Zeolite and silica diagenesis and sandstone petrography at DSDP Sites 57-438 and 57-439

We detected authigenic clinoptilolites in two core samples of tuffaceous, siliceous mudstone in the lower Miocene section of Hole 439. They occur as prismatic and tabular crystals as long as 0.03 mm in various voids of dissolved glass shards, radiolarian shells, calcareous foraminifers, and calcareous algae. They are high in alkalies, especially Na, and in silica varieties. There is a slight difference in composition among them. The Si : (Al+ Fe3+) ratio is highest (4.65) in radiolarian voids, intermediate (4.34) in dissolved glass voids, and lowest (4.26) in voids of calcareous organisms. This difference corresponds to the association of authigenic silica minerals revealed by the scanning electron microscope: There are abundant opal-CT lepispheres in radiolarian voids, low cristobalite and some lepispheres in dissolved glass voids, and a lack of silica minerals in the voids of calcareous organisms. Although it contains some silica from biogenic opal and alkalies from trapped sea water, clinoptilolite derives principally from dissolved glass. Although they are scattered in core samples of Quaternary through lower Miocene diatomaceous and siliceous deposits, acidic glass fragments react with interstitial water to form clinoptilolite only at a sub-bottom depth of 935 meters at approximately 25°C. Analcimes occur in sand-sized clasts of altered acidic vitric tuff in the uppermost Oligocene sandstones. The analcimic tuff clasts were probably reworked from the Upper Cretaceous terrain adjacent to Site 439. Low cristobalite and opal-CT are found in tuffaceous, siliceous mudstone of the middle and lower Miocene sections at Sites 438 and 439. Low cristobalite derives from acidic volcanic glass and opal-CT from biogenic silica. Both siliceous organic remains and acidic glass fragments occur in sediments from the Quaternary through lower Miocene sections. However, the shallowest occurrence is at 700 meters subbottom in Hole 438A, where temperature is estimated to be 21°C. The d(101) spacing of opal-CT varies from 4.09 to 4.11 Å and that of low cristobalite from 4.04 to 4.06 Å. Some opal-CT lepispheres are precipitated onto clinoptilolites in the voids of radiolarian shells at a sub-bottom depth of 950 meters in Hole 439. Sandstone interlaminated with Upper Cretaceous shale is chlorite- calcite cemented and feldspathic. Sandstones in the uppermost Oligocene section are lithic graywacke and consist of large amounts of lithic clasts grouped into older sedimentary and weakly metamorphosed rocks, younger sedimentary rocks, and acidic volcanic rocks. The acidic volcanic clasts probably originated from the volcanic high, which supplied the basal conglomerate with dacite gravels. The older sedimentary and weakly metamorphosed rocks and green rock correspond to the lithologies of the lower Mesozoic to upper Paleozoic Sorachi Group, including the chert, limestone, and slate in south-central Hokkaido. However, the angular shape and coarseness of the clasts and the abundance of carbonate rock fragments indicate a nearby provenance, which is probably the southern offshore extension of the Sorachi Group. The younger sedimentary rocks, including mudstone, carbonaceous shale, and analcime-bearing tuff, correspond to the lithologies of the Upper Cretaceous strata in south-central Hokkaido. Their clasts were reworked from the southern offshore extension of the strata. Because of the discontinuity of the zeolite zoning due to burial diagenesis, an overburden several kilometers thick must have been denuded before the deposition of sediments in the early Oligocene.

Calcareous nannofossil biostratigraphy of ODP Leg 134 sites

Seven sites drilled in the central New Hebrides Island Arc during Ocean Drilling Program Leg 134 yielded varying quantities of upper Eocene through Pleistocene calcareous nannofossils. Most of the Miocene and Pliocene strata were absent from Sites 827-831 drilled along the collisional boundary between the Australia and Pacific plates where the North d'Entrecasteaux Ridge and Bougainville Guyot are being subducted. Sites 832 and 833, drilled in the intra-arc North Aoba Basin, contained upper Miocene through Pleistocene and early Pliocene through Pleistocene nannofossils, respectively. Detailed range charts displaying species abundances and age interpretations are presented for all of the sites. Despite problems of reworked assemblages, poor preservation, overgrowths and/or dilution from volcaniclastics, the nannofossil biostratigraphy delineates several repeated sections at Site 829 in the accretionary prism adjacent to Espiritu Santo Island. Paleogene pelagic sediments equivalent to those in a reference section at Site 828 appear to have been scraped from the downgoing North d'Entrecasteaux Ridge and accreted onto the forearc during the Pleistocene. Other sediments in the forearc include Pleistocene olistostromal trench-fill deposits containing clasts of various ages and compositions. Some of the clasts and olistoliths have affinities to rocks exposed on the neighboring islands and environs, whereas others are of uncertain origin. The matrix of the olistostromes is predominately Pleistocene, however, matrices of mixed nannofossil ages are frequently encountered. Comparisons of the mixed nannofossil ages in the matrices with sedimentological and structural data suggest that sediment mixing resulting from fault movement is subordinate to that occurring during deposition.

