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.

Mineralogy and stable isotopic composition of carbonates and sulfide minerals from ODP Leg 164 sites

During Ocean Drilling Program Leg 164, gas hydrates were recovered in the Blake Ridge where the top of the gas hydrate zone lies at about 200 meters below seafloor (mbsf) and the bottom-simulating reflector (BSR) is located at about 450 mbsf. There is no sedimentological discontinuity crossing the BSR. The BSR is disrupted by the salt piercement of the Cape Fear Diapir. The authigenic carbonates (dolomite and siderite) are always present in small amounts (a few weight percent) in the sediments; they are also concentrated in millimeter- to centimeter-sized nodules and layers composed of dolomite above the top of the gas hydrate reservoir, and of siderite below the BSR. In the Blake Ridge, the dolomite/siderite boundary is located near 140 mbsf. The distribution with depth of the d18O values of dolomite and siderite shows a sharp decrease from high values (maximum 7.5 per mil) in the topmost 50 m, to very low values (minimum -2.7 per mil) at 140 mbsf, and at greater depth increase to positive values within the range of 1.8 per mil to 5.0 per mil. The d13C distribution is marked by the rapid increase with greater depth from low values (-31.3 per mil to -11.4 per mil) near 50 mbsf to positive values at 110 mbsf, which remain in the range of 1.7 to 5.4 down to 700 mbsf. Diagenetic carbonates were precipitated in pore waters in which d18O and d13C values were highly modified by strong fractionation effects, both in the water and in the CO2-CH4 systems associated with the formation and dissociation of gas hydrates.

Spectral reflectance of ODP Leg 178 holes

The routine use of spectrophotometry on the sediment surfaces of archive halves of each section during the onboard sedimentological core description process is a great stride toward development of real-time noninvasive characterization of deep-sea sediments. Spectral reflectance data have been used so far for mineral composition studies as well as for lithostratigraphic correlation between sites (Balsam and Deaton, 1991; Balsam et al., 1997; Mix et al., 1995; Ortiz et al., 1999). Their results demonstrate that spectrophotometry can estimate CaCO3 content by using the 4.65-, 5.25-, and 5.55-µm wavelength spectrums. A detailed overview of various other noninvasive methods is given in Ortiz and Rack (1999). The purpose of this study is to test whether spectrophotometry in the visible band can be used as a tool to gather further information about grain-size variation, sorting, compaction, and porosity, which are directly linked to the sedimentation process. From remote sensing data analyses, it is known that diffuse spectral reflectance data in the visible band in the wavelength window of 7.0-6.5 µm are sensitive to grain-size variations. It appears that a relationship between grain size and signal absorption exists only in this wavelength window. (e.g., Clark, 1999; Gaffey, 1986; Gaffey et al., 1993). Variations in grain size during a sedimentation process are linked to depositional energy, which affects sorting, compaction, and porosity of sediment deposits. As an example, we study here the spectrophotometric data of the sedimentary sequence of Hole 1098C, which was deposited under widely varying environmental conditions. Alternating turbidite and finely laminated sediments were recovered from Hole 1098C. The turbidites are related to a high depositional energy environment; the finely laminated sediments are related to a low depositional energy environment. Data from Hole 1098C were therefore used to test whether the spectral reflectance data can provide a proxy for these different depositional environments.

Silicoflagellates of ODP Leg 119 samples

The occurrence of Quaternary and Oligocene silicoflagellates at two Ocean Drilling Program (ODP) Leg 119 Holes (736A and 744A) on the Kerguelen Plateau in the Southern Ocean was investigated to compare species distributions to Northern Hemisphere floras. This abstract gives the data determined (Tables 1 and 2) for 24 samples and few preliminary remarks. Quaternary assemblages of Hole 736A are noteworthy for the absences of key North Pacific zonal guide species such as Bachmannocena quadrangula, Dictyocha aculeata, Dictyocha subarctios, and Distephanus octangulatus (Bukry and Monechi, 1985). Other species such as Distephanus floridus, Distephanus speculum elongatus, and Mesocena octagona show limited ranges in Hole 736A and may help to subdivide the Quaternary locally. The late Oligocene assemblages of Hole 744A contain widely distributed species of Distephanus and Naviculopsis, which permit correlation to lower latitude assemblages. They also contain the high-latitude acme of Distephanus raupii which was first noted at Deep Sea Drilling Project (DSDP) Hole 278 (56°3.42'S, 160°04.29'E, water depth 3689 m) by Perch-Nielsen (1975) and Bukry (1975). Study of Hole 744A assemblages suggests that D. raupii developed from pentagonal Dictyocha deflandrei deflandrei. A final note on the Hole 744A assemblages is the brief late Oligocene acme (25%) of Dictyocha sp. aff. D. spinosa in Sample 119-744A-13H-4, 65-67 cm, which provides a direct correlation to the acme (16%) in DSDP Sample 29-278-31R-CC (Perch-Nielsen, 1975) in the Southern Ocean. Most of the taxonomy used in the tables is documented in earlier publications of the DSDP Initial Reports (see Bukry in Volumes 16, 35, 37, 40, 44, 49, 54, 67, 68, 69, 81, and 95). Also, see Loeblich et al. (1968) and Perch-Nielsen (1985) for extensive taxonomy and illustrations.

