Chemical, and Sr and Li isotopic composition of pore fluids and sediments from ODP Leg 170 and Leg 205 sites

Pore fluid and sediment chemical and isotopic data were obtained for samples from Ocean Drilling Program (ODP) Leg 205 Sites 1253, 1254, and 1255 in the Costa Rica subduction zone. The chemical and isotopic data reported here were generated in our shore-based laboratories to complement shipboard inorganic geochemical data. Li isotopic analyses were carried out by L.-H. Chan at Louisiana State University (USA). The data reported herein include fluoride, bromide, rubidium, cesium, and barium concentrations; Li and Sr isotopic compositions in pore fluids; and Rb, Cs, and Ba concentrations in representative bulk sediments. The data also include new pore fluid fluoride and bromide concentrations from corresponding ODP Leg 170 Sites 1039, 1040, and 1043. O.M. Saether's Site 1039 and 1040 fluoride concentration data are shown for comparison. Basal sediment fluoride concentrations and Li and Sr isotope ratios at both Sites 1253 and 1039 show reversals that approach modern seawater values. Br/Cl ratios are, however, conservative throughout the sediment section at Sites 1039 and 1253. The observed sharp F and Br concentration maxima, Rb and K concentration minima, the most radiogenic 87Sr/86Sr ratios, and highest 7Li values along the décollement and fracture zone (Sites 1040, 1043, 1254, and 1255) strengthen the evidence obtained during Leg 170 that a deeply sourced fluid, originating from fluid-rock reactions at ~150°C and corresponding to between 10 and 15 km depth, is transporting solutes to the ocean.

Geochemistry of the oceanic crust from ocean drilling samples

This book presents new data on chemical and mineral compositions and on density of altered and fresh igneous rocks from key DSDP and ODP holes drilled on the following main tectonomagmatic structures of the ocean floor: 1. Mid-ocean ridges and abyssal plains and basins (DSDP Legs 37, 61, 63, 64, 65, 69, 70, 83, and 91 and ODP Legs 106, 111, 123, 129, 137, 139, 140, 148, and 169); 2. Seamounts and guyots (DSDP Legs 19, 55, and 62 and ODP Legs 143 and 144); 3. Intraplate rises (DSDP Legs 26, 33, 51, 52, 53, 72, and 74 and ODP Legs 104, 115, 120, 121, and 183); and 4. Marginal seas (DSDP Legs 19, 59, and 60 and ODP Legs 124, 125, 126, 127, 128, and 135). Study results of altered gabbro from the Southwest Indian Ridge (ODP Leg 118) and serpentinized ultramafic rocks from the Galicia margin (ODP Leg 103) are also presented. Samples were collected by the authors from the DSDP/ODP repositories, as well as during some Glomar Challenger and JOIDES Resolution legs. The book also includes descriptions of thin sections, geochemical diagrams, data on secondary mineral assemblages, and recalculated results of chemical analyses with corrections for rock density. Atomic content of each element can be quantified in grams per standard volume (g/1000 cm**3). The suite of results can be used to estimate mass balance, but parts of the data need additional work, which depends on locating fresh analogs of altered rocks studied here. Results of quantitative estimation of element mobility in recovered sections of the upper oceanic crust as a whole are shown for certain cases: Hole 504B (Costa Rica Rift) and Holes 856H, 857C, and 857D (Middle Valley, Juan de Fuca Ridge).

Stable isotope record and lithic fragments distribution in sediments of MIS9-14 of the North Atlantic

