Sedimentology and gas hydrates of IODP Expedition 311 samples

Expedition 311 of the Integrated Ocean Drilling Program (IODP) to northern Cascadia recovered gas-hydrate bearing sediments along a SW-NE transect from the first ridge of the accretionary margin to the eastward limit of gas-hydrate stability. In this study we contrast the gas gas-hydrate distribution from two sites drilled ~ 8 km apart in different tectonic settings. At Site U1325, drilled on a depositional basin with nearly horizontal sedimentary sequences, the gas-hydrate distribution shows a trend of increasing saturation toward the base of gas-hydrate stability, consistent with several model simulations in the literature. Site U1326 was drilled on an uplifted ridge characterized by faulting, which has likely experienced some mass wasting events. Here the gas hydrate does not show a clear depth-distribution trend, the highest gas-hydrate saturation occurs well within the gas-hydrate stability zone at the shallow depth of ~ 49 mbsf. Sediments at both sites are characterized by abundant coarse-grained (sand) layers up to 23 cm in thickness, and are interspaced within fine-grained (clay and silty clay) detrital sediments. The gas-hydrate distribution is punctuated by localized depth intervals of high gas-hydrate saturation, which preferentially occur in the coarse-grained horizons and occupy up to 60% of the pore space at Site U1325 and > 80% at Site U1326. Detailed analyses of contiguous samples of different lithologies show that when enough methane is present, about 90% of the variance in gas-hydrate saturation can be explained by the sand (> 63 µm) content of the sediments. The variability in gas-hydrate occupancy of sandy horizons at Site U1326 reflects an insufficient methane supply to the sediment section between 190 and 245 mbsf.

Age models for ODP Leg 172 sites

Ten ODP sites drilled in a depth transect (2164-4775 m water depth) during Leg 172 recovered high-deposition rate (>20 cm/kyr) sedimentary sections from sediment drifts in the western North Atlantic. For each site an age model covering the past 0.8-0.9 Ma has been developed. The time scales have a resolution of 10-20 kyr and are derived by tuning variations of estimated carbonate content to the orbital parameters precession and obliquity. Based on the similarity in the signature of proxy records and the spectral character of the time series, the sites are divided into two groups: precession cycles are better developed in carbonate records from a group of shallow sites (2164-2975 m water depth, Sites 1055-1058) while the deeper sites (2995-4775 m water depth, Sites 1060-1063) are characterized by higher spectral density in the obliquity band. The resulting time scales show excellent coherence with other dated carbonate and isotope records from low latitudes. Besides the typical Milankovitch cyclicity significant variance of the resulting carbonate time series is concentrated at millennial-scale changes with periods of about 12, 6, 4, 2.5, and 1.5 kyr. Comparisons of carbonate records from the Blake Bahama Outer Ridge and the Bermuda Rise reveal a remarkable similarity in the time and frequency domain indicating a basin-wide uniform sedimentation pattern during the last 0.9 Ma.

