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.

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.

Radiometric age determinations for basements of ODP Sites 123-765 and 123-766

The results of experiments in 40Ar/39Ar age dating using fresh basement material from Sites 765 and 766 of Leg 123 of the Ocean Drilling Program are inconsistent and cannot be used to constrain the basement age of the Argo Abyssal Plain in the Indian Ocean. However, a celadonite sample, which was precipitated during a low-temperature alteration event that affected the basement at Site 765, yielded a K-Ar age of 155.3 ±3.4 Ma. Celadonites, which have been dated using Rb-Sr methods for basement in the Atlantic Ocean (Staudigel et al., 1981, doi:10.1016/0012-821X(81)90186-2) and by K-Ar methods for the Troodos Ophiolite (Staudigel et al., 1986, doi:10.1130/0091-7613(1986)14<72:AASAOC>2.0.CO;2), and for sediments from the Pacific Ocean (Peterson et al., 1986, doi:10.2973/dsdp.proc.92.132.1986) yield ages that are up to 15 Ma younger than the age for the formation of basement. Thus, the celadonite age is retained as a reliable minimum age for basement at Site 765. This radiometric age is inconsistent with biostratigraphic ages, which indicate a maximum of late Berriasian (approximately 140 Ma) for Site 765, but is consistent with geophysical interpretations of marine magnetic anomalies and with the early north-south seafloor spreading history of the Argo Abyssal Plain region of the Indian Ocean.

Pore-water chemistry of ODP sites 111-677 and 111-678

Sites 677 and 678 were drilled on ODP Leg 111 to test hypotheses about the nature and pattern of hydrothermal circulation on a mid-ocean ridge flank. Together with earlier results from DSDP Site 501/504 and several heatflow and piston coring surveys covering a 100-km**2 area surrounding the three drill sites, they confirm that hydrothermal circulation persists in this 5.9-m.y.-old crust, both in basement and through the overlying sediments (Langseth et al., 1988, doi:10.2973/odp.proc.ir.111.102.1988). Profiles of sediment pore-water composition with depth at the three drill sites show both vertical and horizontal gradients. The shapes of the profiles and their variation from one site to another result from a combination of vertical and horizontal diffusion, convection, and reaction in the sediments and basement. Chemical species that are highly reactive in the siliceous-calcareous biogenic sediments include bicarbonate (alkalinity), ammonium, sulfate, manganese, calcium, strontium, lithium, silica, and possibly potassium. Reactions include bacterial sulfate reduction, mobilization of Mn2+, precipitation of CaCO3, and recrystallization of calcareous and siliceous oozes to chalk, limestone, and chert. Species with profiles more affected by reaction in basaltic basement than in the sediments include Mg, Ca, Na, K, and oxygen isotopes. Reaction in basement at 60?C and at higher temperatures has produced a highly altered basement formation water that is uniform in composition over distances of several kilometers. As inferred from the composition of the basal sediment pore water at the three sites, this uniformity extends from up flow zone to downflow zone in basement and the sediments. It exists in spite of large variations in heat flow and depth to basement, apparently as a result of homogenization by hydrothermal circulation in basement. Profiles for chlorinity, Na, Mg, and other species in the sediment pore waters confirm that Site 678, drilled on a localized heatflow high identified by Langseth et al. (1988), is a site of long-lived upwelling of warm water from basement through the sediments at velocities of 1 to 2 mm/yr. The upflow through the anomalously thin sediments is apparently localized above an uplifted fault block in basement. This site and other similar sites in the survey area give rise to lateral diffusion and possibly flow through the sediments, which produces lateral gradients in sediment pore-water composition at sites such as 501/504. The complementary pore-water profiles at the low-heatflow Site 677 2 km to the south indicate that downflow is occurring through the sediments there, at comparable rates of 1 to 2 mm/yr.

Porosity, gas permeability and grain density of ODP Leg 194 sites

We report analyses of porosity and permeability of core samples from Site 1193 in the Northern Marion Platform, Sites 1196 and 1199 in the Southern Marion Platform, and Sites 1194, 1195, 1197, and 1198 from the slopes of these platforms. The samples include 415 horizontal 1-in plugs, 290 vertical 1-in plugs, and 23 whole-core pieces. Porosity and permeability analyses were possible for most, but not all, samples. Grain density measurements were also obtained for the horizontal plugs. Representative photomicrographs are provided of thin sections from 139 of the horizontal plugs and the 23 whole-core pieces.

