Pore water chemistry of ODP Sites 201-1225, 201-1226 and 201-1231

High-resolution analyses of the oxygen isotope ratio (18O/16O) of dissolved sulfate in pore waters have been made to depths of >400 meters below seafloor (mbsf) at open-ocean and upwelling sites in the eastern equatorial Pacific Ocean. d18O values of dissolved sulfate (d18O-SO4) at the organic-poor open-ocean Site 1231 gave compositions close to modern seawater (+9.5 per mil vs. Vienna-standard mean ocean water, providing no chemical or isotopic evidence for microbial sulfate reduction (MSR). In contrast, the maximum d18O values at Sites 1225 and 1226, which contain higher organic matter contents, are +20 per mil and +28 per mil, respectively. Depth-correlative trends of increasing d18O-SO4, alkalinity, and ammonium and the presence of sulfide indicate significant oxidation of sedimentary organic matter by sulfate-reducing microbial populations at these sites. Although sulfate concentration profiles at Sites 1225 and 1231 both show similarly flat trends without significant net MSR, d18O-SO4 values at Site 1225 reveal the presence of significant microbial sulfur-cycling activity, which contrasts to Site 1231. This activity may include contributions from several processes, including enzyme-catalyzed equilibration between oxygen in sulfate and water superimposed upon bacterial sulfate reduction, which would tend to shift d18O-SO4 toward higher values than MSR alone, and sulfide oxidation, possibly coupled to reduction of Fe and Mn oxides and/or bacterial disproportionation of sulfur intermediates. Large isotope enrichment factors observed at Sites 1225 and 1226 (epsilon values between 42 per mil and 79 per mil) likely reflect concurrent processes of kinetic isotope fractionation, equilibrium fractionation between sulfate and water, and sulfide oxidation at low rates of sulfate reduction. The oxygen isotope ratio of dissolved pore water sulfate is a powerful tool for tracing microbial activity and sulfur cycling by the deep biosphere of deep-sea sediments.

Chemical and isotopic compositions of deep-sea carbonate sediments and interstitial waters from DSDP Sites 30-288 and 30-289

Interstitial waters and sediments from DSDP sites 288 and 289 contain information on the chemistry and diagenesis of carbonate in deep-sea sediments and on the role of volcanic matter alteration processes. Sr/Ca ratios are species dependent in unaltered foraminifera from site 289 and atom ratios (0.0012-0.0016) exceed those predicted by distribution coefficent data (~0.0004). During diagenesis Sr/Ca ratios of carbonates decrease and reach the theoretical distribution at a depth which is identical to the depth of Sr isotopic equilibration, where 87Sr/86Sr ratios of interstitial waters and carbonates converge. Mg/Ca ratios in the carbonates do not increase with depth as found in some other DSDP sites, possibly because of diagenetic re-equilibration with interstitial waters showing decreasing Mg(2+)/Ca(2+) ratios with depth due to Ca input and Mg removal by alteration of volcanic matter. Interstitial 18O/16O ratios increase with depth at site 289 to d18O = 0.67? (SMOW), reflecting carbonate recrystallization at elevated temperatures (>/= 20°C), the first recorded evidence of this effect in interstitial waters. Interstitial Sr2+ concentrations reach high levels, up to 1 mM, chiefly because of carbonate recrystallization. However, 87Sr/86Sr ratios decrease from 0.7092 to less than 0.7078, lower than for contemporaneous sea water, showing that there is a volcanic input of strontium at depth. This volcanic component is recorded in the Sr isotopic composition of recrystallized calcites. Isotopic compositions of the unrecrystallized calcites suggests that the rate of increase of the 87Sr/86Sr ratio of sea water with time has been faster since 3 my ago than in the preceding 13 my.

Cenozoic clay mineralogy of DSDP Sites 93-604 and 93-605

Examination of the clay mineralogy of Cenozoic sediment samples from Deep Sea Drilling Project Sites 604 and 605 on the upper continental rise off New Jersey indicates that sediment deposition of two different clay mineral facies has occurred. These sites are marked by Paleogene deposition of illite with subordinate kaolinite and smectite covarying in inverse proportion, and by Neogene deposition dominated by illite with subordinate kaolinite and chlorite. Leg 93 results agree with the clay mineral facies proposed by Hathaway (1972), which defined a "Northern facies" consisting of illite and chlorite, with feldspar and hornblende, from erosion of rocks north of Cape Hatteras, and a "Southern facies" composed of smectite, kaolinite, and mixed-layer illite-smectites. Neogene and Quaternary sediments at Sites 604 and 605 contain the "Northern facies," and Paleogene sediments contain the "Southern facies" minerals. Feldspar is exclusively found in Neogene-Quaternary sediments, as is the majority of the amphibole found in these samples. Widespread Paleogene volcanic source materials are suggested by the presence of smectite throughout the early Paleocenemiddle Eocene sediments recovered at Site 605. The clay mineral stratigraphy at Leg 93 sites is comparable to the record at nearby DSDP sites on the lower continental rise and abyssal plain of the northwestern Atlantic (DSDP Sites 388, 105, and 106), and also with the sediments recovered by drilling on the Mazagan Plateau off northwestern Morocco (DSDP Sites 544-547) in the eastern North Atlantic.