Chemical and germanium isotopic compositions of sediments and sedimentary rocks from ODP Sites 129-801 and 185-1149

A new technique for the precise and accurate determination of Ge stable isotope compositions has been developed and applied to silicate rocks and biogenic opal. The analyses were performed using a continuous flow hydride generation system coupled to a MC-ICP-MS. Samples have been purified through anion- and cation-exchange resins to separate Ge from matrix elements and eliminate potential isobaric interferences. Variations of 74Ge/70Ge ratios are expressed as d74Ge values relative to our internal standard and the long-term external reproducibility of the data is better than 0.2? for sample size as low as 15 ng of Ge. Data are presented for igneous and sedimentary rocks, and the overall variation is 2.4? in d74Ge, representing 12 times the uncertainty of the measurements and demonstrating that the terrestrial isotopic composition of Ge is not unique. Co-variations of 74Ge/70Ge, 73Ge/70Ge and 72Ge/70Ge ratios follow a mass-dependent behaviour and imply natural isotopic fractionation of Ge by physicochemical processes. The range of d74Ge in igneous rocks is only 0.25? without systematic differences among continental crust, oceanic crust or mantle material. On this basis, a Bulk Silicate Earth reservoir with a d74Ge of 1.3+/-0.2? can be defined. In contrast, modern biogenic opal such as marine sponges and authigenic glauconite displayed higher d74Ge values between 2.0? and 3.0?. This suggests that biogenic opal may be significantly enriched in light isotopes with respect to seawater and places a lower bound on the d74Ge of the seawater to +3.0?.This suggests that seawater is isotopically heavy relative to Bulk Silicate Earth and that biogenic opal may be significantly fractionated with respect to seawater. Deep-sea sediments are within the range of the Bulk Silicate Earth while Mesozoic deep-sea cherts (opal and quartz) have d74Ge values ranging from 0.7? to 2.0?. The variable values of the cherts cannot be explained by binary mixing between a biogenic component and a detrital component and are suggestive of enrichment in the light isotope of diagenetic quartz. Further work is now required to determine Ge isotope fractionation by siliceous organisms and to investigate the effect of diagenetic processes during chert lithification.

Mineralogy and petrographic summary of ODP Leg 198 sites and DSDP Hole 62-463, Shatsky Rise

This petrological study of the lower Aptian Oceanic Anoxic Event (OAE1a) focused on the nature of the organic-rich interval as well as the tuffaceous units above and below it. The volcaniclastic debris deposited just prior to the OAE1a is consistent with reactivation of volcanic centers across the Shatsky Rise, concurrent with volcanism on the Ontong Java Plateau. This reactivation may have been responsible for the sub-OAE1a unconformity. Soon after this volcanic pulse, anomalous amounts of organic matter accumulated on the rise, forming a black shale horizon. The complex textures in the organic-rich intervals suggest a history of periodic anoxia, overprinted by bioturbation. Components include pellets, radiolarians, and fish debris. The presence of carbonate-cemented radiolarite under the OAE1a intervals suggests that there has been large-scale remobilization of carbonate in the system, which in turn may explain the absence of calcareous microfossils in the section. The volcanic debris in the overlying tuffaceous interval differs in that it is significantly epiclastic and glauconitic. It was likely derived from an emergent volcanic edifice.