Upper Cretaceous-Paleogene stratigraphy of ODP Sites 113-689 and 113-690

This contribution summarizes the biostratigraphy of planktonic foraminifers, calcareous nannofossils, and benthic foraminifers, in combination with the magnetostratigraphy, carbon and oxygen isotope stratigraphy of benthic foraminifers, and CaCO3 stratigraphy for the Maestrichtian through Paleogene calcareous sequences recovered at Sites 689 and 690 on Maud Rise (at about 65°S, eastern Weddell Sea, Antarctica). These data represent the southernmost calciumcarbonate record available for that interval, and thus extend the biostratigraphic and isotopic database to higher latitudes. Sites 689 and 690 form the southernmost anchor of a north-south transect through the Atlantic Ocean for Paleogene biostratigraphy and chemostratigraphy.

Oxygen isotopes and hydrocarbon composition of gas hydrate and hydrate water from ODP Leg 165 sites

Ocean Drilling Program (ODP) Leg 164 recovered a number of large solid gas hydrate from Sites 994, 996, and 997 on the Blake Ridge. Sites 994 and 997 samples, either nodular or thick massive pieces, were subjected to laboratory analysis and measurements to determine the structure, molecular and isotopic composition, thermal conductivity, and equilibrium dissociation conditions. X-ray computed tomography (CT) imagery, X-ray diffraction, nuclear magnetic resonance (NMR), and Raman spectroscopy have revealed that the gas hydrates recovered from the Blake Ridge are nearly 100% methane gas hydrate of Structure I, cubic with a lattice constant of a = 11.95 ± 0.05 angström, and a molar ratio of water to gas (hydration number) of 6.2. The d18O of water is 2.67 per mil to 3.51 per mil SMOW, which is 3.5-4.0 heavier than the ambient interstitial waters. The d13C and dD of methane are -66 per mil to -70 per mil and -201 per mil to -206 per mil, respectively, suggesting that the methane was generated through bacterial CO2 reduction. Thermal conductivity values of the Blake Ridge hydrates range from 0.3 to 0.5 W/(m K). Equilibrium dissociation experiments indicate that the three-phase equilibrium for the specimen is 3.27 MPa at 274.7 K. This is almost identical to that of synthetic pure methane hydrate in freshwater.

Calcareous nannofossil stratigraphy, mass accumulation rates and bulk density of sediments from ODP Leg 173 sites

Drilling on the Iberia Abyssal Plain during Ocean Drilling Program Leg 173 allowed us to recover Upper Cretaceous through Paleocene sediments at Sites 1068 and 1069 and only upper Paleocene sediments at Site 1067, which expands considerably the Upper Cretaceous to Paleocene record for this region. Of these three sites, Site 1068 recovered uppermost Cretaceous sediments as well as the most complete Paleocene record, whereas Site 1067 yielded only uppermost Paleocene sediments (Zone CP8). Site 1069 provided a rather complete upper Campanian through Maastrichtian section but a discontinuous Paleocene record. After a detailed calcareous nannofossil biostratigraphy was documented in distribution charts, we calculated mass accumulation rates for Holes 1068A and 1069A. Sediments in Hole 1068A apparently record the final stages of burial of a high basement block by turbidity flows. Accumulation rates through the Upper Cretaceous indicate relatively high rates, 0.95 g/cm**2/k.y., but may be unreliable because of the lack of datum points and/or possible hiatuses. Accumulation rates in the Paleocene section of Hole 1068A fluctuated every few million years from lower (~0.35 g/cm**2/k.y.) to higher rates (~0.85 g/cm**2/k.y.) until the latest Paleocene, when rates increased to an average of ~2.0 g/cm**2/k.y. Mass accumulation rates for the Upper Cretaceous in Hole 1069A indicate a steady rate of ~0.60 g/cm**2/k.y. from 75 to 72 Ma. There may have been one or more hiatuses between 72 and 68 Ma (combined Zone CC24 through Subzone CC25b), as indicated by the very low accumulation rate of 0.15 g/cm**2/k.y. The Paleocene section of Hole 1069A does not show the same continuous record, which may result from fluctuations in the carbonate compensation depth and poor recovery (average = 40%). Zones CP4 and CP5 are missing within a barren interval; this and numerous other barren intervals affect the precision of the nannofossil zonation and calculation of mass accumulation rates. However, in spite of these missing zones, mass accumulation rates do not seem to indicate the presence of hiatuses as the rates for this barren interval average ~1.0 g/cm**2/k.y. This study set out to test the hypothesis that a reliable biostratigraphic record could be constructed from sediments derived from turbidity flows deposited below the carbonate compensation depth. As illustrated here, not only could a reliable biostratigraphic record be determined from these sediments, but sedimentation and mass accumulation rates could also be determined, allowing inferences to be drawn concerning the sedimentary history of this passive margin. The reliability of this record is confirmed by independent verification by the establishment of a magnetostratigraphy for the same cores.