Calcareous nannofossil abundance and datums of sediments from ODP Leg 170 sites

Three Pleistocene, five Pliocene, and thirteen late and middle Miocene calcareous nannofossil datums have been identified in the Leg 170 cored sequences collected from a transect across the Middle America Trench off the Nicoya Peninsula. Although some nannofossil zones could not be delineated, particularly in the Pliocene and upper Miocene, there appears to be a complete or very nearly complete Pleistocene through lower Miocene section at Sites 1039 and 1040. The oldest assemblages, observed at Site 1039 and 1040, are latest early Miocene in age (nannofossil Zone NN4). These assemblages are associated with gabbro intrusions into the basal sediments (one contact metamorphic hornfels sample contains relict nannofossils), indicating an age for the intrusion event of between 15.6 and 18.2 Ma at both Sites 1039 and 1040. Reference Site 1039, located on the Cocos plate, provides the best-preserved sequence of sediments of late Pleistocene to latest early Miocene age. The sediments cored in the prism sections at Sites 1040, 1041, 1042, and 1043 all indicate that the age of nannofossil assemblages in the prism sediments, including the toe, wedge, and apron, are all Pleistocene with a considerable amount of upper Miocene reworking. A period of low sediment accumulation rates (~5.3 m/m.y.) is recorded for Pliocene and upper Miocene sediments at Sites 1039, 1040, and 1043. Pliocene calcareous nannofossil assemblages characteristic of the ~2.5- to 3.75-m.y. time interval (nannofossil Zones NN16 and equivalent nannofossil Subzones CN12b and CN12a) were not resolved at any site. Nannofossil Zones NN15, NN14, NN13, and NN12 (early late Pliocene to early Pliocene) could not be resolved at any site either because of the absence of marker species. Within the Miocene at Sites 1039 and 1040, nannofossil Zones NN10-NN6 were difficult to differentiate because of the absence of several species that define the zonal boundaries. These intervals, where the nannofossil zones have not been resolved or are partially resolved, are primarily composed of carbonate ooze deposited during an ~8.5-m.y. (2.5-11 Ma) low sediment accumulation rate time interval. The absence of many of the marker species is attributed to warmer water conditions during those periods. Many of the same marker species are absent in the sediments recovered from nearby Deep Sea Drilling Project Site 155 in the Panama Basin.

Pore-water chemistry of ODP Sites 124-767 and 124-768

The combination of multiple sediment sources and varying rates of sediment accumulation in the Celebes and Sulu seas have had significant impact on the processes of diagenesis, mineralization, and pore-fluid flow. Isotopic and mass-balance calculations help elucidate the various reactions taking place in these western Pacific basins, where ash alteration and basalt-seawater interactions are superimposed on the effects of sulfate oxidation of organic carbon and biogenic methane and of dolomitization of biogenic carbonates. Based on the shape of the calcium and magnesium depth profiles, two major reactive zones have been identified. The first is located near the zone of sulfate depletion and is characterized by carbonate recrystallization, dolomitization and ash alteration reactions at both Ocean Drilling Program Sites 767 and 768. The second reactive zone corresponds to the bottom of the sedimentary sequence and is characterized by alteration reactions in the basement (Site 767) and in the pyroclastic deposits beneath the sediment column (Site 768).