Carbon/oxygen ratios, clay composition and gas-hydrate saturation of ODP Leg 164 sites

The analyses of downhole log data from Ocean Drilling Program (ODP) boreholes on the Blake Ridge at Sites 994, 995, and 997 indicate that the Schlumberger geochemical logging tool (GLT) may yield useful gas hydrate reservoir data. In neutron spectroscopy downhole logging, each element has a characteristic gamma ray that is emitted from a given neutron-element interaction. Specific elements can be identified by their characteristic gamma-ray signature, with the intensity of emission related to the atomic elemental concentration. By combining elemental yields from neutron spectroscopy logs, reservoir parameters including porosities, lithologies, formation fluid salinities, and hydrocarbon saturations (including gas hydrate) can be calculated. Carbon and oxygen elemental data from the GLT was used to determine gas hydrate saturations at all three sites (Sites 994, 995, and 997) drilled on the Blake Ridge during Leg 164. Detailed analyses of the carbon and oxygen content of various sediments and formation fluids were used to construct specialized carbon/oxygen ratio (COR) fan charts for a series of hypothetical gas hydrate accumulations. For more complex geologic systems, a modified version of the standard three-component COR hydrocarbon saturation equation was developed and used to calculate gas hydrate saturations on the Blake Ridge. The COR-calculated gas hydrate saturations (ranging from about 2% to 14% bulk volume gas hydrate) from the Blake Ridge compare favorably to the gas hydrate saturations derived from electrical resistivity log measurements.

Physical properties of ODP Sites 123-765 and 123-766

During Ocean Drilling Program Leg 123, two sites were drilled in the deep Indian Ocean. Physical properties were measured in soft Quaternary and Lower Cretaceous sediments to relatively fresh, glass-bearing pillow lavas and massive basalts. Porosities ranged from 89% near the seafloor to 1.6% for the dense basalts. This self-consistent set of measurements permitted some descriptive models of physical properties to be more rigorously tested than before. Predictive relationships between porosity and compressional-wave velocity have generally been based upon the Wyllie time average equation. However, this equation does not adequately describe the actual relationship between these two parameters, and many have attempted to improve it. In most cases, models were derived by testing them against a set of data representing a relatively narrow range of porosity values. Similarly, the use of the Wyllie equation has often been justified by a pseudolinear fit to the data over a narrow range of porosity values. The limitations of the Wyllie relationship have been re-emphasized here. A semi-empirical acoustic impedance equation is developed that provides a more accurate porosity-velocity transform, using realistic material parameters, than has hitherto been possible. A closer correlation can be achieved with this semi-empirical relationship than with more theoretically based equations. In addition, a satisfactory empirical equation can be used to describe the relationship between thermal conductivity and porosity. If enough is known about core sample lithologies to provide estimates of the matrix and pore water parameters, then these predictive equations enable one to describe completely the behavior of a saturated rock core in terms of compressional-wave velocity, thermal conductivity, porosity, and bulk density.

Shell size variation of Neogloboquadrina pachyderma sin. in the Norwegian-Greenland Sea during the last 1.3 Myr

We present measurements of the maximum diameter of the planktonic foraminifer Neogloboquadrina pachyderma sin. from six sediment cores (Ocean Drilling Program sites 643, 644, 907, 909, 985 and 987) from the Norwegian-Greenland Sea. Our data show a distinct net increase in mean shell size of N. pachyderma sin. at all sites during the last 1.3 Ma, with largest shell sizes reached after 0.4 Ma. External factors such as glacial-interglacial variability and carbonate dissolution alone cannot account for the observed variation in mean shell size of N. pachyderma sin. We consider the observed shell size increase to mirror an evolutionary trend towards better adaptation of N. pachyderma sin. to the cold water environment after 1.1-1.0 Ma. Probably, the Mid Pleistocene climate shift and the associated change of amplitude and frequency of glacial-interglacial fluctuations have triggered the evolution of this planktonic foraminifer. Oxygen and carbon stable isotope analyses of different shell size classes indicate that the observed shell size increase could not be explained by the functional concept that larger shells promote increasing sinking velocities during gametogenesis. For paleoceanographic reconstructions, the evolutionary adaptation of Neogloboquadrina pachyderma sin. to the cold water habitat has significant implications. Carbonate sedimentation in highest latitudes is highly dependent on the presence of this species. In the Norwegian-Greenland Sea, carbonate-poor intervals before 1.1 Ma are, therefore, not necessarily related to severe glacial conditions. They are probably attributed to the absence of this not yet polar-adapted species. Further, transfer function and modern analog techniques used for the reconstruction of surface water conditions in high latitudes could, therefore, contain a large range of errors if they were applied to samples older than 1.1-1.0 Myrs.