Jurassic sedimentation history at DSDP Hole 76-534A

Site 534 reflects a complex interplay of global, basinal, and local influences on sedimentation during the Callovian and Late Jurassic. Rifting and rapid subsidence of the continental margins of the North Atlantic-Tethys seaway occurred during the late Early Jurassic (Sinemurian-Pliensbachian), but rapid spreading between the North American margin (Blake Spur Ridge and magnetic lineation) and the northwest African margin did not commence until the Bathonian or earliest Callovian. Site 534, drilled on marine magnetic anomaly "M-28" of Bryan et al. (1980), was initially about 150 km from either continental margin. The ?middle Callovian basal sediments are dusky red silty marl. Callovian transgression led to active carbonate platforms on the margin, recorded at Site 534 as a rise in the CCD (carbonate compensation depth), then arrival of lime-rich turbidites from the Blake Plateau platform across the Blake Spur Ridge. The host pelagic sediment is greenish black, organic-rich, radiolarian-rich, silty claystone. Hydrothermal activity on the nearby spreading ridge enriched this lower unit in metals. In the Oxfordian, the input of terrestrial silt rapidly diminished; radiolarians or other bioclasts were not preserved. The dark variegated claystone has fine-grained marl and reddish claystone turbidite beds. The late Callovian-Oxfordian Western Tethys has radiolarian chert deposition, marine hiatuses, or organic-rich sediments. The Kimmeridgian and Tithonian had a stable or receding sea level. Near the end of the Jurassic many of the carbonate platforms of the margins were buried beneath prograding fan or alluvial deposits. Carbonate deposition shifted to the deep sea. Site 534 records the deepening of the CCD and ACD (aragonite compensation depth) during the Kimmeridgian and early Tithonian, then a rise of the ACD in the middle Tithonian. Similar trends occurred throughout the Western Tethys-Atlantic. High nannofossil productivity of the seaway led to deposition of very widespread white micritic limestone in the late Tithonian-Berriasian. The underlying sediment had a slower deposition rate of carbonate, therefore its higher clay and associated Fe content produced a red marl. A short sea-level incursion occurred on the Atlantic margins during the Kimmeridgian and is reflected in the Site 534 greenish gray marl unit by numerous turbidite beds of shallow-water carbonates.

Pleistocene stable isotope record of planktonic foraminifera of ODP Site 138-847

We present Pleistocene oxygen and carbon isotope records from two planktonic foraminifer species (Globigerinoides sacculifer and Neogloboquadrina dutertrei) from Ocean Drilling Program Site 847 (0°16'N, 95°19'W; 3334 m water depth). An average sample resolution of 4500 yr was obtained by sampling at an interval of 15 cm through a continuous 35-m section from 0 to 1.15 Ma. Our d18O-based chronology is similar to that derived independently by astronomically tuning the gamma-ray attenuation porosity evaluator (GRAPE) record (Shackleton et al., 1995), though offsets as large as ± 30 k.y. occur on occasion. The surface waters at eastern equatorial Pacific Site 847, 380 km west of the Galapagos, are characterized by strong and constant upwelling, elevated nutrient concentrations, and high productivity. The isotopic composition of G. sacculifer (300-355 µm) reflects conditions in the thin-surface mixed layer, and the composition of N. dutertrei (355-425 µm) monitors the subsurface waters of the permanent shallow (10-40 m) thermocline. The Pleistocene d18O difference (N. dutertrei minus G. sacculifer, Dd18Od-s) averages 0.9 per mil and ranges from 0 per mil to 1.7 per mil. Neglecting species effects and shell size, the average Pleistocene d13C difference (G. sacculifer minus N. dutertrei, Dd13Cs-d) is 0.0 per mil and ranges from -0.5 per mil to 0.5 per mil. The Dd18Od-s and Dd13Cs-d records are used to infer vertical contrasts in upper ocean water temperature and nutrient concentration, though d13C may also be influenced by other factors, such as CO2 gas exchange. Variations in the isotopic differences are often synchronous with glacial/interglacial climate change. Glacial periods are characterized by smaller vertical contrasts in both temperature and nutrient concentration, and by notably greater accumulation rates of N. dutertrei and CaCO3. We attribute these responses to greater upwelling at the equatorial divergence. Superimposed on the glacial/interglacial Dd18Od-s pattern is a long-term trend possibly associated with the advection of Peru Current waters. The temporal fluctuations in the isotopic contrasts are strikingly similar to those observed at Site 851 (Ravelo and Shackleton, this volume), suggesting that the inferred changes in thermal and chemical profiles occurred over a broad region in the equatorial Pacific.