Geochemistry of Early Cretaceous basaltic rocks from ODP Sites 123-765 and 123-766

The Early Cretaceous basaltic rocks obtained from Sites 765 and 766 in the eastern Indian Ocean floor were mostly iron-rich normal mid-ocean ridge basalts (N-MORB), which were derived from a depleted mantle source having strongly light rare earth element (LREE)-depleted rare-earth patterns and a high titanium/zirconium (Ti/Zr) ratio. Basaltic rocks in the upper part of the Site 765 basement section include megacrysts and gabbroic fragments of widely varying mineral chemistry. These megacrysts range from An90 plagioclase, including highly magnesian basaltic glass coexisting with augite of Mg# (= 100 Mg/[Fe+Mg]) at 85, to An50 plagioclase coexisting with hypersthene. This varying mineralogy of megacrysts and gabbroic fragments indicates that a considerable degree of fractional crystallization took place in the magma chamber. The unusual negative correlation between incompatible elements (e.g., TiO2) and FeO*/MgO observed among Site 765 basement basalts and fresh volcanic glasses suggest source-mantle heterogeneity in terms of FeO*/MgO. Strontium isotope ratios (87Sr/86Sr) of the basaltic rocks from both sites are between 0.7027 and 0.7033 and are comparable to those of mid-Indian Ocean ridge basalts (MIORB). The basalt pebbles encountered in the sedimentary section may have been transported from the basement highs nearer the Australian continent and include basaltic compositions ranging from primitive N-MORBs to evolved enriched (E)-MORBs. Their mantle source was not as depleted as that of the basement basalts. These rocks may be the products of earlier volcanism that took place during the rifting of the Australian continent.

Geochemical and mineralogical analyses of clay-rich intervals in ODP Sites 166-1006 and 166-1007

The western flank of the Great Bahama Bank, drilled during ODP Leg 166 at seven sites, represents a prograding carbonate sequence from late Oligocene to Holocene [Eberli et al., Proc. ODP Init. Reports 166 (1997)]. The signatures of the detrital input and of diagenetic alteration are evident in clay enriched intervals from the most distal Sites 1006 and 1007 in the Straits of Florida. Mineralogical and chemical investigations (XRD, TEM, SEM, ICP-MS) run on bulk rocks and on the clay fractions enable the origin and evolution of silicate parageneses to be characterized. Plio-Pleistocene silt and clay interbeds contain detrital clay assemblages comprising chlorite, illite, interstratified illite smectite, smectite, kaolinite and palygorskite. The greater smectite input within late Pliocene units than in Pleistocene oozes may relate either varying source areas or change in paleoclimatic conditions and weathering intensity. The clay intervals from Miocene-upper Oligocene wackestone sections are fairly different, with prevalent smectite in the fine fraction, whose high crystallinity and Mg contents that point towards an authigenic origin. The lower Miocene section, below 1104 mbsf, at depths where compaction features are well developed, is particularly characterized by abundant authigenic Na-K-clinoptilolite filling foraminifer tests. The authigenic smectite and clinoptilolite paragenesis is recorded by the chemical trends, both of the sediment and the interstitial fluid. This diagenetic evolution implies Si- and Mg rich fluids circulating in deeper and older sequences. For lack of any local volcaniclastic input, the genesis of zeolite and the terms of water rock interaction are discussed. The location of the diagenetic front correlates with that of the seismic sequence boundary P2 dated as 23.2 Ma. This correspondence may allow the chronostratigraphic significance of some specific seismic reflections to be reassessed.

Total organic carbon content, methane isotopic composition and hydrocarbon characteristics of ODP Leg 180 sites

The organic geochemistry of Sites 1108 and 1109 of the Woodlark Basin, offshore Papua New Guinea, was studied to determine whether thermally mature hydrocarbons were present in the penetrated section and, if present, whether they are genetically related to the penetrated "coaly" interval. Both the organic carbon and pyrolysis data indicate that there is no significant hydrocarbon source-rock potential at Site 1108. The hydrocarbons encountered during drilling appear to be indigenous and not migrated products or contaminants. In contrast, the coaly interval at Site 1109 contains zones with significant hydrocarbon-generation potential. Several independent lines of evidence indicate that the coaly sequence encountered at Site 1109 is thermally immature. The Site 1108 methane stable-carbon isotope composition does not display a clear trend with depth as would be expected if it was solely reflecting a maturation profile. The measured isotopic composition of methane has most probably been altered by fractionation during sample handling and storage. This fractionation would result in isotopically heavier values than would be obtained on free gas. The organic geochemical data gathered indicate that Site 1108 can be safely revisited and that the organic-rich sediments encountered at Site 1109 were not the source of the gas encountered at Site 1108.