(Table T1) Mineralogy of ODP Leg 199 and DSDP Hole 16-162 sediments - comparison of methods

During Ocean Drilling Program Leg 199 in the equatorial Pacific, visible and near-infrared spectroscopy (VNIS) was used to measure the reflectance spectra (350-2500 nm) of 1343 sediment samples. Reflectance spectra were also measured for a suite of 60 samples of known mineralogy, thereby providing a local ground-truth calibration of spectral features to percentages of calcite, opal, smectite, and illite. The associated algorithm was used to calculate mineral percentages from the 1343 spectra. Using multiple regression and VNIS mineralogy, multisensor track physical properties and light spectroscopy data were then converted into continuous high-resolution mineralogy logs.

Geochemistry of serpentine muds of ODP Leg 125 holes

The <63-µm fractions of serpentinite muds from two seamounts on the Mariana and Izu-Bonin forearcs were analyzed for mineral composition by X-ray diffraction and for chemical composition by X-ray fluorescence. The silt fraction of the muds consists predominantly of chrysotile, brucite, and ample amorphous constituents. Chlorite and smectite are less abundant components. Of special interest is the occurrence of iowaite, a brucite-like, Cl-bearing mineral with a layered structure. Iowaite was not found in the samples from the summit site of one of the seamounts drilled; however, it is scattered throughout the strata, composing the flanks of both seamounts investigated. No systematic change of the iowaite abundance with depth was observed. The distribution of iowaite is confined to the surface of the flanks of the seamount. Based on the distribution on the mineral and its chemical composition, we suggest that the iowaite formed by oxidation of some of the ferrous iron in brucite contained in the serpentine mud as it contacted abyssal seawater during protrusion onto the seafloor. The resulting positive charge imparted to the brucite was compensated by the uptake of seawater chloride. Consequently, the formation of iowaite is restricted to the seafloor where oxygen and chloride are available for these reactions. The availability of oxygen is considered the limiting factor. We conclude that iowaite formation cannot be a major cause for the low chlorinity of pore fluids inside the seamounts.

Tie points and log-adjusted depth scales for ODP Leg 207 Sites

Multiple copies of Cretaceous black shales extending from the early Cenomanian to the end of the Santonian were recovered at five sites on Demerara Rise during Leg 207 of the Ocean Drilling Program. These sediments are primarily composed of laminated organic-rich claystones interbedded with coarser, lightly laminated foraminferal-bearing packstones and wackestones. The black shales represent the local expression of widespread organic-rich sedimentation in the Atlantic during the mid-Cretaceous. However, incomplete recovery prevented construction of continuous composite sections, resulting in uncertainties concerning the correct stratigraphic placement of individual cores. By combining high-resolution measurements of bulk density collected shipboard on the multisensor track with continuous downhole measurements of formation resistivity using the Formation MicroScanner, an equivalent logging depth scale was constructed for black shales recovered from Sites 1258, 1260, and 1261. The integrated depths approach centimeter-scale resolution and are supported by comparisons of coarser resolution natural gamma ray emissions collected on cores and through downhole logging operations. The new depths highlight the extent of both intra- and intercore gaps and provide an opportunity to further constrain temporal and spatial paleoceanographic changes captured in proxy records from these sediments.