Stable isotope and ice-rafted debris records from three core sites in the mid-latitude North Atlantic (IODP Site U1313, MD01-2446, MD03-2699) are combined with records of ODP Sites 1056/1058 and 980 to reconstruct hydrographic conditions during the middle Pleistocene spanning Marine Isotope Stages (MIS) 9-14 (300-540 ka). Core MD03-2699 is the first high-resolution mid-Brunhes record from the North Atlantic's eastern boundary upwelling system covering the complete MIS 11c interval and MIS 13. The array of sites reflect western and eastern basin boundary current as well as north to south transect sampling of subpolar and transitional water masses and allow the reconstruction of transport pathways in the upper limb of the North Atlantic's circulation. Hydrographic conditions in the surface and deep ocean during peak interglacial MIS 9 and 11 were similar among all the sites with relative stable conditions and confirm prolonged warmth during MIS 11c also for the mid-latitudes. Sea surface temperature (SST) reconstructions further reveal that in the mid-latitude North Atlantic MIS 11c is associated with two plateaus, the younger one of which is slightly warmer. Enhanced subsurface northward heat transport in the eastern boundary current system, especially during early MIS 11c, is denoted by the presence of tropical planktic foraminifer species and raises the question how strongly it impacted the Portuguese upwelling system. Deep water ventilation at the onset of MIS 11c significantly preceded surface water ventilation. Although MIS 13 was generally colder and more variable than the younger interglacials the surface water circulation scheme was the same. The greatest differences between the sites existed during the glacial inceptions and glacials. Then a north - south trending hydrographic front separated the nearshore and offshore waters off Portugal. While offshore waters originated from the North Atlantic Current as indicated by the similarities between the records of IODP Site U1313, ODP Site 980 and MD01-2446, nearshore waters as recorded in core MD03-2699 derived from the Azores Current and thus the subtropical gyre. Except for MIS 12, Azores Current influence seems to be related to eastern boundary system dynamics and not to changes in the Atlantic overturning circulation.

Organic matter preservation in sediments of the Peru and Oman continental margin

Detailed petrographical and bulk geochemical investigations of organic matter (OM) have been performed on sediments deposited below or close to upwelling areas offshore Peru (ODP-Leg 112; Sites 679, 681, 688) and Oman (ODP-Leg 117; Sites 720, 723, 724) in order to obtain a quantitative understanding of its accumulation and degradation. Microscopical as well as nanoscopical investigations reveal that the OM in sediments affected by upwelling mechanisms mainly (up to 98%) consists of unstructured (amorphous) organic aggregates without any apparent biological structures. In sediments which are not or to a lesser extent affected by upwelling (Site 720) terrestrial OM predominates. Organic carbon (TOC) contents are highly variable and range between 9.8% in sediments deposited below upwelling cells and 0.2% in sediments outside the upwelling zone. The TOC/sulphur ratios of the sediments scatter widely. The samples from the deep-water locations (Sites 688 and 720), show C/S-ratios of "normal" marine sediments, whereas at the other locations no correlation or even a negative correlation between sulphur and TOC concentration exists. In most of the upwelling-influenced sediments OM contains a significant amount of sulphur. The incorporation of sulphur into the OM followed microbial sulphate reduction and occurred in the upper meters of the sedimentary column. Below, OM is still present in vast amounts and relatively hydrogen-rich, but is nevertheless non-metabolizable and becomes the limiting factor for bacterial sulphate reduction. According to mass balance calculations 90-99% of the OM produced in the photic zone was remineralized and 1-3% was consumed by microbial sulphate reduction. The aerobic and anaerobic processes have greatly affected degradation and conservation of OM.

Molecular properties of gases of ODP Leg 204 sites

The recognition of finely disseminated gas hydrate in deep marine sediments heavily depends on various indirect techniques because this mineral quickly decomposes upon recovery from in situ pressure and temperature conditions. Here, we discuss molecular properties of closely spaced gas voids (formed as a result of core recovery) and gas hydrates from an area of relatively low gas flux at the flanks of the southern Hydrate Ridge offshore Oregon (ODP Sites 1244, 1245 and 1247). Within the gas hydrate occurrence zone (GHOZ), the concentration of ethane (C2) and propane (C3) in adjacent gas voids shows large variability. Sampled gas hydrates are enriched in C2 relative to void gases but do not contain C3. We suggest that the observed variations in the composition of void gases is a result of molecular fractionation during crystallization of structure I gas hydrate that contains C2 but excludes C3 from its crystal lattice. This hypothesis is used to identify discrete intervals of finely disseminated gas hydrate in cored sediments. Variations in gas composition help better constrain gas hydrate distribution near the top of the GHOZ along with variations in pore water chemistry and core temperature. Sediments near the base of the gas hydrate stability zone are relatively enriched in C2+ hydrocarbon gases. Complex and poorly understood geological and geochemical processes in these deeper sediments make the identification of gas hydrate based on molecular properties of void gases more ambiguous. The proposed technique appears to be a useful tool to better understand the distribution of gas hydrate in marine sediments and ultimately the role of gas hydrate in the global carbon cycle.