Sedimentation rate, bulk density, accumulation rate of terrigenous material and grain sizes of ODP Leg 167 sites

The terrigenous mineral fraction of sediments recovered by drilling during Ocean Drilling Program Leg 167 at Sites 1018 and 1020 is used to evaluate changes in the source and transport of fine-grained terrigenous sediment and its relation to regional climates and the paleoceanographic evolution of the California Current system during the late Pleistocene. Preliminary time scales developed by correlation of oxygen isotope stratigraphies with the global SPECMAP record show average linear sedimentation rates in excess of 100 m/m.y., which provide an opportunity for high-resolution studies of terrigenous flux, grain size, and mineralogy. The mass flux of terrigenous minerals at Site 1018 varies from 5 to 30 g/(cm**2 x k.y.) and displays a general trend toward increased flux during glacials. The terrigenous record at Site 1020 shows a similar pattern of increased glacial input, but overall accumulation rates are significantly lower. Spectral analysis demonstrates that most of this variability is concentrated in frequency bands related to orbital cycles of eccentricity, tilt, and precession. Detailed grain-size analysis performed on the isolated terrigenous mineral fraction shows that sediments from Site 1018 are associated with higher energy transport and depositional regimes than those found at Site 1020. Grain-size data are remarkably uniform throughout the last 500 k.y., with no discernible difference observed between glacial and interglacial size distributions within each site. X-ray diffraction analysis of the <2-µm clay component suggests that the deposition of minerals found at Site 1020 is consistent with transport from a southern source during intervals of increased terrigenous input.

Stable oxygen and carbon isotopes from ODP sites on Maud Rise and Kerguelen Plateau

Paleogene stable oxygen and carbon isotopes were measured in formainifera from ODP Sites 689 and 690 at Maud Rise in the Atlantic Ocean sector of the Southern Ocean, and from Sites 738, 744, 748 and 749 at the southern Kerguelen Plateau in the Indian Ocean sector. These data were compared with sedimentological data from the same sample set. Both benthic and planktic d18O values document a cooling trend beginning around 49.5 Ma at all sites. During the late middle Eocene planktic d18O values indicate a steepening latitudinal temperature gradient from 14°C at the northern sites towards 10°C at the southernmost sites. Terrigeneous sand grains of probably ice rafted origin and clay mineral assemblages point to the existence of a limited East Antarctic ice cap with some glaciers reaching sea level as early as middle Eocene time around 45.5 Ma. Between 45 and 40 Ma, average paleotemperatures were between 5° and 7°C in deep and intermediate water masses, while near-surface water masses ranged between 6° and 10°C. During the late Eocene, between 40 and 36 Ma, average temperatures further decreased to 4°-5°C in the deep and intermediate water masses and to 5°-8°C near the sea surface. Abruptly increasing d18O values at approximately 35.9 Ma exactly correlate with a sharp pulse in the deposition of ice-rafted material on the Kerguelen Plateau, a dramatic change in clay mineral composition, and an altered Southern Ocean circulation indicated by a differentiation of benthic d13C values between sites, increasing opal concentrations and decreasing carbonate contents. For planktic and benthic foraminifera this d18O increase ranges between 1.0 and 1.3 per mil, and between 0.9 and 1.4 per mil, respectively. We favour a hypothesis that explains most of the d18O shift at 35.9 Ma with a buildup of a continental East Antarctic ice sheet. Consequently, relatively warm Oligocene Antarctic surface water temperatures probably are explained by a temperate, wet-based nature of the ice sheet. This would also aid in the fast build-up of an ice sheet by enhancing the moisture transport on to the continent.

Stable isotope ratios and geochemical composition of authigenic carbonates from ODP Sites 186-1150 and 186-1151

Several carbonaceous layers or fragments were recovered from sediments of Sites 1150 and 1151 on the deep-sea terrace of the Japan Trench during Leg 186. The X-ray diffraction analysis (XRD) data indicate that these are predominantly dolomitic. In this study, carbon and oxygen isotopes of these carbonates recovered at Sites 1150 and 1151 are presented. The oxygen isotope ratios of the dolomites analyzed range from +0.4 per mil to +4.1 per mil vs. Peedee formation belemnite (PDB) and those of calcites from +0.6 per mil to +2.8 per mil PDB. The isotopic composition of carbon varies from -7.0 per mil to +12.3 per mil PDB in dolomite and from -13.4 per mil to -24.1 per mil PDB in calcite. The wide range of carbon isotopic compositions indicates that the carbonate samples were formed by the decomposition of organic matter through reactions such as oxidation, sulfate reduction, and methane formation during diagenesis.