Organic carbon chemistry of late Tertiary to Quaternary sediments ODP Leg 107

We analyzed samples from ODP Holes 652A and 654A (Leg 107, Tyrrhenian Sea) for the amount, type, and thermal maturity of organic matter. The sediments encompass clastic and biogenic lithologies, which were deposited on the passive margin east of Sardinia since the late Miocene to the Pleistocene. Marine, hypersaline/evaporitic, lacustrine/riverine, and finally hemipelagic marine conditions with occasional anoxic(?) interludes gave rise to very diverse sedimentary facies. The majority of samples is lean in organic matter (<0.2% TOC). Notable exceptions are Tortonian sediments (TOC average 0.3%), Messinian oil shales from Core 107-652A-64R (up to 11% TOC), Messinian lacustrine/fluvial sediments from Hole 652A (TOC average 0.42%,), and Pleistocene sapropel samples (>2% TOC). The Messinian oil shale in Hole 652A appears to be the only mature hydrocarbon source rock. In general, Pliocene sediments are the leanest and least mature samples. Pleistocene and Pliocene samples derive organic matter from a marine source. In spite of obvious facies differences in the Messinian between the two sites, pyrolysis results are not conclusive in separating hypersaline facies of Site 654 from the fresh water facies of Site 652, because both appear to have received terrestrial organic tissue as the main component of TOC. It is apparent from the distribution of maximum pyrolysis temperatures that heat flow must have been considerably higher at Site 652 on the lower margin in the Messinian. Molecular maturity indices in lipid extracts substantiate the finding that the organic matter in Tortonian and Messinian samples from Hole 654A is immature, while thermal maturation is more advanced in coeval samples from Hole 652A. Analyses of lipid biomarkers showed that original odd-even predominance was preserved in alkanes and alkylcyclohexanes from Messinian samples in Hole 654A, while thermal maturation had removed any odd-even predominance in Hole 652A. Isomerization data of hopanes and steranes support these differences in thermal history for the two sites. Hopanoid distribution further suggests that petroleum impregnation from a deeper, more mature source resulted in the co-occurrence of immature and mature groups of pentacyclic biomarkers. Even though the presence of 4-methylsteranes may imply that dinoflagellates were a major source for organic matter in the oil shale interval of Hole 652, we did not find intact dinoflagellates or related nonskeletal algae during microscopic investigation of the organic matter in the fine laminations. Morphologically, the laminations resemble bacterial mats.

Geochemical and palynological measurements from the ODP Leg 189 at Site 1172 on the East Tasman Plateau

A brief (~150 kyr) period of widespread global average surface warming marks the transition between the Paleocene and Eocene epochs, ~56 million years ago. This so-called "Paleocene-Eocene thermal maximum" (PETM) is associated with the massive injection of 13C-depleted carbon, reflected in a negative carbon isotope excursion (CIE). Biotic responses include a global abundance peak (acme) of the subtropical dinoflagellate Apectodinium. Here we identify the PETM in a marine sedimentary sequence deposited on the East Tasman Plateau at Ocean Drilling Program (ODP) Site 1172 and show, based on the organic paleothermometer TEX86, that southwest Pacific sea surface temperatures increased from ~26 °C to ~33°C during the PETM. Such temperatures before, during and after the PETM are >10 °C warmer than predicted by paleoclimate model simulations for this latitude. In part, this discrepancy may be explained by potential seasonal biases in the TEX86 proxy in polar oceans. Additionally, the data suggest that not only Arctic, but also Antarctic temperatures may be underestimated in simulations of ancient greenhouse climates by current generation fully coupled climate models. An early influx of abundant Apectodinium confirms that environmental change preceded the CIE on a global scale. Organic dinoflagellate cyst assemblages suggest a local decrease in the amount of river run off reaching the core site during the PETM, possibly in concert with eustatic rise. Moreover, the assemblages suggest changes in seasonality of the regional hydrological system and storm activity. Finally, significant variation in dinoflagellate cyst assemblages during the PETM indicates that southwest Pacific climates varied significantly over time scales of 103 - 104 years during this event, a finding comparable to similar studies of PETM successions from the New Jersey Shelf.

Grain size composition of sediments from ODP Leg 164 sites

This research was designed to check the assumption of the grain-size control on a gas hydrate presence in the Blake Ridge sediments; the assumption had originated from the data gained at Deep Sea Drilling Project (DSDP) Site 533. Granulometric analysis (the combined pipette-sieve method) of the 345 sediment samples obtained after pore-water squeezing from Ocean Drilling Program (ODP) Sites 994, 995, and 997 has provided support for this assumption. The zone of negative anomalies of pore-water chlorinity, which is generally recognized to be gas hydrate bearing, is confined, as a whole, to the interval of comparatively coarse-grained sediments in each of the three site columns because content of the fine fractions <0.05, <0.01, <0.005, and <0.001 mm is lower there (although the character of this control changes from site to site). The individual chlorinity anomalies also coincide, for the most part, with relatively coarse-grained sediments.

