be explained by a change in the relative abundance of quartz, clay minerals, and carbonates.

Carbon and oxygen isotopic composition and age dating of sediments from ODP Leg 170 sites and Hole 205-1253A

In this data report we present results from stable isotope measurements (d13C and d18O) on bulk sediment at several sites located on a transect along a subduction margin offshore Costa Rica (Ocean Drilling Program Sites 1039, 1040, and 1253). Comparison of stable isotope compositions (d13C and d18O) of the pelagic carbonates Subunit U3C between the reference sites (Site 1039 and 1253) and the underthrust section (Site 1040) reveals similar d13C values and minor differences in d18O values within four specific intervals. Isotope stratigraphy was then used to further constrain the shipboard age models based on bio- and magnetostratigraphy. The resulting age models are in agreement with those derived from biostratigraphy and confirm that the sedimentation rate of the lower Subunit 3C is roughly constant on the order of 50 m/m.y. This is in contrast with the postulated very high sedimentation rates at ~12.7 Ma and lower sedimentation rates (~18 m/m.y.) in the lower part of the section between 16 and 13 Ma, as suggested by shipboard magnetostratigraphic datums.

Chemical and isotope composition of poor fluid from gas-hydrate samples of ODP Site 146-892

Although the presence of extensive gas hydrate on the Cascadia margin, offshore from the western U.S. and Canada, has been inferred from marine seismic records and pore water chemistry, solid gas hydrate has only been found at one location. At Ocean Drilling Program (ODP) Site 892, offshore from central Oregon, gas hydrate was recovered close to the sediment-water interface at 2-19 m below the seafloor (mbsf) at 670 m water depth. The gas hydrate occurs as elongated platy crystals or crystal aggregates, mostly disseminated irregularly, with higher concentrations occurring in discrete zones, thin layers, and/or veinlets parallel or oblique to the bedding. A 2- to 3-cm thick massive gas hydrate layer, parallel to bedding, was recovered at ~17 mbsf. Gas from a sample of this layer was composed of both CH4 and H2S. This sample is the first mixed-gas hydrate of CH4-H2S documented in ODP; it also contains ethane and minor amounts of CO2. Measured temperatures of the recovered core ranged from 2 to -1.8°C and are 6 to 8 degrees lower than in-situ temperatures. These temperature anomalies were caused by the partial dissociation of the CH4-H2S hydrate during recovery without a pressure core sampler. During this dissociation, toxic levels of H2S (delta34S, +27.4?) were released. The delta13C values of the CH4 in the gas hydrate, -64.5 to -67.5? (PDB), together with deltaD values of -197 to -199? (SMOW) indicate a primarily microbial source for the CH4. The delta18O value of the hydrate H2O is +2.9? (SMOW), comparable with the experimental fractionation factor for sea-ice. The unusual composition (CH4-H2S) and depth distribution (2-19 mbsf) of this gas hydrate indicate mixing between a methane-rich fluid with a pore fluid enriched in sulfide; at this site the former is advecting along an inclined fault into the active sulfate reduction zone. The facts that the CH4-H2S hydrate is primarily confined to the present day active sulfate reduction zone (2-19 mbsf), and that from here down to the BSR depth (19-68 mbsf) the gas hydrate inferred to exist is a >=99% CH4 hydrate, suggest that the mixing of CH4 and H2S is a geologically young process. Because the existence of a mixed CH4-H2S hydrate is indicative of moderate to intense advection of a methane-rich fluid into a near surface active sulfate reduction zone, tectonically active (faulted) margins with organic-rich sediments and moderate to high sedimentation rates are the most likely regions of occurrence. The extension of such a mixed hydrate below the sulfate reduction zone should reflect the time-span of methane advection into the sulfate reduction zone.