Stable carbon isotope compositions and concentrations of biphytanes from IODP Hole 311-U1327C and 311-U1328B

We have investigated the distributions and carbon isotopic compositions of archaeal membrane lipids in gas-hydrate-bearing sediments collected from the northern Cascadia Margin offshore from Vancouver Island (Sites U1327 and U1328) by the R/V JOIDES Resolution during IODP Expedition 311. Archaeal lipid biomarkers, including glycerol dialkyl glycerol tetraethers (GDGTs), tend to become abundant below 100 mbsf (meters below sea floor). Tricyclic biphytane (BP[3]; which is a robust biomarker derived from GDGT), crenarchaeol, and other BPs exhibit d13C values of ca. -20 per mil, and become abundant between 130 and 230 mbsf at Site U1328. In this depth range, concentrations of ammonium and phosphate in interstitial waters also increase, suggesting that a larger population and higher activity of heterotrophic community consisting of crenarchaeota and other archaea decompose the sedimentary organic matter, thereby liberating ammonium and phosphate. Such crenarchaeotic activity can produce other metabolic products such as molecular hydrogen by fermentation of organic matter during diagenesis. Furthermore, near the organic matter decomposition zone (130 to 230 mbsf), a probable methanogen biomarker (13C-depleted BP[1] with d13C values as low as -48.8 per mil) becomes abundant, indicating that methanogens utilize these diagenetic products. The molecular and isotopic distributions of archaeal lipid biomarkers indicate that the archaeal community plays an important role in the biogeochemical cycles of deep-sea sediments, including both methanogenesis and nutrient recycling.

Isopollen maps for 18,000 years B.P. of the offshore of Northwest Africa: Evidence for paleowind circulation

Distribution patterns of the most important pollen types from southern European and northwest African source areas for the 18,000 years B.P. time slice are reconstructed from pollen records of 14 well-dated deep-sea cores located between 37° and 9°N and compared with the modern pollen distribution in this area. It is concluded that the belt with maximum African Easterly Jet transport did not shift latitudinally during the last glacial-interglacial transition but remained at about 20°N. Furthermore, it is substantiated that the trade winds did not shift latitudinally during the last glacial-interglacial transition. This evidence is not compatible with an atmospheric circulation model that assumes a zone of surface westerlies in the northern part of northwest Africa. Trade winds during glacial episodes did, however, intensify, especially from about 36° to 24° N.

Dinoflagellate cysts of ODP Leg 101 holes

The Albian-Cenomanian sediments in Holes 627B and 635B contain diverse dinoflagellate-cyst assemblages, which show affinities with coeval assemblages from offshore Morocco and northwest Europe. A total of 34 samples were analyzed from the shallow-water platform sediments and neritic marly chalk of Hole 627B and from the argillaceous chalk and limestone of Hole 635B. Dinoflagellate cysts indicate that the top of the shallow-water platform drilled at Hole 627B must be attributed to the late Albian. Dinocysts also date the drowning of the carbonate platform of the Blake Plateau. This drowning started in the latest Albian (Vraconian) and continued into the Cenomanian. The site area changed from an inner to intermediate or outer(?) neritic environment. The area around Hole 635B from the late Albian appears to have been situated in a deeper environment than the area around Hole 627B during the same period. The new dinoflagellate-cyst species Compositosphaeridiuml bahamaensis n. sp., Maghrebinia breviornata n. sp., and Subtilisphaeral habibi n. sp. are described, and Pervosphaeridium truncatum is emended. Additional taxonomic remarks about other species are included.

Molecular and isotopic properties of gases from ODP Holes of ODP Leg 204

We report and discuss molecular and isotopic properties of hydrate-bound gases from 55 samples and void gases from 494 samples collected during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge offshore Oregon. Gas hydrates appear to crystallize in sediments from two end-member gas sources (deep allochthonous and in situ) as mixtures of different proportions. In an area of high gas flux at the Southern Summit of the ridge (Sites 1248-1250), shallow (0-40 m below the seafloor [mbsf]) gas hydrates are composed of mainly allochthonous mixed microbial and thermogenic methane and a small portion of thermogenic C2+ gases, which migrated vertically and laterally from as deep as 2- to 2.5-km depths. In contrast, deep (50-105 mbsf) gas hydrates at the Southern Summit (Sites 1248 and 1250) and on the flanks of the ridge (Sites 1244-1247) crystallize mainly from microbial methane and ethane generated dominantly in situ. A small contribution of allochthonous gas may also be present at sites where geologic and tectonic settings favor focused vertical gas migration from greater depth (e.g., Sites 1244 and 1245). Non-hydrocarbon gases such as CO2 and H2S are not abundant in sampled hydrates. The new gas geochemical data are inconsistent with earlier models suggesting that seafloor gas hydrates at Hydrate Ridge formed from gas derived from decomposition of deeper and older gas hydrates. Gas hydrate formation at the Southern Summit is explained by a model in which gas migrated from deep sediments, and perhaps was trapped by a gas hydrate seal at the base of the gas hydrate stability zone (GHSZ). Free gas migrated into the GHSZ when the overpressure in gas column exceeded sealing capacity of overlaying sediments, and precipitated as gas hydrate mainly within shallow sediments. The mushroom-like 3D shape of gas hydrate accumulation at the summit is possibly defined by the gas diffusion aureole surrounding the main migration conduit, the decrease of gas solubility in shallow sediment, and refocusing of gas by carbonate and gas hydrate seals near the seafloor to the crest of the local anticline structure.

Coccolithophore taxa and PCA factor analysis of ODP Site 1233

We provide high-resolution sea surface temperature (SST) and paleoproductivity data focusing on Termination 1. We describe a new method for estimating SSTs based on multivariate statistical analyses performed on modern coccolithophore census data, and we present the first downcore reconstructions derived from coccolithophore assemblages at Ocean Drilling Project (ODP) Site 1233 located offshore Chile. We compare our coccolithophore SST record to alkenone-based SSTs as well as SST reconstructions based on dinoflagellates and radiolaria. All reconstructions generally show a remarkable concordance. As in the alkenone SST record, the Last Glacial Maximum (LGM, 19-23 kyr B.P.) is not clearly defined in our SST reconstruction. After the onset of deglaciation, three major warming steps are recorded: from 18.6 to 18 kyr B.P. (~2.6°C), from 15.7 to 15.3 kyr B.P. (~2.5°C), and from 13 to 11.4 kyr B.P. (~3.4°C). Consistent with the other records from Site 1233 and Antarctic ice core records, we observed a clear Holocene Climatic Optimum (HCO) from ~8-12 kyr B.P. Combining the SST reconstruction with coccolith absolute abundances and accumulation rates, we show that colder temperatures during the LGM are linked to higher coccolithophore productivity offshore Chile and warmer SSTs during the HCO to lower coccolithophore productivity, with indications of weak coastal upwelling. We interpret our data in terms of latitudinal displacements of the Southern Westerlies and the northern margin of the Antarctic Circumpolar Current system over the deglaciation and the Holocene.

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.