Carbon and deuterium isotopes and C ratios in gas hydrates of ODP Leg 204 sites

Sediments at the southern summit of Hydrate Ridge display two distinct modes of gas hydrate occurrence. The dominant mode is associated with active venting of gas exsolved from the accretionary prism and leads to high concentrations (15%-40% of pore space) of gas hydrate in seafloor or near-surface sediments at and around the topographic summit of southern Hydrate Ridge. These near-surface gas hydrates are mainly composed of previously buried microbial methane but also contain a significant (10%-15%) component of thermogenic hydrocarbons and are overprinted with microbial methane currently being generated in shallow sediments. Focused migration pathways with high gas saturation (>65%) abutting the base of gas hydrate stability create phase equilibrium conditions that permit the flow of a gas phase through the gas hydrate stability zone. Gas seepage at the summit supports rapid growth of gas hydrates and vigorous anaerobic methane oxidation. The other mode of gas hydrate occurs in slope basins and on the saddle north of the southern summit and consists of lower average concentrations (0.5%-5%) at greater depths (30-200 meters below seafloor [mbsf]) resulting from the buildup of in situ-generated dissolved microbial methane that reaches saturation levels with respect to gas hydrate stability at 30-50 mbsf. Net rates of sulfate reduction in the slope basin and ridge saddle sites estimated from curve fitting of concentration gradients are 2-4 mmol/m**3/yr, and integrated net rates are 20-50 mmol/m**2/yr. Modeled microbial methane production rates are initially 1.5 mmol/m**3/yr in sediments just beneath the sulfate reduction zone but rapidly decrease to rates of <0.1 mmol/m**3/yr at depths >100 mbsf. Integrated net rates of methane production in sediments away from the southern summit of Hydrate Ridge are 25-80 mmol/m**2/yr. Anaerobic methane oxidation is minor or absent in cored sediments away from the summit of southern Hydrate Ridge. Ethane-enriched Structure I gas hydrate solids are buried more rapidly than ethane-depleted dissolved gas in the pore water because of advection from compaction. With subsidence beneath the gas hydrate stability zone, the ethane (mainly of low-temperature thermogenic origin) is released back to the dissolved gas-free gas phases and produces a discontinuous decrease in the C1/C2 vs. depth trend. These ethane fractionation effects may be useful to recognize and estimate levels of gas hydrate occurrence in marine sediments.

Chemistry of interstitial waters of ODP Leg 112 samples

Two distinct hydrogeochemical regimes currently dominate the Peruvian continental margin. One, in shallower water (150-450 m) shelf to upper-slope regions, is characterized by interstitial waters with strong positive chloride gradients with depth. The maximum measured value of 1043 mM chloride at Site 680 at ITS corresponds to a degree of seawater evaporation of ~2 times. Major ion chemistry and strontioum isotopic composition of the interstitial waters suggest that a subsurface brine that has a marine origin and is of pre-early Miocene "age," profoundly influences the chemistry and diagenesis of this shelf environment. Site 684 at ~9°S must be closest to the source of this brine, which becomes diluted with seawater and/or interstitial water as it flows southward toward Site 686 at ~13?S (and probably beyond) at a rate of approximately 3 to 4 cm/yr, since early Miocene time. The other regime, in deep water (3000-5000 m) middle to lower-slope regions, is characterized by interstitial waters with steep negative and nonsteady-state chloride gradients with depth. The minimum measured value of 454 mM chloride, at Site 683 at ITS, corresponds to ~20% dilution of seawater chloride The most probably sources of these low-chloride fluids are gas hydrate dissociation and mineral (particularly clay) dehydration reactions. Fluid advection is consistent with (1) the extent of dilution shown in the chloride profiles, (2) the striking nonsteady-state depth profiles of chlorides at Sites 683 and 688 and of 87Sr/86Sr ratios at Site 685, and (3) the temperatures resulting from an average geothermal gradient of 50°C/km and required for clay mineral dehydration reactions. Strontium isotope data reveal two separate fluid regimes in this slope region: a more northerly one at Sites 683 and 685 that is influenced by fluids with a radiogenic continental strontium signature, and a southerly one at Sites 682 and 688 that is influenced by fluids with a nonradiogenic oceanic signatures. Stratigraphically controlled fluid migration seems to prevail in this margin. Because of its special tectonic setting, Site 679 at ITS is geochemically distinct. The interstitial waters are characterized by seawater chloride concentrations to -200 mbsf and deeper by a significantly lower chloride concentration of about two-thirds of the value in seawater, suggesting mixing with a meteoric water source. Regardless of the hydrogeochemical regime, the chemistry and isotopic compositions of the interstitial waters at all sites are markedly modified by diagenesis, particularly by calcite and dolomite crystallization.