Carbon and Nitrogen concentrations and isotopic composition of ODP Site 170-1040 and Leg 205 sites

We determined the C and N concentrations and isotopic compositions of sediments in the prism sampled during Ocean Drilling Program Legs 170 and 205 offshore Costa Rica, with the goals of evaluating sediment sources and extents of diagenesis and identifying any effects of infiltrating fluids on the sedimentary C and N. The sediments from Leg 170 Site 1040 contain 0.85-1.96 wt% total organic carbon (TOC) with Vienna Peedee belemnite (VPDB) d13CVPDB from -26.3 per mil to -22.5 per mil, and 832-2221 ppm total nitrogen (TN) with d15Nair from +3.5 per mil to +6.6 per mil. Sediment TN concentrations and d15N values show dramatic downhole increases within the uppermost 130 m of the section and more gradual downhole decreases from 130 meters below seafloor (mbsf) to the base of the décollement at ~370 mbsf. Concentrations and isotopic compositions of TOC are relatively uniform within the entire section, showing some minor perturbation within the décollement zone. In the uppermost 100 m, upsection increases in TN concentrations at constant TOC concentrations produce significant increases in atomic TOC/TN ratios from ~8 to ~18. Carbonate (calcite) contents in the wedge sediments are generally low (<4 wt%), but the d13C and Vienna standard mean ocean water (VSMOW) d18OVSMOW values vary significantly from -26.1 per mil to +4.1 per mil and from +30.0 per mil to +35.3 per mil, respectively. Concentrations and isotopic compositions of TOC and TN for sediments from Leg 205 Sites 1254 and 1255 overlap well with C-N data for sediments from the same depth intervals obtained during Leg 170 at Site 1040.

Pressure core barrel characteristics and composition of gases at DSDP Site 76-533

A pressure core barrel (PCB), developed by the Deep Sea Drilling Project, was used successfully to recover, at in situ pressure, sediments of the Blake Outer Ridge, offshore the southeastern United States. The PCB is a unique, wire-line tool, 10.4 m long, capable of recovering 5.8 m of core (5.8 cm in diameter), maintained at or below in situ pressures of 34.4 million Pascals (MPa), and 1.8 m of unpressurized core (5.8 cm in diameter). All excess internal pressure above the operating pressure of 34.4 MPa is automatically vented off as the barrel is retrieved. The PCB was deployed five times at DSDP Site 533 where geophysical evidence suggests the presence of gas hydrates in the upper 600 m of sediment. Three cores were obtained holding average in situ pressures of 30 MPa. Two other cores did not maintain in situ pressures. Three of the five cores were intermittently degassed at varying intervals of time, and portions of the vented gas were collected for analysis. Pressure decline followed paths indicative of gas hydrates and/or dissolved gas. The released gas was dominantly methane (usually greater than 90%), along with higher molecular-weight hydrocarbon gases and carbon dioxide. During degassing the ratio of methane to ethane did not vary significantly. On the other hand, concentrations of higher molecular-weight hydrocarbon gases increased, as did carbon dioxide concentrations. The results from the PCB experiments provide tentative but equivocal evidence for the presence of .gas hydrates at Site 533. The amount of gas hydrate indicated is small. Nevertheless, this work represents the first successful study of marine gas hydrates utilizing the PCB.