Geochemistry of ODP Hole 135-841B

Two igneous rock units were recovered at Site 841. More than 200 m of island-arc rhyolites, rhyolitic tuffs, lapilli tuffs, and pumice breccias, divided into five units, compose the basement at the site. These rhyolitic volcanics are late middle Eocene or older and formed part of a subaerial rhyolitic volcano. These low-K rhyolites were produced by fractional crystallization of a more mafic arc-tholeiitic lava or by dehydration melting of lower crustal arc tholeiites. The Site 841 basement rocks are similar in composition to high-SiO2 lavas in the Eocene basement on 'Eua and crystallized from depleted island-arc-tholeiitic basalts like those exposed on 'Eua. No evidence is present in the rhyolites, or in the clasts enclosed within them, for boninite series magmas at Site 841. The Site 841 rhyolitic complex bears no resemblance to Cretaceous rhyolites from the Lord Howe Rise, which are enriched in K and incompatible elements. The volcanic rocks at Site 841 are part of a widely distributed Eocene volcanic episode that marked the earliest phases of subduction in the Tonga region; they are not part of an older crustal fragment. The second igneous sequence is a series of basaltic dikes and sills that intruded Miocene sediments. These basalts have trace element abundances and ratios identical to upper Miocene lavas from the Lau Ridge. The Site 841 basalts do not have any geochemical characteristics that suggest they were generated by unusual thermal conditions in the shallow sub-forearc mantle. They are most reasonably interpreted as intrusions fed by basement dikes propagated from the associated active arc. No evidence for local serpentinite exposures, like those that are common in the Mariana forearc, was found at Site 841. The results from Site 841 provide strong support for hypotheses of forearc evolution that have been advanced for the Izu-Bonin-Mariana system.

Sedimentology and Cd/Ca ratios of benthic foraminifera from ODP Site 172-1060 in the western Nort Atlantic

The Western Boundary Undercurrent (WBUC), off eastern America, is an important component of the Atlantic Meridional Overturning circulation and is the principal route for southward transport of North Atlantic waters and southward return of Southern Source Water (SSW). Here a direct flow speed proxy (mean grain size of the sortable silt) is used to infer the vigour of flow of the palaeo-WBUC at Blake Outer Ridge, (ODP Site 1060, depth 3481 m) during Marine Isotope Stage (MIS) 3. The overall shape of the flow speed proxy record shows a complex pattern of variability, with generally more vigorous flow and larger-scale flow variations between 35 and 60 ka than in the younger part of MIS 3 and MIS 2 (b35 ka). Six events of reduced bottom flow vigour (Slow Events, SEs) occur. These appear uncorrelated with Heinrich events, but are instead synchronous with the warming phases of Antarctic Warm Events A-1 to A-4 (with one new one, A-1a and one poorly defined, 'A-0'). This indicates that Antarctic climate exerts a stronger control on deep flow vigour in the North Atlantic during MIS 3 than Northern Hemisphere climate. The correspondence of SEs with Antarctic warming suggests a weaker WBUC flow due to reduced volume flux at SSW source or reduced SSW density. Because the variability of the lower limb of the WBUC was not connected to sharp North Atlantic changes in temperature, it is unlikely that the Dansgaard/Oeschger cycles were associated with a mode of MOC variation involving wholeocean overturn, but more likely with perturbations of only the shallow Glacial Gulf Stream-Glacial Northern Source Intermediate Water cell. Nutrient proxies (benthic carbon isotopes and Cd/Ca of Uvigerina peregrina) at this site show similar trends to the GRIP delta18O record. This correlation has previously been attributed mainly to hydrographic and flow changes but is here shown to be better explained by variations in surface ocean productivity and subsequent decomposition of 12C rich organic material on the sea floor.

Rhenium and platinum-group element concentrations and Os isotope data for Philippine Sea Plate basalts from DSDP Legs 31, 58, and 59