Two-way traveltimes of internal layers and ice thickness between Dome C - Vostok - Dome A

Chinese scientists will start to drill a deep ice core at Kunlun station near Dome A in the near future. Recent work has predicted that Dome A is a location where ice older than 1 million years can be found. We model flow, temperature and the age of the ice by applying a three-dimensional, thermomechanically coupled full-Stokes model to a 70 × 70 km**2 domain around Kunlun station, using isotropic non-linear rheology and different prescribed anisotropic ice fabrics that vary the evolution from isotropic to single maximum at 1/3 or 2/3 depths. The variation in fabric is about as important as the uncertainties in geothermal heat flux in determining the vertical advection which in consequence controls both the basal temperature and the age profile. We find strongly variable basal ages across the domain since the ice varies greatly in thickness, and any basal melting effectively removes very old ice in the deepest parts of the subglacial valleys. Comparison with dated radar isochrones in the upper one third of the ice sheet cannot sufficiently constrain the age of the deeper ice, with uncertainties as large as 500 000 years in the basal age. We also assess basal age and thermal state sensitivities to geothermal heat flux and surface conditions. Despite expectations of modest changes in surface height over a glacial cycle at Dome A, even small variations in the evolution of surface conditions cause large variation in basal conditions, which is consistent with basal accretion features seen in radar surveys.

Annual average Sr/Ca measurements from Porites lutea coral at Ha'afera Island, Tonga

In the South Pacific Convergence Zone (SPCZ), the variability in a sub-seasonally resolved microatoll Porites colony Sr/Ca record from Tonga and a previously published high-resolution record from Fiji are strongly influenced by sea surface temperature (SST) over the calibration period from 1981 to 2004 (R^2 = 0.67 - 0.68). However, the Sr/Ca-derived SST correlation to instrumental SST decreases back in time. The lower frequency secular trend (~1°C) and decadal-scale (~2 - 3°C) modes in Sr/Ca-derived SST are almost two times larger than that observed in instrumental SST. The coral Sr/Ca records suggest that local effects on SST generate larger amplitude variability than gridded SST products indicate. Reconstructed d18O of seawater (d18Osw) at these sites correlate with instrumental sea surface salinity (SSS; r = 0.64 - 0.67) but not local precipitation (r = -0.10 to - 0.22) demonstrating that the advection and mixing of different salinity water masses may be the predominant control on d18Osw in this region. The Sr/Ca records indicate SST warming over the last 100 years and appears to be related to the expansion of the western Pacific warm pool (WPWP) including an increasing rate of expansion in the last ~20 years. The reconstructed d18Osw over the last 100 years also shows surface water freshening across the SPCZ. The warming and freshening of the surface ocean in our study area suggests that the SPCZ has been shifting (expanding) southeast, possibly related to the southward shift and intensification of the South Pacific gyre over the last 50 years in response to strengthened westerly winds.