P-wave velocities and applied bed thickness and velocity changes for synthetic seismograms, ODP Leg 188 and Leg 119 sites

Synthetic seismograms provide a crucial link between lithologic variations within a drill hole and reflectors on seismic profiles crossing the site. In essence, they provide a ground-truth for the interpretation of seismic data. Using a combination of core and logging data, we created synthetic seismograms for Ocean Drilling Program Sites 1165 and 1166, drilled during Leg 188, and Site 742, drilled during Leg 119, all in Prydz Bay, Antarctica. Results from Site 1165 suggest that coring penetrated a target reflector initially thought to represent the onset of drift sedimentation, but the lithologic change across the boundary does not show a change from predrift to drift sediments. The origin of a shallow reflector packet in the seismic line across Site 1166 and a line connecting Sites 1166 and 742 was resolved into its constituent sources, as this reflector occurs in a region of large-scale, narrowly spaced impedance changes. Furthermore, Site 1166 was situated in a fluvio-deltaic system with widely variable geology, and bed thickness changes were estimated between the site and both seismic lines.

Abundance of planktic foraminiferal species in sediments at DSDP Sites 10-95, 77-536, and 77-540

Over most of the Gulf of Mexico and Caribbean a hiatus is present between the lower upper Maastrichtian and lowermost Tertiary deposits; sedimentation resumed ~200 ka (upper zone Pla) after the K-T boundary. Current-bedded volcaniclastic sedimentary rocks at Deep Sea Drilling Project (DSDP) Sites 536 and 540, which were previously interpreted as impact-generated megawave deposits of K-T boundary age, are biostratigraphically of pre-K-T boundary age and probably represent turbidite or gravity-How deposits. The top 10 to 20 cm of this deposit at Site 536 contains very rare Micula prinsii, the uppermost Maastrichtian index taxon, as well as low values of Ir (0.6 pbb) and rare Ni-rich spinels. These indicate possible reworking of sediments of K-T boundary age at the hiatus. Absence of continuous sediment accumulation across the K-T boundary in the 16 Gulf of Mexico and Caribbean sections examined prevents their providing evidence of impact-generated megawave deposits in this region. Our study indicates that the most complete trans-K-T stratigraphic records may be found in onshore marine sections of Mexico, Cuba, and Haiti. The stratigraphic records of these areas should be investigated further for evidence of impact deposits.

Geochemistry of sands and sandstones in ODP Leg 126 sites

During Ocean Drilling Program Leg 126, six sites were cored in a young backarc rift basin and its flanks (rift onset 1.1-3.56 Ma) and in the forearc basin of the Izu-Bonin Arc. In the backarc area, strata are younger than about 4.5 Ma, whereas in the forearc, ages are about 0-31 Ma in sections punctuated by important Miocene unconformities. Bulk chemical analyses of volcaniclastic turbidite sands and sandstones, derived directly from the arc, were obtained from 271 atomic absorption analyses (major elements), 253 XRF analyses (trace elements) and 16 ICP-MS analyses (trace and rare-earth elements). Of the 271 samples, 78 come from the backarc area and the remainder from the forearc. The sands and sandstones reflect the igneous compositions of their sources. Most are formed of materials derived from subalkaline, low-K andesites, and dacites, although compositions range from basalt to rhyolite. Basic and acid andesites are predominant in Oligocene rocks; in contrast, Pliocene-Pleistocene sediments were derived from acid andesitic to rhyolitic sources. The oldest sandstones, estimated to have an age of about 31 Ma, were derived from an arc tholeiitic, not boninitic, source. The 26-31 Ma sandstones furthest to the north, at Sites 787 and 792, have higher relative concentrations of Ti, Zr, and Y than do those at southern Site 793. Data from younger samples indicate that, for more than 30 m.y., the average composition of volcaniclastic sediments and volcanism near Aoga Shima was more basic than to the south, near Sumisu Jima. Using the sandstones as igneous proxies, we conclude that magmas erupted along the arc have become more depleted in light-rare-earth elements (LREE) with time. There was a major change in rare-earth-element (REE) concentrations in the late Oligocene, from essentially flat patterns (normalized La/Yb about 1-1.5) to LREE-depleted patterns (normalized La/Yb about 0.5). At the same time, Zr/Y ratios decreased from about 2-4 to about 1.5-2.5. These changes may reflect a shift in provenance, or changes in the composition of the mantle wedge beneath the arc. In the backarc area, lithic clasts and glass shards of rift-facies basalt are present in sediments as old as 2.35-3.15 Ma. Two samples of mafic sand from the backarc basin have flat REE patterns (normalized La/Yb about 1.0), like some of the <1-Ma rift lavas and unlike pre-rift sand and sandstone samples. These possibly represent the local effects of sedimentary mixing of detritus from arc and backarc eruptions because no evidence from the arc itself exists to suggest a recent change in the REE content of magmas.