Platinum-group elements (PGE), rhenium and osmium isotope data are reported for basalts from Deep Sea Drilling Project cores in the Philippine Sea Plate (PSP). Lithophile trace element and isotopic characteristics indicate a range of source components including DMM, EMII and subduction-enriched mantle. MORB-like basalts possess smooth, inclined chondrite-normalised PGE patterns with high palladium-PGE/iridium-PGE ratios, consistent with previously published data for MORB, and with the inferred compatibility of PGE. In contrast, while basalts with EMII-type lithophile element chemistry possess high Pt/Ir ratios, many have much lower Pd/Ir and unusually high Ru/Ir of >10. Similarly, back-arc samples from the Shikoku and Parece-Vela basins have very high Ru/Ir ratios (>30) and Pd/Ir as low as 1.1. Such extreme Pd/Ir and Ru/Ir ratios have not been previously reported in mafic volcanic suites and cannot be easily explained by variable degrees of melting, fractional crystallisation or by a shallow-level process such as alteration or degassing. The data appear most consistent with sampling of at least two mantle components with distinct PGE compositions. Peridotites with the required PGE characteristics (i.e. low Pd, but relatively high Ru and Re) have not been documented in oceanic mantle, but have been found in sub-continental mantle lithosphere and are the result of considerable melt depletion and selective metasomatic enrichment (mainly Re). The long-term presence of subduction zones surrounding the Philippine Sea Plate makes this a prime location for metasomatic enrichment of mantle, either through fluid enrichment or infiltration by small melt fractions. The Re-Os isotope data are difficult to interpret with confidence due to low Os concentrations in most samples and the uncertainty in sample age. Data for Site 444A (Shikoku Basin) give an age of 17.7+/-1.3 Ma (MSWD = 14), consistent with the proposed age of basement at the site and thus provides the first robust radiometric age for these samples. The initial 187Os/188Os of 0.1298+/-0.0069 is consistent with global MORB, and precludes significant metasomatic enrichment of Os by radiogenic slab fluids. Re-Os data for Sites 446A (two suites, Daito Basin) and 450 (Parece-Vela Basin) indicate ages of 73, 68 and 43 Ma, which are respectively, 30, 17 and >12 Ma older than previously proposed ages. The alkalic and tholeiitic suites from Site 446A define regression lines with different 187Os/188Osinitial (0.170+/-0.033 and 0.112+/-0.024, respectively) which could perhaps be explained by preferential sampling of interstitial, metasomatic sulphides (with higher time-integrated Re/Os ratios) by smaller percentage alkalic melts. One sample, with lithophile elements indistinguishable from MORB, is Os-rich (146 pg/g) and has an initial 187Os/188Os of 0.1594, which is at the upper limit of the accepted OIB range. Given the Os-rich nature of this sample and the lack of evidence for subduction or recycled crust inputs, this osmium isotope ratio likely reflects heterogeneity in the DMM. The dataset as a whole is a striking indication of the possible PGE and Os isotope variability within a region of mantle that has experienced a complex tectonic history.

Turonian to Coniacian planktic foraminiferal assemblages of ODP Site 207-1259

Abundance patterns of planktic and benthic foraminifera from a tropical Atlantic drill site (Ocean Drilling Program Site 1259, Demerara Rise, Suriname margin) display a pronounced 400 kyr cyclicity, uninterrupted throughout our ~87.8-92 Ma record, between two clearly distinguishable assemblages: (1) a pelagic foraminifer fauna, which represents a deep oxygen minimum zone, and (2) another assemblage representing a shallow oxygen minimum zone where the foraminifer fauna is dominated by a higher diversity population of mostly small clavate and biserial species common in epicontinental seas. The cyclic changes in the long eccentricity band (400 kyr) between these two assemblages are proposed to reflect changes in the mean latitudinal position of the Intertropical Convergence Zone (ITCZ). Associated fluctuations in precipitation and trade wind strength may have influenced the upwelling regime at Demerara Rise leading to the observed cyclicity of planktic foraminiferal assemblages. The severe Turonian to Coniacian paleoclimatic and paleoceanographic changes in the Atlantic Ocean (e.g., gateway opening, cooling, and glaciation), however, seem to have no influence on the composition of tropical planktic foraminiferal faunas. There is no apparent relationship between foraminifer abundances and a major deflection in the stable isotope record interpreted elsewhere as a sign of the growth and decay of a large polar ice sheet.

