Element and isotope composition of selected volcanics from the Bicol arc, Philippines

Pliocene to recent volcanic rocks from the Bulusan volcanic complex in the southern part of the Bicol arc (Philippines) exhibit a wide compositional range (medium- to high-K basaltic-andesites, andesites and a dacite/rhyolite suite), but are characterised by large ion lithophile element enrichments and HFS element depletions typical of subduction-related rocks. Field, petrographic and geochemical data indicate that the more silicic syn- and post-caldera magmas have been influenced by intracrustal processes such as magma mixing and fractional crystallisation. However, the available data indicate that the Bicol rocks as a group exhibit relatively lower and less variable 87Sr/86Sr ratios (0.7036-0.7039) compared with many of the other subduction-related volcanics from the Philippine archipelago. The Pb isotope ratios of the Bicol volcanics appear to be unlike those of other Philippine arc segments. They typically plot within and below the data field for the Philippine Sea Basin on 207Pb/204Pb versus 206Pb/204Pb and 208Pb/204Pb versus 206Pb/204Pb diagrams, implying a pre-subduction mantle wedge similar to that sampled by the Palau Kyushu Ridge, east of the Philippine Trench. 143Nd/144Nd ratios are moderately variable (0.51285-0.51300). Low silica (<55 wt%) samples that have lower 143Nd/144Nd tend to have high Th/Nd, high Th/Nb, and moderately low Ce/Ce* ratios. Unlike some other arc segments in the Philippines (e.g. the Babuyan-Taiwan segment), there is little evidence for the involvement of subducted terrigenous sediment. Instead, the moderately low 143Nd/144Nd ratios in some of the Bicol volcanics may result from subduction of pelagic sediment (low Ce/Ce*, high Th/Nd, and high Th/Nb) and its incorporation into the mantle wedge via a slabderived partial melt.

Hydrocarbon contents and carbon isotope composition of organic matter from holes of DSDP Legs 50 and 64

The book is devoted to fundamental problems of organic geochemistry of ocean sediments. It is based on materials of organic matter and gas studies in cores from DSDP Legs 50 and 64. Experimental results obtained in the Laboratory of Carbon Geochemistry (V.I. Vernadsky Institute of Geochemistry and Analytical Chemistry, Moscow) take the main part of the book. Evolution of organic matter in specific environment of deep ocean sediments, sources of organic matter in the ocean and methods of their identification based on isotopic analysis and other methods are under discussion. Gas geochemistry in normal conditions of diagenesis, and in conditions under intense heating is studied.

Stable oxygen isotope composition of the sea water in the Mediterranean Sea

During the cruises No 17 and 22 of the German research vessel "Meteor", 45 water samples were taken at 4 stations in the central part of the Mediterranean Sea. Mass spectrometrical analyses showed that systematic, but time variable changes of the oxygen isotope ratios occur. Deep water samples (T> 500 m) have a ± constant isotopic composition of d18O = +1.79? (SMOW) and a Chlorinity of 21.399?. These data are discussed with respect to paleotemperature determinations.

Stable isotope composition and ice rafted debris in early Late Pliocene sediments from Maud Rise, South Atlantic

We have conducted an integrated study of ice-rafted debris (IRD) and oxygen isotopes (measured on Cibicides, Globigerina bulloides, and Neogloboquadrina pachyderma, using identical samples). We used samples from the early Late Pliocene Gauss Chron from ODP Site 114-704 on the Meteor Rise in the subantarctic South Atlantic. During the early Gauss Chron, the oxygen isotopic ratios are generally up to 0.5?-0.6? less than their respective Holocene values. The lowest values in this record can accommodate a warming of about 2.5°C or a sea-level rise of about 50 m, but not both, and probably result from some warming and a small reduction in global ice volume. Starting with isotope stage MG2 [ 3.23 Ma on the Berggren et al. ( 1985) time scale; 3.38 on the Shackleton et al. ( 1995b) time scale] oxygen-isotopic values generally increase (and oscillate about a Holocene mean). The first significant IRD appears at the same time. There is a subsequent increase in IRD amounts upsection. In order to reach the site, this material must have been transported by large, tabular icebergs derived from Antarctic ice shelves or ice tongues, similar to occasional, large modern icebergs. This combined record suggests strongly that the Antarctic ice sheet was essentially intact; some warming at the drill site is indicated, but not a major reduction in ice-volume on Antarctica.