Grain counts and XRD mineralogy of turbidite sand and hemipelagic mud from ODP Leg 168 sites

Sequences of late Pliocene to Holocene sediment lap onto juvenile igneous crust within 20 km of the Juan de Fuca Ridge in northwestern Cascadia Basin, Pacific Ocean. The detrital modes of turbidite sands do not vary significantly within or among sites drilled during Leg 168 of the Ocean Drilling Program. Average values of total quartz, total feldspar, and unstable lithic fragments are Q = 35, F = 35, and L = 30. Average values of monocrystalline quartz, plagioclase, and K-feldspar are Qm = 46, P = 49, and K = 5, and the average detrital modes of polycrystalline quartz, volcanic-rock fragments, and sedimentary-rock plus metamorphic-rock fragments are Qp = 16, Lv = 43, and Lsm = 41. Likely source areas include the Olympic Peninsula and Vancouver Island; sediment transport was focused primarily through the Strait of Juan de Fuca, Juan de Fuca Channel, Vancouver Valley, and Nitinat Valley. Relative abundance of clay minerals (<2-µm-size fraction) fluctuate erratically with depth, stratigraphic age, and sediment type (mud vs. turbidite matrix). Mineral abundance in mud samples are 0%-35% smectite (mean = 8%), 18%-59% illite (mean = 40%), and 29%-78% chlorite + kaolinite (mean = 52%). We attribute the relatively low content of smectite to rapid mechanical weathering of polymictic source terrains, with little or no input of volcanic detritus from the Columbia River. The scatter in clay mineralogy probably was caused by converging of surface currents, turbidity currents, and near-bottom nepheloid clouds from several directions, as well as subtle changes in glacial vs. interglacial weathering products.

Distribution of foraminifera and other components in ODP Leg 188 sites

During Leg 188 of the Ocean Drilling Program (ODP), employing JOIDES Resolution, we drilled holes at three sites in the southern Indian Ocean in and near Prydz Bay, East Antarctica, between 28 January and 29 February 2000. The objectives of the voyage were to: - Core through sediments deposited when Antarctica underwent the transition from "greenhouse" to the modern "icehouse" state late in the Eocene or early in the Oligocene, at sites obtaining their sediment from the currently subglacial Gamburtsev Mountains that probably were the site of nucleation of the ice sheet (principally Site 1166); - Obtain a sediment record from times at which major changes in the ice sheet volume and characteristics took place as judged from oxygen isotope records, especially at ~23.7 Ma (Oligocene/Miocene boundary), 12-16 Ma (middle Miocene), and 2.7 Ma (late Pliocene) (mainly Site 1165); and - Sample through the upper Pliocene and Quaternary in an attempt to document fluctuations in the extent of the ice sheet over the continental shelf during the Quaternary (especially Site 1167). Paleogene foraminifer-bearing marine sections were not intersected, and thus discussion of marine sections is restricted to the Neogene. Foraminifers are not major contributors to Leg 188 chronostratigraphy but contribute to paleoenvironmental interpretation, to issues such as carbonate compensation depth (CCD) effects and source and history of sediment, and provide a basis for Sr and d18O studies. Chronostratigraphy for the various sections was compiled from diatoms, radiolarians, and paleomagnetism (Shipboard Scientific Party, 2001, doi:10.2973/odp.proc.ir.188.101.2001). Foraminifers were sporadic rather than continuous except in short intervals; however, the Neogene foraminifers from the region are very poorly known and the new records proved to be of significant value in paleoenvironmental interpretation. Only at Site 1167 did drilling intersect a section that yielded foraminifers virtually throughout. Other than for the very young section at each site, there is virtually no continuity of assemblages between sites and thus each section is treated here as separate and unrelated.