Uranium concentrations and isotope ratios Bahamas seawater and ODP holes pore-water

The geometry, timing, and rate of fluid-flow through carbonate margins and platforms is not well constrained. In this study, we use U concentrations and isotope ratios measured on small volumes of pore-water from Bahamas slope sediment, coupled with existing chlorinity data, to place constraints on the fluid-flow in this region and, by implication, other carbonate platforms. These data also allow an assessment of the behaviour of U isotopes in an unusually well constrained water-rock system. We report pore-water U concentrations which are controlled by dissolution of high-U organic material at shallow depths in the sediment and by reduction of U to its insoluble 4+ state at greater depths. The dominant process influencing pore-water (234U/238U) is alpha recoil. In Holocene sediments, the increase of pore-water (234U/238U) due to recoil provides an estimate of the horizontal flow rate of 11 cm/year, but with considerable uncertainty. At depths in the sediment where conditions are reducing, features in the U concentration and (234U/238U) profiles are offset from one another which constrains the effective diffusivity for U in these sediments to be c. 1-2 * 10**-8 cm**2/s. At depths between the Holocene and these reducing sediments, pore-water (234U/238U) values are unusually low due to a recent increase in the dissolution rate of grain surfaces. This suggests a strengthening of fluid flow, probably due to the flooding of the banks at the last deglaciation and the re-initiation of thermally-driven venting of fluid on the bank top and accompanying recharge on the slopes. Interpretation of existing chlorinity data, in the light of this change in flow rate, constrain the recent horizontal flow rate to be 10.6 ( 3.4) cm/year. Estimates of flow rate from (234U/238U) and Cl[-] are therefore in agreement and suggest flow rates close to those predicted by thermally-driven models of fluid flow. This agreement supports the idea that flow within the Bahamas Banks is mostly thermally driven and suggests that flow rates on the order of 10 cm/year are typical for carbonate platforms where such flow occurs.

Biochemical, geochemical and sedimentological study of ODP Leg 112 samples

Organic-rich diatomaceous muds from Ocean Drilling Program Leg 112 (offshore Peru) are the subject of a comprehensive organic diagenetic study covering the burial interval, <1 to >100 m. The organic matter has been classified in terms of its elemental, biochemical, and geochemical compositions. About 60% of the organic carbon in sediments from <1 m can be attributed to hydrolyzable, biochemical constituents, while at 22 m this figure decreased to 20%. Pyrolysis-gas chromatography and gas chromatography-mass spectrometry chromatograms of these same sediments contain mainly hydrocarbons and nitrogenous compounds, with low amounts of other heteroatomic compounds, even though the total organic matter is rich in oxygen (about 35 atoms per 100 carbon atoms) and sulfur (1 to 5 atoms per 100 C atoms). Overall, the organic matter in these sediments, even at these shallow depths and young ages, has many of the geochemical features of far more deeply buried sediments, providing further strong evidence for the claim that "kerogen-formation" is a very early diagenetic process.

Pliocene/Pleistocene benthic foraminiferal abundances from six drilling cores

Twenty percent (19 genera, 95 species) of cosmopolitan, deep-sea (500-4000 m), benthic foraminiferal species became extinct during the late Pliocene-Middle Pleistocene (3-0.12 Ma), with the peak of extinctions (76 species) occurring during the mid-Pleistocene Climate Transition (MPT, 1.2-0.55 Ma). One whole family (Stilostomellidae, 30 species) was wiped out, and a second (Pleurostomellidae, 29 species) was decimated with just one species possibly surviving through to the present. Our studies at 21 deep-sea core sites show widespread pulsed declines in abundance and diversity of the extinction group species during more extreme glacials, with partial interglacial recoveries. These declines started in the late Pliocene in southern sourced deep water masses (Antarctic Bottom Water, Circumpolar Deep Water) and extending into intermediate waters (Antarctic Intermediate Water, North Atlantic Deep Water) in the MPT, with the youngest declines in sites farthest downstream from high-latitude source areas for intermediate waters. We infer that the unusual apertural types that were targeted by this extinction period were adaptations for a specific kind of food source and that it was probably the demise of this microbial food that resulted in the foraminiferal extinctions. We hypothesize that it may have been increased cold and oxygenation of the southern sourced deep water masses that impacted on this deep water microbial food source during major late Pliocene and Early Pleistocene glacials when Antarctic ice was substantially expanded. The food source in intermediate water was not impacted until major glacials in the MPT when there were significant expansion of polar sea ice in both hemispheres and major changes in the source areas, temperature, and oxygenation of global intermediate waters.