Bulk and clay mineral composition of ODP Leg 189 sites

Bulk and clay mineral investigations were conducted on ~750 samples from four sites drilled during Ocean Drilling Program Leg 189 on the western Tasmanian margin (Site 1168), the South Tasman Rise (Sites 1170 and 1171), and the East Tasman Plateau (Site 1172). The mineralogy of the bulk sediment is very similar at all sites, and major changes coincide with the boundaries of the three main lithologic units described in the Leg 189 Initial Reports volume. The clay mineral assemblages show significant regional differences, but their major variations coincide at all sites and with major changes in regional tectonics and climate.

Distribution, depositional form and geochemical composition of tephra horizons in ODP Sites 186-1150 and 186-1151

Major element geochemical composition was established for 59 tephra horizons from Ocean Drilling Program Sites 1150 and 1151, located in the Japan forearc. These data, encompassing typically between 15 and 30 individual shard analyses per tephra horizon, were used to investigate the degree to which sediment reworking, postdepositional geochemical alteration, and geochemical uniqueness of individual eruptives facilitate or impede the potential for establishing a tephrostratigraphical framework for the Japan Trench, as well as usage of the tephra record to document arc evolution. Evidence was found that hydration (termed phase 1 alteration) of glass shards increases with age in the Pliocene-Pleistocene, but there is no indication that element leaching (phase 2 alteration) has occurred. Post- or syn-depositional differences in preservational style are shown to have no significant bearing on tephrogeochemical homogeneity and suitability for tephrostratigraphical analysis. Overall, therefore, the volcaniclastic record is suitable for investigating medium- to long-term changes in arc geochemistry and, provided consideration is given to the potential for nonunique geochemical signatures, is suitable for erecting tephrochronological frameworks. A limited number of Pleistocene tephra correlations are suggested in furtherance of this framework goal.

Quaternary benthic foraminifers from DSDP Sites 95-612 and 95-613

The Quaternary benthic foraminifers from Leg 95 Sites 612 and 613 were examined with respect to paleoceanographic trends. Data from the two sites indicate the presence of markedly different bottom-water masses, during both glacial and interglacial periods. The dominant interglacial species at Site 612 is Uvigerinct peregrina, which is barely present in corresponding intervals at Site 613. Dominant glacial species are Elphidium excavatum and Cassidulina reniforme at Site 612 and Epistominella takayanagii at Site 613.

Benthic foraminifera and stable isotope record of ODP Leg 182 sites

Cores from Sites 1129, 1131, and 1132 (Ocean Drilling Program (ODP) Leg 182) on the uppermost slope at the edge of the continental shelf in the Great Australian Bight reveal the existence of upper Pleistocene bryozoan reef mounds, previously only detected on seismic lines. Benthic foraminiferal oxygen isotope data for the last 450,000 years indicate that bryozoan reef mounds predominantly accumulated during periods of lower sea level and colder climate since stage 8 at Sites 1129 and 1132 and since stage 4 at the deeper Site 1131. During glacials and interstadials (stages 2-8) the combination of lowered sea level, increased upwelling, and absence of the Leeuwin Current probably led to an enhanced carbon flux at the seafloor that favored prolific bryozoan growth and mound formation at Site 1132. At Site 1129, higher temperatures and downwelling appear to have inhibited the full development of bryozoan mounds during stages 2-4. During that time, favorable hydrographic conditions for the growth of bryozoan mounds shifted downslope from Site 1129 to Site 1131. Superimposed on these glacial-interglacial fluctuations is a distinct long-term paleoceanographic change. Prior to stage 8, benthic foraminiferal assemblages indicate low carbon flux to the seafloor, and bryozoan mounds, although present closer inshore, did not accumulate significantly at Sites 1129 and 1132, even during glacials. Our results show that the interplay of sea level change (eustatic and local, linked to platform progradation), glacial-interglacial carbon flux fluctuations (linked to local hydrographic variations), and possibly long-term climatic change strongly influenced the evolution of the Great Australian Bight carbonate margin during the late Pleistocene.