Mineral composition, major element oxides and trace element concentration of sediments from ODP Leg 180 sites

Middle Miocene to Holocene fine-grained argillaceous sediments (clays, claystones/muds, and mudstones), which volumetrically dominated the sediment recovery in the Woodlark Basin during Leg 180, were chemically analyzed for major elements, trace elements, and some rare earth elements by X-ray fluorescence. Selected samples also underwent X-ray diffraction (XRD) analysis for mineral determination. The results shed light on sediment provenance when combined with shipboard sediment descriptions, smear slide study, and XRD. The oldest sediments recovered (Site 1108) of middle-late Miocene age include volcanogenic muds with distinctive high MgO and K2O, indicative of a relatively basic calc-alkaline source related to an inferred Miocene forearc succession. The forearc basement, composed of diabase and basalt, was locally exposed (Site 1109) and eroded in the late Miocene (<5.4-9.93 Ma), giving rise to fluvial conglomerates (Sites 1109, 1115, and 1118). Chemically distinctive fine-grained claystones and siltstones (with relatively high Ti, low K) are compatible with derivation from tropically weathered basic igneous rocks, correlated with the Paleogene Papuan ophiolite. Overlying latest Miocene-Pleistocene fine-grained sediments throughout the Woodlark Basin were partly derived from calc-alkaline volcanic sources. However, relatively high abundances of Al2O3 and related element oxides (K2O and Na2O) and trace elements (e.g., Rb and Y) reflect an additional terrigenous input throughout the basin, correlated with pelitic metamorphic rocks exposed on Papua New Guinea and adjacent areas. In addition, sporadic high abundances of Cr and Ni, some other trace metals, and related minerals (talc, crysotile, and chlorite) reflect input from an ophiolitic terrain dominated by ultramafic rocks, correlated with the Paleogene Papuan ophiolite. The source areas possibly included serpentinized ultramafic ophiolitic rocks exposed in the Papua New Guinea interior highlands. Chemical evidence further indicates that fine-grained terrigenous sediment reached the Woodlark Basin throughout its entire late Miocene-Holocene history. Distinctive high-K volcanogenic muds rich in tephra and volcanic ash layers that appear at <2.3 Ma (Sites 1109 and 1115) are indicative of high-K calc-alkaline volcanic centers, possibly located in the Dawson Strait, Moresby Strait, or Dobu Seamount area. Chemical diagenesis of fine-grained sediments within the Woodlark Basin is reflected in clay neomorphism and localized formation of minerals including dolomite, ankerite, and zeolite but has had little effect on the bulk chemical composition of most samples.

Planktonic foraminiferal stratigraphy and datum levels of ODP Leg 182 sites

Planktonic foraminifers from Ocean Drilling Program Leg 182, Holes 1126B and 1126C, 1128B and 1128C, 1130A and 1130B, 1132B, and 1134A and 1134B confirm the neritic record that during the early Miocene the Great Australian Bight region was in a cool-temperate regime with abundant Globoturborotalita woodi. Warm marine environments started to develop in the later part of the early Miocene, and the region became warm temperate to subtropical in the early middle Miocene with abundant Globigerinoides, Orbulina, and Globorotalia, corresponding to global warming at the Miocene climatic optimum. Fluctuations between cool- and warm-temperate conditions prevailed during the late Miocene, as indicated by abundant Globoconella conoidea and Menardella spp. A major change in planktonic foraminiferal assemblages close to the Miocene/Pliocene boundary not only drove many Miocene species into extinction but also brought about such new species as Globorotalia crassaformis and Globoconella puncticulata. Warm-temperate environments continued into the early and mid-Pliocene before being replaced by cooler conditions, supporting numerous Globoconella inflata and Globigerina quinqueloba. Based on data from this study and published results from the Australia-New Zealand region, we established a local planktonic foraminifer zonation scheme for separating the southern Australian Neogene (SAN) into Zones SAN1 to SAN19 characterizing the Miocene and Zones SAN20 to SAN25 characterizing the Pliocene. The Neogene sections from the Great Australian Bight are bounded by hiatuses of ~0.5 to >3 m.y. in duration, although poor core recovery in some holes obscured a proper biostratigraphic resolution. A total of 15 hiatuses, numbered 1 to 15, were identified as synchronous events from the base of the Miocene to the lower part of the Pleistocene. We believe that these are local manifestations of major third-order boundaries at about (1) 23.8, (2) 22.3, (3) 20.5, (4) 18.7, (5) 16.4, (6) 14.8, (7) 13.5, (8) 11.5, (9) 9.3, (10) 7.0, (11) 6.0, (12) 4.5, (13) 3.5, (14) 2.5, and (15) 1.5 Ma, respectively. This hiatus-bounded Neogene succession samples regional transgressions and stages of southern Australia and reveals its stepwise evolutionary history.