Anundance of phytoplankton at time series station DYNAPROC

A general study of biogeochemical processes (DYNAPROC cruise) was conducted in May 1995 at a time-series station in the open northwestern Mediterranean Sea where horizontal advection was weak. Short-term variations of the vertical distributions of pico- and nanophytoplankton were investigated over four 36-h cycles, along with parallel determinations of metabolic CO2 production rates and amino acid-containing colloid (AACC) concentrations at the chlorophyll maximum depth. The vertical (0-1000-m depth) distributions of (i) AACC, (ii) suspended particles and (iii) metabolic CO2 production rate were documented during the initial and final stages of these 36-h cycles. This study was concerned with diel vertical migration (DVM) of zooplankton, which provided periodic perturbations. Accordingly, the time scale of the experimental work varied from a few hours to a few days. Although all distributions exhibited a periodic behaviour, AACC distributions were generally not linked to diel vertical migrations. In the subsurface layer, Synechococcus made the most abundant population and large variations in concentration were observed both at day and at night. The corresponding integrated (over the upper 90 m) losses of Synechococcus during one night pointed to a potential source of exported organic matter amounting to 534 mg C/m**2. This study stresses the potential importance of organic matter export from the euphotic zone through the daily grazing activity of vertically migrating organisms, which would not be accounted for by measurements at longer time scales. The metabolic CO2 production exhibited a peak of activity below 500 m that was shifted downward, apparently in a recurrent way and independently of the vertical distributions of AACC or of suspended particulate material. To account for this phenomenon, a 'sustained wave train» hypothesis is proposed that combines the effect of the diel superficial faecal pellet production by swarming migrators and the repackaging activity of the nonmigrating midwater populations. Our results confirm the recent finding that the particulate compartment is not the major source of the observed instantaneous remineralisation rate and shed a new light on the fate of organic matter in the aphotic zone.

Temperature observation of CORK installation during ODP Leg 168

Four boreholes, drilled a few tens of meters into igneous basement on the eastern flank of the Juan de Fuca Ridge during ODP Leg 168, were sealed and instrumented for long-term monitoring to observe the hydrologic state of young sediment-sealed oceanic crust. The thermal regime is dominated by the effects of rapid fluid circulation in uppermost igneous basement driven by very small non-hydrostatic pressure gradients. Upper basement temperatures are uniform laterally between pairs of holes over distances of hundreds of meters to kilometers. In the case of two holes drilled into a sediment-buried basement ridge and adjacent valley, basement temperatures differ by less than 2 K despite the 2.2 km lateral separation of the sites and the 2.5:1 contrast in sediment cover thickness. Under conductive conditions, upper basement temperatures would differ by roughly 50 K. By comparison with modeling results, the observed degree of isothermality suggests a fluid flux of at least 10**-6 m/s (30 m/yr), and an effective permeability in the range of 10**-10 to 10**-9 m**2 in the uppermost igneous crust. The pressure difference available to drive this rapid flux between the ridge and valley, estimated by comparing the observed pressures via the isothermal upper basement hydrostat that is inferred to connect the two sites, is small (~2 kPa) and also suggests high permeability. Relative to the hydrostats defined by the local conductive sediment geotherms, substantial super-hydrostatic pressure (+18 kPa) is present within the buried basement ridge, and sub-hydrostatic pressure is present in the adjacent valley (-26 kPa). Such pressure differentials are the direct consequence of the advection-dominated thermal regime and small pressure losses in high-permeability basement, and are available to drive fluid seepage through sediment sections vertically up above and horizontally away from buried ridges, and down above valleys. No constraints are provided by any of the observations on the depth in the crust to which thermally or chemically significant flow might extend, although just as in the overlying sediments, the pattern of deep flow may be affected by the near-isothermal and near-hydrostatic conditions present in the permeable uppermost crustal section.