Dinoflagellate and other palynomorph abundance in sediments from ODP Leg 189 sites

At Ocean Drilling Program (ODP) Leg 189 Sites 1170-1172, the climatologically critical Eocene-Oligocene (E-O) transition is barren of any calcareous microfossils but contains rich marine organic walled dinoflagellate cyst (dinocyst) and diatom assemblages, suitable for detailed biostratigraphic and paleoenvironmental analysis. The resulting first-ever integrated dinocyst/diatom magnetostratigraphy allows confident correlation of the E-O interval between all Leg 189 sites, including Site 1168. Our correlations indicate that the (deep) opening of the Tasmanian Gateway occurred quasi-synchronously throughout the Tasmanian region, starting at ~35.5 Ma. At Sites 1170-1172, quantitatively, three distinct dinocyst assemblages may be distinguished that reflect the relatively rapid and pronounced stepwise environmental changes associated with the E-O transition in the Tasmanian region, from a pro-deltaic setting to a deep marine pelagic setting. Moreover, synchronous with the deepening of the gateway, at the southern and eastern Sites 1170-1172, typical endemic Antarctic assemblages were replaced by more cosmopolitan dinocyst communities. In marked contrast, at Site 1168 off western Tasmania, endemic Antarctic taxa are virtually absent during the E-O transition. At Sites 1170-1172, the endemic Antarctic dinocyst assemblage (Transantarctic Flora) drastically changes into a more cosmopolitan assemblage at ~35.5 Ma, with a more offshore character, reflecting the arrival of different oceanographic and environmental conditions associated with the deepening of the Tasmanian Gateway. In turn, this assemblage grades at ~34 Ma into one more typical for even more offshore and/or upwelling conditions at Site 1172. In slightly younger deposits at all sites, organic microfossils are virtually absent, reflecting winnowing and oxidation, indicative of a next step of oceanographic development. This phase may be dated as close to the Oceanic Anoxic (Oi)-1 18O (Antarctic glaciation) event (~33.3 Ma). In a single productive sample from the earliest Oligocene the northern Site 1172, a relatively warm-water cosmopolitan assemblage has been recovered. This aspect contrasts findings from coeval deposits from the Ross Sea, where endemic Antarctic species remain dominant. Somewhere between the paleogeographic positions of Site 1172 and the Ross Sea, a strong differentiation of surface waters occurred in the earliest Oligocene, possibly reflecting the onset of the Antarctic Circumpolar Current.

Cenomanian/Turonian sea surface temperatures of the equatorial Atlantic reconstructed from geochemical data

Oceanic anoxic event 2 (OAE-2) occurring during the Cenomanian/Turonian (C/T) transition is evident from a globally recognized positive stable carbon isotopic excursion and is thought to represent one of the most extreme carbon cycle perturbations of the last 100 Myr. However, the impact of this major perturbation on and interaction with global climate remains unclear. Here we report new high-resolution records of sea surface temperature (SST) based on TEX86 and d 18O of excellently preserved planktic foraminifera and stable organic carbon isotopes across the C/T transition from black shales located offshore Suriname/French Guiana (Demerara Rise, Ocean Drilling Program Leg 207 Site 1260) and offshore Senegal (Cape Verde Basin, Deep Sea Drilling Project Leg 41 Site 367). At Site 1260, where both SST proxy records can be determined, a good match between conservative SST estimates from TEX86 and d 18O is observed. We find that late Cenomanian SSTs in the equatorial Atlantic Ocean (33°C) were substantially warmer than today (27°-29°C) and that the onset of OAE-2 coincided with a rapid shift to an even warmer (35°-36°C) regime. Within the early stages of the OAE a marked (4°C) cooling to temperatures lower than pre-OAE conditions is observed. However, well before the termination of OAE-2 the warm regime was reestablished and persisted into the Turonian. Our findings corroborate the view that the C/T transition represents the onset of the interval of peak Cretaceous warmth. More importantly, they are consistent with the hypotheses that mid-Cretaceous warmth can be attributed to high levels of atmospheric carbon dioxide (CO2) and that major OAEs were capable of triggering global cooling through the negative feedback effect of organic carbon-burial-led CO2 sequestration. Evidently, however, the factors that gave rise to the observed shift to a warmer climate regime at the onset of OAE-2 were sufficiently powerful that they were only briefly counterbalanced by the high rates of carbon burial attained during even the most extreme interval of organic carbon burial in the last 100 Myr.