Polarity chron boundaries and foraminiferal 87Sr/86Sr ratios of ODP Sites 162-986 and 162-987

Cores recovered at Sites 986 and 987 comprise glacial fan sedimentation associated with the Svalbard-Barents Sea and Greenland Ice Sheets, respectively. At Site 986, the top 150 m and the basal 250 m yielded interpretable magnetic stratigraphies. The record from the intervening 550 m is compromised by drilling-related core deformation, poor recovery, and numerous debris flows. The uppermost 150 m appears to record the Brunhes/Matuyama boundary and the Jaramillo Subchron. The base of the drilled section (at ~950 meters below seafloor [mbsf]) is interpreted to lie within the Matuyama Chron (age <2.58 Ma) with an apparent normal polarity interval in the ~730-750 mbsf interval. Dinoflagellate cyst biostratigraphy and Sr isotopic ratios are consistent with a Matuyama age for the base of the drilled section and with the normal polarity interval as the Olduvai Subchron. On the other hand, the last occurrence of Neogloboquadrina atlantica (sinistral) and the last common occurrence of the warm-dwelling Globigerina bulloides at 647-650 mbsf in Hole 986D indicate an age for this level of ~2.3 Ma, inconsistent with the designation of the Olduvai Subchron in the ~730-750 mbsf interval. If the age at 647-650 mbsf in Hole 986D is taken as 2.3 Ma and the base of the hole lies within the Matuyama Chron, then the sedimentation rate in the basal 300 m of the cored section averages 1 m/k.y. At Site 987, the magnetic stratigraphy is fairly unambiguous throughout the section and yields an age of 7.5 Ma (Chron 4n) for the base of the drilled section. The paucity of calcareous and siliceous microfossils precludes biostratigraphic corroboration of the magnetostratigraphic interpretation, although dinoflagellate cysts provide general support, particularly at the base of the section. The age model indicates relatively low sedimentation rates (~5 cm/k.y.) at the base of the section with rates at least four to five times greater during intervals of debris flows at ~5-4.6 and ~2.6 Ma.

(Table 1) Crystal sizes of measured samples from the Bush Hill region in the Gulf of Mexico and from ODP Leg 204 at the Hydrate Ridge offshore Oregon

The grain sizes of gas hydrate crystallites are largely unknown in natural samples. Single grains are hardly detectable with electron or optical microscopy. For the first time, we have used high-energy synchrotron diffraction to determine grain sizes of six natural gas hydrates retrieved from the Bush Hill region in the Gulf of Mexico and from ODP Leg 204 at the Hydrate Ridge offshore Oregon from varying depth between 1 and 101 metres below seafloor. High-energy synchrotron radiation provides high photon fluxes as well as high penetration depth and thus allows for investigation of bulk sediment samples. Gas hydrate grain sizes were measured at the Beam Line BW 5 at the HASYLAB/Hamburg. A 'moving area detector method', originally developed for material science applications, was used to obtain both spatial and orientation information about gas hydrate grains within the sample. The gas hydrate crystal sizes appeared to be (log-)normally distributed in the natural samples. All mean grain sizes lay in the range from 300 to 600 µm with a tendency for bigger grains to occur in greater depth. Laboratory-produced methane hydrate, aged for 3 weeks, showed half a log-normal curve with a mean grain size value of c. 40 µm. The grains appeared to be globular shaped.

(Table S1, S4) Campanian-Maastrichtian benthic foraminifera from ODP Hole 113-690C