Hydrocarbon concentrations from pressurized cores in the northern Gulf of Mexico

Two newly developed coring devices, the Multi-Autoclave-Corer and the Dynamic Autoclave Piston Corer were deployed in shallow gas hydrate-bearing sediments in the northern Gulf of Mexico during research cruise SO174 (Oct-Nov 2003). For the first time, they enable the retrieval of near-surface sediment cores under ambient pressure. This enables the determination of in situ methane concentrations and amounts of gas hydrate in sediment depths where bottom water temperature and pressure changes most strongly influence gas/hydrate relationships. At seep sites of GC185 (Bush Hill) and the newly discovered sites at GC415, we determined the volume of low-weight hydrocarbons (C1 through C5) from nine pressurized cores via controlled degassing. The resulting in situ methane concentrations vary by two orders of magnitudes between 0.031 and 0.985 mol kg**-1 pore water below the zone of sulfate depletion. This includes dissolved, free, and hydrate-bound CH4. Combined with results from conventional cores, this establishes a variability of methane concentrations in close proximity to seep sites of five orders of magnitude. In total four out of nine pressure cores had CH4 concentrations above equilibrium with gas hydrates. Two of them contain gas hydrate volumes of 15% (GC185) and 18% (GC415) of pore space. The measurements prove that the highest methane concentrations are not necessarily related to the highest advection rates. Brine advection inhibits gas hydrate stability a few centimeters below the sediment surface at the depth of anaerobic oxidation of methane and thus inhibits the storage of enhanced methane volumes. Here, computerized tomography (CT) of the pressure cores detected small amounts of free gas. This finding has major implications for methane distribution, possible consumption, and escape into the bottom water in fluid flow systems related to halokinesis.

Distribution of Florisphaera profunda and Helicosphaera carteri in down core and surface sediments

A detailed assessment of the respective roles of production, export, and subsequent preservation of organic carbon (Corg) in the eastern Mediterranean (EMED) sediments during the formation of sapropels remains elusive. Here we present new micropaleontological results for both surface samples taken at several locations in the EMED and last interglacial sapropel S5 from core LC21 in the southeastern Aegean Sea. A strong exponential anticorrelation between relative abundances of the lower photic zone coccolithophore Florisphaera profundain the surface sediments and modern concentrations of chlorophyll a (Chl-a) at the sea surface suggests thatF. profunda percentages can be used to track past productivity changes in the EMED. Prior to S5 deposition, an abrupt and large increase of F. profunda percentages in LC21 coincided (within the multidecadal resolution of the records) with the marked freshening of EMED surface waters. This suggests a strong coupling between freshwater-bound surface to intermediate water (density) stratification and enhanced upward advection of nutrients to the base of the photic zone, fuelling a productive deep chlorophyll maximum (DCM) underneath a nutrient-starved surface layer. Our findings imply that (at least) at the onset of sapropel formation physical and biogeochemical processes likely operated in tandem, enabling high Corg accumulation at the seafloor.

(Table 1) Estimated e-Nd(0) input calculated using the relative fraction of ODP Hole 105-647A amphibole grains originated from different provinces of the North America

Many marine radiogenic isotope records show both spatial and temporal variations, reflecting both the degree of mixing of distinct sources in the oceans and changes in the distribution of chemical weathering on the continents. However, changes in weathering and transport processes may themselves affect the composition of radiogenic isotopes released into seawater. The provenance of physically weathered material in the Labrador Sea, constrained through the use of Ar-Ar ages of individual detrital minerals, has been used to estimate the relative contributions of chemically weathered terranes releasing radiogenic isotopes into the Labrador Sea. A simple box-model approach for balancing observed Nd-isotope variations has been used to constrain the relative importance of localised input in the Labrador Sea, and the subsequent mixing of Labrador Sea Water into North Atlantic Deep-Water. The long-term pattern of erosion and deep-water formation around the North Atlantic seems to have been a relatively stable feature since 1.5 Ma, although there has been a dramatic shift in the nature of physical and chemical weathering affecting the release of Hf and Pb isotopes. The modelled Nd isotopes imply a relative decrease in water mass advection into the Labrador Sea between 2.4 and 1.5 Ma, accompanied by a decrease in the rate of overturning, possibly caused by an increased freshwater input into the Labrador Sea.