Miocene dissolution facies and microfacies at Northwest Atlantic Deep Sea Drilling Project Site 93-603

Depth fluctuations of the lysocline and calcite compensation depth (CCD) through time were investigated at Deep Sea Drilling Project Site 603, Leg 93. The CCD fell during the middle Miocene at the onset of the Western Boundary Undercurrent, correlated with seismic Horizon X. Subsequently deposited units show fluctuations of the dissolution curve. Major changes in dissolution facies correspond with lithologic boundaries.

40Ar-39Ar dating and isotopic composition of groundmass and felspar samples from core AND-2A

The AND-2A drillcore (Antarctic Drilling Program-ANDRILL) was successfully completed in late 2007 on the Antarctic continental margin (Southern McMurdo Sound, Ross Sea) with the aim of tracking ice proximal to shallow marine environmental fluctuations and to document the 20-Ma evolution of the Erebus Volcanic Province. Lava clasts and tephra layers from the AND-2A drillcore were investigated from a petrographic and stratigraphic point of view and analyzed by the 40Ar-39Ar laser technique in order to constrain the age model of the core and to gain information on the style and nature of sediment deposition in the Victoria Land Basin since Early Miocene. Ten out of 17 samples yielded statistically robust 40Ar-39Ar ages, indicating that the AND-2A drillcore recovered <230 m of Middle Miocene (~128-358 m below sea floor, ~11.5-16.0 Ma) and >780 m of Early Miocene (~358-1093 m below sea floor, ~16.0-20.1 Ma). Results also highlight a nearly continuous stratigraphic record from at least 358 m below sea floor down hole, characterized by a mean sedimentation rate of ~19 cm/ka, possible oscillations of no more than a few hundreds of ka and a break within ~17.5-18.1 Ma. Comparison with available data from volcanic deposits on land, suggests that volcanic rocks within the AND-2A core were supplied from the south, possibly with source areas closer to the drill site for the upper core levels, and from 358 m below sea floor down hole, with the 'proto-Mount Morning' as the main source.

Dinoflagellate abundance and events of ODP Site 189-1172 sediments

Palynomorphs were studied in samples from Ocean Drilling Program (ODP) Leg 189, Holes 1172A and 1172D (East Tasman Plateau; 2620 m water depth). Besides organic walled dinoflagellate cysts (dinocysts), broad categories of other palynomorphs were quantified in terms of relative abundance. In this contribution, we provide an overview of the dinocyst distribution from the Maastrichtian to lowermost Oligocene and Quaternary intervals and illustrate main trends in palynomorph distribution. The uppermost Cretaceous-lowermost Oligocene succession of Site 1172 has a confident biomagnetostratigraphy, enabling us to tie early Paleogene Southern Hemisphere dinocyst events to the geomagnetic polarity timescale for the first time. Dinocyst species from the Maastrichtian to earliest Oligocene at Site 1172 are largely endemic ("Transantarctic Flora") or bipolar; cosmopolitan taxa are present in the background as well. The Maastrichtian-early late Eocene dinocyst assemblages are indicative of shallow-marine to restricted marine, pro-deltaic conditions, closely tied to a massive siliciclastic sequence. By middle late Eocene times (~35.5 Ma), the siliciclastic sequence gave way to a thin glauconitic unit, considered to reflect the deepening of the Tasmanian Gateway. This transition coincides with the most prominent change in dinocyst associations of the Paleogene. The turnover is inferred to reflect a change from marginal marine to more offshore conditions, with increased winnowing and oxidation. Overlying pelagic carbonate ooze of middle early Oligocene and younger age is virtually barren of organic microfossils, although Quaternary assemblages have been recovered. This aspect is taken to reflect average low sedimentation rates and well-oxygenated water masses during most of the Oligocene and Neogene. The few palynologically productive samples from the Oligocene-Quaternary interval have a stronger cosmopolitan to subtropical signature, with warm-water species being common to abundant.