During the latest Cretaceous cooling phase, a positive shift in benthic foraminiferal d18O values lasting about 1.5 Myr (71.5-70 Ma) can be observed at a global scale (Campanian-Maastrichtian Boundary Event, CMBE). This d18O excursion is interpreted as being influenced by a change in intermediate- to deep-water circulation or by temporal build-up of Antarctic ice sheets. Here we test whether benthic foraminiferal assemblages from a southern high-latitudinal site near Antarctica (ODP Site 690) are influenced by the CMBE. If the d18O transition reflects a change in intermediate- to deep-water circulation from low-latitude to high-latitude water masses, then this change would result in cooler temperatures, higher oxygen concentration, and possibly lower organic-matter flux at the seafloor, resulting in a major benthic foraminiferal assemblage change. If, however, the d18O transition was mainly triggered by ice formation, no considerable compositional difference in benthic foraminiferal assemblages would be expected. Our data show a separation of the studied succession into two parts with distinctly different benthic foraminiferal assemblages. Species dominating the older part (73.0-70.5 Ma) tolerate less bottom water oxygenation and are typical components of low-latitude assemblages. In contrast, the younger part (70.0-68.0 Ma) is characterized by species that indicate well-oxygenated bottom waters and species common in high-latitude assemblages. We interpret the observed change in benthic foraminiferal assemblages toward a well-oxygenated environment to reflect the onset of a shift from low-latitude toward high-latitude dominated intermediate- to deep-water sources. This implies that a change in oceanic circulation was at least a major component of the CMBE.

Lithology, mineralogy and geochemistry of ODP Hole 118-735B and 176-735B respectively

Ocean Drilling Program (ODP) Hole 735B, located on Atlantis Bank on the Southwest Indian Ridge, penetrated 1508 meters below seafloor with an average recovery of 87%, providing a nearly continuous sample of a significant part of oceanic Layer 3. Based on variations in texture and mineralogy, 12 major lithologic units are recognized in the section, ranging from 39.5 to 354 m thick. The principal lithologies include troctolite, troctolitic gabbro, olivine gabbro and microgabbro, gabbro, gabbronorite and Fe-Ti oxide gabbro, gabbronorite, and microgabbro. Highly deformed mylonites, cataclasites, and amphibole gneisses are locally present, as are small quantities of pyroxenite, anorthositic gabbro, and trondhjemite. Downhole variations in mineral composition, particularly for olivine and clinopyroxene, show a number of cyclic variations. Plagioclase compositions show the widest variations and correspond to different degrees of deformation and alteration as well as primary processes. Downhole chemical variations correspond reasonably well with variations in mineral compositions. Iron and titanium mainly reflect the presence of Fe-Ti oxide gabbros but show some cyclical variations in the lower part of the core where oxide gabbros are sparse. CaO is highly variable but shows a small but consistent increase downhole. MgO is more uniform than CaO and shows a very small downward increase. Sulfur and CO2 contents are generally low, but S shows significant enrichment in lithologic Unit IV, which consists of Fe-Ti oxide gabbro, reflecting the presence of sulfide minerals in the sequence. The lithologic, mineralogical, and geochemical data provided here will allow detailed comparisons with ophiolite sections as well as sections of in situ ocean crust drilled in the future.

Iron isotope and chemical compositions of sediments and basalts drilled seaward of the Mariana Trench

The purpose of this work is to study the mobility and budget of Fe isotopes in the oceanic crust and in particular during low-temperature interaction of seawater with oceanic basalt. We carried out this investigation using samples from Ocean Drilling Program (ODP) Site 801C drilled during Leg 129 and Leg 185 in Jurassic Pacific oceanic crust seaward of the Mariana Trench. The site comprises approximately 450 m of sediment overlying a section of 500 m of basalt, which includes intercalated pelagic and chemical sediments in the upper basaltic units and two low-temperature (10-30°C) ocherous Si-Fe hydrothermal deposits. Fe was chemically separated from 70 selected samples, and 57Fe/54Fe ratios were measured by MC-ICP-MS Isoprobe. The isotopic ratios were measured relative to an internal standard solution and are reported relative to the international Fe-standard IRMM-14. Based on duplicate measurements of natural samples, an external precision of 0.2? (2 sigma) has been obtained. The results indicate that the deep-sea sediment section has a restricted range of d57Fe, which is close to the igneous rock value. In contrast, large variations are observed in the basaltic section with positive d57Fe values (up to 2.05?) for highly altered basalts and negative values (down to ?2.49?) for the associated alteration products and hydrothermal deposits. Secondary Fe-minerals, such as Fe-oxyhydroxides or Fe-bearing clays (celadonite and saponite), have highly variable d57Fe values that have been interpreted as resulting from the partial oxidation of Fe(2+) leached during basalt alteration and precipitated as Fe(3+)-rich minerals. In contrast, altered basalts at Site 801C, which are depleted in Fe (up to 80%), display an increase in d57Fe values relative to fresh values, which suggest a preferential leaching of light iron during alteration. The apparent fractionation factor between dissolved Fe(2+) and Fe remaining in the mineral is from 0.5? to 1.3? and may be consistent with a kinetic isotope fractionation where light Fe is stripped from the minerals. Alternatively, the formation of secondary clays minerals, such as celadonite during basalt alteration may incorporate preferentially the heavy Fe isotopes, resulting in the loss of light Fe isotopes in the fluids. Because microbial processes within the oceanic crust are of potential importance in controlling rates of chemical reactions, Fe redox state and Fe-isotope fractionation, we evaluated the possible effect of this deep biosphere on Fe-isotope signatures. The Fe-isotope systematics presented in this study suggest that, even though iron behavior during seafloor weathering may be mediated by microbes, such as iron-oxidizers, d57Fe variations of more than 4? may also be explained by abiotic processes. Further laboratory experiments are now required to distinguish between various processes of Fe-isotope fractionation during seafloor weathering.