Gas hydrate structures and C1-C5 hydrocarbons at individual sites in the Gulf of Mexico

Gas hydrate samples from various locations in the Gulf of Mexico (GOM) differ considerably in their microstructure. Distinct microstructure characteristics coincide with discrete crystallographic structures, gas compositions and calculated thermodynamic stabilities. The crystallographic structures were established by X-ray diffraction, using both conventional X-ray sources and high-energy synchrotron radiation. The microstructures were examined by cryo-stage Field-Emission Scanning Electron Microscopy (FE-SEM). Good sample preservation was warranted by the low ice fractions shown from quantitative phase analyses. Gas hydrate structure II samples from the Green Canyon in the northern GOM had methane concentrations of 70-80% and up to 30% of C2-C5 of measured hydrocarbons. Hydrocarbons in the crystallographic structure I hydrate from the Chapopote asphalt volcano in the southern GOM was comprised of more than 98% methane. Fairly different microstructures were identified for those different hydrates: Pores measuring 200-400 nm in diameter were present in structure I gas hydrate samples; no such pores but dense crystal surfaces instead were discovered in structure II gas hydrate. The stability of the hydrate samples is discussed regarding gas composition, crystallographic structure and microstructure. Electron microscopic observations showed evidence of gas hydrate and liquid oil co-occurrence on a micrometer scale. That demonstrates that oil has direct contact to gas hydrates when it diffuses through a hydrate matrix.

Physical properties, grain size distribution and clay mineralogy of ODP Leg 117 sites

The fabric of sediments recovered at sites drilled on the Indus Fan, Owen Ridge, and Oman margin during Ocean Drilling Program Leg 117 was examined by scanning electron microscopy to document changes that accompany sediment burial. Two sediment types were studied: (1) biogenic sediments consisting of a variety of marly nannofossil and nannofossil oozes and chalks and (2) terrigenous sediments consisting of fine-grained turbidites deposited in association with the Indus Fan. Biogenic sediments were examined with samples from the seafloor to depths of 306 m below seafloor (mbsf) on the Owen Ridge (Site 722) and 368 mbsf on the Oman margin (Sites 723 and 728). Over these depth ranges the biogenic sediments are characterized by a random arrangement of microfossils and display little chemical diagenetic alteration. The microfossils are dispersed within a fine-grained matrix that is predominantly microcrystalline carbonate particles on the Owen Ridge and clay and organic matter on the Oman margin. Sediments with abundant siliceous microfossils display distinct, open fabrics with high porosity. Porosity reduction resulting from gravitational compaction appears to be the primary process affecting fabric change in the biogenic sediment sections. Fabric of illite-rich clayey silts and silty claystones from the Indus Fan (Site 720) and Owen Ridge (Sites 722 and 731) was examined for a composite section extending from 45 to 985 mbsf. In this section fabric of the fine-grained turbidites changes from one with small flocculated clay domains, random particle arrangement, and high porosity to a fabric with larger domains, strong preferred particle orientation roughly parallel to bedding, and lower porosity. These changes are accomplished by a growth in domain size, primarily through increasing face-to-face contacts, and by particle reorientation which is characterized by a sharp increase in alignment with bedding between 200 and 400 mbsf. Despite extensive particle reorientation, flocculated clay fabric persists in the deepest samples examined, particularly adjacent to silt grains, and the sediments lack fissility. Fabric changes over the 45-985 mbsf interval occur in response to gravitational compaction. Porosity reduction and development of preferred particle orientation in the Indus Fan and Owen Ridge sections occur at greater depths than outlined in previous fabric models for terrigenous sediments as a consequence of a greater abundance of silt and a greater abundance of illite and chlorite clays.

Geochemical data derived from an absolutely dated shell-based chronology for the Irish Sea

The identification in various proxy records of periods of rapid (decadal scale) climate change over recent millennia, together with the possibility that feedback mechanisms may amplify climate system responses to increasing atmospheric CO2, highlights the importance of a detailed understanding, at high spatial and temporal resolutions, of forcings and feedbacks within the system. Such an understanding has hitherto been limited because the temperate marine environment has lacked an absolute timescale of the kind provided by tree-rings for the terrestrial environment and by corals for the tropical marine environment. Here we present the first annually resolved, multi-centennial (489-year), absolutely dated, shell-based marine master chronology. The chronology has been constructed by detrending and averaging annual growth increment widths in the shells of multiple specimens of the very long-lived bivalve mollusc Arctica islandica, collected from sites to the south and west of the Isle of Man in the Irish Sea. The strength of the common environmental signal expressed in the chronology is fully comparable with equivalent statistics for tree-ring chronologies. Analysis of the 14C signal in the shells shows no trend in the marine radiocarbon reservoir correction (DR), although it may be more variable before ~1750. The d13C signal shows a very significant (R**2 = 0.456, p < 0.0001) trend due to the 13C Suess effect.