Calcareous nannofossil biostratigraphy of ODP Leg 108 sediments

Calcareous nannofossils were examined from the 400 cores recovered at 12 sites during Ocean Drilling Program Leg 108 in the eastern equatorial Atlantic Ocean and along the northwest African margin, representing a transect spanning 24° of latitude. Thirty calcareous nannofossil biohorizons were recognized in the Neogene and Quaternary sequences; only Site 661, located in water depths of 3500 m, contains a fossiliferous record older than the Oligocene. At Site 661, a 200-m-thick sequence of Upper Cretaceous sediments yielded Maestrichtian and uppermost Campanian nannofossils, yet a continuous Cretaceous/Tertiary boundary was not recovered. Widespread sediment slumps and turbidites deposited at many sites interrupted the pelagic sedimentation. A careful study of calcareous nannofossil and foraminifer assemblages correlated to paleomagnetic records suggests that "slumped" units at most sites were added as extra sediments to rapidly deposited pelagic sediments, with minor disturbance of the surrounding layers. Nannofossils are generally common to abundant and moderately preserved at all sites except for those located in two upwelling areas, where placoliths are etched and discoasters overgrown. Typical low-latitudinal zonal markers were used during this study, yet some of them were considered to be of little biostratigraphic value because of their inconsistent stratigraphic ranges and low abundances. This is especially apparent for the intervals representing the Miocene/Pliocene and Oligocene/Miocene boundaries. Characteristic nannofossils of cool-water conditions and low discoaster abundances occur at the coastal African upwelling and along the south equatorial divergence sites, signifying a stronger advection of cold waters toward the equator within the Canary and Benguela eastern boundary currents.

Stable oxygen isotope record and age determination of sediments from the North Atlantic Ocean

Sea surface temperature and salinity estimates reconstructed using planktonic foraminiferal abundance and delta18O records from core SU90-03 (40°N, 32°W, 2475 m water depth) reveal large climatic fluctuations linked to major instabilities in Northern Hemisphere ice sheets over the last 150 000 years. Episodes of enhanced ice rafted detritus (IRD) input were accompanied by discrete temperature minima, representing coolings of between 4 and 8°C, and reductions in surface salinity of up to 2.5-3.5 per mil. Several additional cooling episodes of a similar magnitude were documented during intervals of low IRD input that appear to be synchronous, within the limits of dating, with ice rafting events spatially confined to higher latitudes. Accelerator mass spectrometer 14C dates for Heinrich events (H1 - 14.2 ka, H2 - 21.4 ka, H3 - 26.7 ka, H4 - 34.8 ka, H5 - 47.2 ka) obtained from core SU90-03 agree well with other published age estimates and suggest a contemporaneous pattern of climate change throughout the North Atlantic during the last glacial period. This interpretation is supported by a comparison of IRD and palaeotemperature records from DSDP site 609 and core SU90-03, which clearly shows that the major climatic fluctuations identified at high latitudes were transmitted toward the subtropics. However, 14C dates suggest that ice rafting episodes may be diachronous to some extent. The northward migration of the polar front after the H1 event at 40°N in the mid-Atlantic occurred at 14 ka, approximately 500 years earlier than along the Portuguese margin, where the southerly advection of polar waters persisted within eastern boundary current system.

Concentration of aerosol components over the Noth Atlantic Ocean (Tab. 2)

Aerosol samples collected over the North Atlantic from ship were analysed for Sodium, Magnesium, Potassium, Calcium and Chloride. A found dependence of sea salt concentrations from wind velocity is compared with earlier results. The mean of the ratio Cl/Na was close to that for sea water; the Mg-, K- and Ca-concentrations in the aerosol, however, were enriched with respect to sea water. It is shown that continental advection influences the measured aerosol components over the North Atlantic.