(Table 2) Radiocarbon contents of TOC and alkenone samples

Radiocarbon age relationships between co-occurring planktic foraminifera, alkenones, and total organic carbon in sediments from the continental margins of southern Chile, northwest Africa, and the South China Sea were compared with published results from the Namibian margin. Age relationships between the sediment components are site-specific and relatively constant over time. Similar to the Namibian slope, where alkenones have been reported to be 1000-4500 years older than co-occurring foraminifera, alkenones were significantly (~1000 years) older than co-occurring foraminifera in the Chilean margin sediments. In contrast, alkenones and foraminifera were of similar age (within 2 sigma error or better) in the NW African and South China Sea sediments. Total organic matter and alkenone ages were similar off Namibia (age difference TOC alkenones: 200-700 years), Chile (100-450 years), and NW Africa (360-770 years), suggesting minor contributions of preaged terrigenous material. In the South China Sea, total organic carbon is significantly (2000-3000 years) older owing to greater inputs of preaged terrigenous material. Age offsets between alkenones and planktic foraminifera are attributed to lateral advection of organic matter. Physical characteristics of the depositional setting, such as seafloor morphology, shelf width, and sediment composition, may control the age of co-occurring sediment components. In particular, offsets between alkenones and foraminifera appear to be greatest in deposition centers in morphologic depressions. Aging of organic matter is promoted by transport. Age offsets are correlated with organic richness, suggesting that formation of organic aggregates is a key process.

Sample information and classification of lower Miocene gravity-flow types of sediment core CRP-1 (Table 1)

Nineteen samples of the Cape Roberts-1 drillcore were taken from Miocene- age deposits, from 90.25 - 146.50 metres below seafloor (mbsf) for thin section and laser grain-size analysis. Using the grain-size distribution, detailed core logging, X-radiography and thin-section analysis of microstructures, coupled with a statistical grouping of the grain-size data, three main styles of gravity-flow sedimentation were revealed. Thin (centimetre-scale) muddy debris-flow deposits are the most common and are possibly tirggered by debris rain-out from sea-ice These deposits are characterised by very poorly sorted, faintly laminated muddy sandstones with coarse granules toward their base. Contacts are gradational to sharp. Variations on this style of mass-wasting deposit are rhythmically stacked sequences of pebbly-coarse sandstones representing successive thin debris-flow events. These suggest very high sedimentation rates on an unstable slope in a shallow-water proximal glacimarine environment. Sandy-silty turbidites appear more common in the lower sections of the core, below approximately 141.00 mbsf, although they occur occasionally with the debris flow deposits The turbidites are characterised by inversely to normally graded, well-laminated siltstones with occasional lonestones, and represent a more distal shallow-water glacimarine environment.

Stable oxygen, hydrogene and chlorine isotopes of mid-Atlantic abyssal peridotites

Serpentinized abyssal peridotites sampled by the Ocean Drilling Program Leg 209 along the mid-Atlantic Ridge near the 15°20'N Fracture Zone have been analyzed for oxygen, hydrogen, and chlorine isotope compositions in order to determine isotopic behavior under a wide range of serpentinization conditions and place constraints on fluid history. Oxygen and hydrogen thermometry suggests peak serpentinization temperatures of 300-500°C. Serpentine separates have low deltaD values possibly due to a magmatic fluid component or low-temperature exchange during seafloor weathering. Chlorine geochemistry focused on three holes: 1274A and 1272A (serpentinized peridotites) and 1268A (serpentinite locally altered to talc). Concentrations of both, water-soluble chloride (WSC) and structurally bound chloride (SBC) are significantly lower at Hole 1268A compared to Holes 1274A and 1272A. The delta37Cl values for WSC and SBC of serpentinites in Holes 1274A and 1272A are slightly positive (avg. WSC = 0.20 per mil, n = 22 and avg. SBC = 0.35 per mil, n = 22), representing typical seawater-hydration conditions commonly determined for abyssal peridotite. The SBC of serpentinites from Hole 1268A are also positive (avg. = 0.63 per mil); whereas, the SBC in talc-dominated samples is negative (avg. = -1.22 per mil). The WSC of both talc- and serpentine-dominated samples are also negative (avg. = -0.15 per mil). We interpret the chlorine isotope data to preserve a record of multiple fluid events. As seawater hydrated the peridotite, 37Cl was preferentially incorporated into the forming serpentine and water-soluble salts, yielding similar delta37Cl values on a regional scale as sampled by Holes 1268A, 1274A and 1272A. The resultant pore fluid was left depleted in 37Cl. Locally (Hole 1268A), this evolved fluid was remobilized possibly due to the initiation of hydrothermal circulation in response to emplacement of a mafic magma body. The low delta37Cl pore fluids attained elevated SiO2 and sulfur concentrations due to interaction with the gabbroic intrusion and, when ascending through the surrounding serpentinite, caused formation of isotopically negative talc. This secondary fluid also flushed the preserved serpentinite of its previously formed salts, resulting in negative delta37Cl WSC values. The delta37Cl SBC values of the serpentinite samples remained unmodified by reaction with the secondary fluid.

(Table 1) Gravity and pressure within the Sleipner area relative to ones at the reference station in 2002 and 2005

At Sleipner, CO2 is being separated from natural gas and injected into an underground saline aquifer for environmental purposes. Uncertainty in the aquifer temperature leads to uncertainty in the in situ density of CO2. In this study, gravity measurements were made over the injection site in 2002 and 2005 on top of 30 concrete benchmarks on the seafloor in order to constrain the in situ CO2 density. The gravity measurements have a repeatability of 4.3 µGal for 2003 and 3.5 µGal for 2005. The resulting time-lapse uncertainty is 5.3 µGal. Unexpected benchmark motions due to local sediment scouring contribute to the uncertainty. Forward gravity models are calculated based on both 3D seismic data and reservoir simulation models. The time-lapse gravity observations best fit a high temperature forward model based on the time-lapse 3D seismics, suggesting that the average in situ CO2 density is about to 530kg/m**3. Uncertainty in determining the average density is estimated to be ±65 kg/m**3 (95% confidence), however, this does not include uncertainties in the modeling. Additional seismic surveys and future gravity measurements will put better constraints on the CO2 density and continue to map out the CO2 flow.

Clay mineralogy and shear strength of subglacial and glaciomarine sediments in the southern Bellingshausen Sea

The Belgica Trough and the adjacent Belgica Trough Mouth Fan in the southern Bellingshausen Sea (Pacific sector of the Southern Ocean) mark the location of a major outlet for the West Antarctic Ice Sheet during the Late Quaternary. The drainage basin of an ice stream that advanced through Belgica Trough across the shelf during the last glacial period comprised an area exceeding 200,000 km**2 in the West Antarctic hinterland. Previous studies, mainly based on marine-geophysical data from the continental shelf and slope, focused on the bathymetry and seafloor bedforms, and the reconstruction of associated depositional processes and ice- drainage patterns. In contrast, there was only sparse information from seabed sediments recovered by coring. In this paper, we present lithological and clay mineralogical data of 21 sediment cores collected from the shelf and slope of the southern Bellingshausen Sea. Most cores recovered three lithological units, which can be attributed to facies types deposited under glacial, transitional and seasonally open-marine conditions. The clay mineral assemblages document coinciding changes in provenance. The relationship between the clay mineral assemblages in the subglacial and proglacial sediments on the shelf and the glacial diamictons on the slope confirms that a grounded ice stream advanced through Belgica Trough to the shelf break during the past, thereby depositing detritus eroded in the West Antarctic hinterland as soft till on the shelf and as glaciogenic debris flows on the slope. The thinness of the transitional and seasonally open-marine sediments in the cores suggests that this ice advance occurred during the last glacial period. Clay mineralogical, acoustic sub-bottom and seismic data furthermore demonstrate that the palaeo-ice stream probably reworked old sedimentary strata, including older tills, on the shelf and incorporated this debris into its till bed. The geographical heterogeneity of the clay mineral assemblages in the sub- and proglacial diamictons and gravelly deposits indicates that they were eroded from underlying sedimentary strata of different ages. These strata may have been deposited during either different phases of the last glacial period or different glacial and interglacial periods. Additionally, the clay mineralogical heterogeneity of the soft tills recovered on the shelf suggests that the drainage area of the palaeo-ice stream flowing through Belgica Trough changed through time.

Chemistry and fluid inclusions of the sheeted dike comples of ODP Holes 137-504B and 140-504B

Fluid inclusions in variably altered diabase recovered from Ocean Drilling Program Legs 137 and 140 at Hole 504B, Costa Rica Rift, exhibit fluid salinities up to 3.7 times that of seawater values (11.7 wt% NaCl equivalent) and exhibit uncorrected homogenization temperatures of 125°C to 202°C. The liquid-dominated inclusions commonly are entrapped in zones of secondary plagioclase and may be primary in origin. Fluid salinities are similar to compositions of fluids venting on the seafloor (0.4-7.0 wt% NaCl) and overlap with those measured in metabasalt samples recovered from near the Kane Fracture Zone on the Mid-Atlantic Ridge and from the Troodos ophiolite, Cyprus. The salinity variations may reflect hydration reactions involving formation of secondary mineral assemblages under rock-dominated conditions, which modify the ionic strength of hydrothermal fluids by consuming or liberating water and chloride ion. Rare CO2-CH4-bearing inclusions, subjacent to zones where talc after olivine becomes an important secondary mineral phase (1700 mbsf), may have formed due to local interaction of seawater and olivine at low water to rock ratios. Corrected average fluid inclusion homogenization temperatures exhibit a gradient from 159°C at a depth of 1370 mbsf to 183°C at a depth of 1992 mbsf and are in apparent equilibrium with the present conductive downhole temperatures. These data indicate that fluid inclusions may be used to estimate downhole temperatures if logging data are unavailable. The compositional and thermal evolution of the diabase-hosted fluids may reflect late-stage, off-axis circulation and conductive heating of compositionally modified seawater in the sheeted dike complex at Hole 504B.

Geochemistry of sediments and interstitial waters of ODP Sites 128-798 and128-799

Interstitial waters in sediments below 400 (Site 798) and 435 meters below seafloor (Site 799) have chloride concentrations of 516-527 and 501-515 mM, respectively, lower than the 540 mM of the modern-day Japan Sea. The chemical composition of interstitial waters, bulk sediments, clay-size sediment fraction, and carbonate nodules from Oki Ridge (Site 798) and Kita-Yamato Trough (Site 799), Japan Sea, reflect in-situ diagenetic processes superimposed on geochemical signals that may indicate freshening of Miocene local marginal basin waters. Interstitial waters at both sites exhibit changes in chemical composition which coincide with the occurrence of low-porosity and high-bulk density layers composed of dolomite and opal-CT, which impede diffusive communication with the overlying interstitial waters. Based on interstitial water stable isotope evidence and mass-balance calculations of chloride dilution, diagenetic reactions that involve the release of structural bound water from opal-A and/or clay minerals contribute to the observed geochemical signals, but cannot account for all the measured chloride dilution.