Oxygen isotope composition of clinoptilolites

Oxygen isotope ratios were obtained from authigenic clinoptilolites from Barbados Accretionary Complex, Yamato Basin, and Exmouth Plateau sediments (ODP Sites 672, 797, and 762) in order to investigate the isotopic fractionation between clinoptilolite and pore water at early diagenetic stages and low temperatures. Dehydrated clinoptilolites display isotopic ratios for the zeolite framework (delta 18Of) that extend from +18.7? to +32.8? (vs. SMOW). In combination with associated pore water isotope data, the oxygen isotopic fractionation between clinoptilolite and pore fluids could be assessed in the temperature range from 25ºC to 40ºC. The resulting fractionation factors of 1.032 at 25ºC and 1.027 at 40ºC are in good agreement with the theoretically determined oxygen isotope fractionation between clinoptilolite and water. Calculations of isotopic temperatures illustrate that clinoptilolite formation occurred at relatively low temperatures of 17ºC to 29ºC in Barbados Ridge sediments and at 33ºC to 62ºC in the Yamato Basin. These data support a low-temperature origin of clinoptilolite and contradict the assumption that elevated temperatures are the main controlling factor for authigenic clinoptilolite formation. Increasing clinoptilolite delta18Of values with depth indicate that clinoptilolites which are now in the deeper parts of the zeolite-bearing intervals had either formed at lower temperatures (17-20ºC) or under closed system conditions.

Oxygen-isotope composition, temperature and depth of formation of chert at DSDP Leg 62 Holes

We measured oxygen-isotope compositions of 16 siliceous rocks from Deep Sea Drilling Project Sites 463, 464, 465, and 466 (Leg 62). Samples are from deposits that range in age from about 40 to 103 m.y. and that occur at sub-bottom depths of 9 to 461 meters. Mean d18O values range from 28.4 to 36.8 per mil and 36.0 ± 0.3 per mil for quartz-rich and opal-CTrich rocks, respectively. d18O values in chert decrease with increasing sub-bottom depth; the slope of the d18O/depth curve is less steep for Site 464 than for the other sites which indicates that chert at Site 464 formed at higher temperatures than chert at Sites 463, 465, and 466. Temperatures of formation of cherts were 7 to 42°C, using the silica-water fractionation factor of Knauth and Epstein (1976), or 19 to 56°C, using the equation of Clayton et al. (1972). Temperatures in the sediment where the cherts now occur are lower than their isotopically determined temperatures of formation, which means that the cherts record an earlier history when temperatures in the sediment section were greater. Estimated sediment temperatures when the cherts formed are comparable to, but generally slightly lower than, those calculated from Knauth and Epstein's equation. The isotopic composition of cherts is more closely related to environment of formation (diagenetic environment) or paleogeothermal gradients, than to paleoclimates (bottom-water temperatures). Opal-CT-rich rocks may better record paleo-bottom-water temperature. In Leg 62 cherts, better crystallinity of quartz corresponds to lower d18O values; this implies progressively higher temperatures of equilibration between quartz and water during maturation of quartz. The interrelationship of d18O and crystallinity is noted also in continental-margin deposits such as the Monterey Formation - but for higher temperatures. The apparent temperature difference between open-ocean and continental-margin deposits can be explained by the dominant control of temperature on silica transformation in the rapidly deposited continental-margin deposits, whereas time, as well as temperature, has a strong influence on the transformations in open-ocean deposits. Comparisons between the chemistry and d18O values of cherts reveal two apparent trends: both boron and SiO2 increase as d18O increases. However, the correspondence between SiO2 and d18O is only apparent, because the two cherts lowest in SiO2 are also the most deeply buried, so the trend actually reflects depth of burial. The correspondence between boron and d18O supports the conclusion that boron is incorporated in the quartz crystal structure during precipitation

Carbonate mineralogy and stable isotope composition of cool-water bryozoans from sediments of ODP Leg 182 sites

The carbon and oxygen isotopic compositions of selected bryozoan skeletons from upper Pleistocene bryozoan mounds in the Great Australian Bight (Ocean Drilling Program Leg 182; Holes 1129C, 1131A, and 1132B) were determined. Cyclostome bryozoans, Idmidronea spp. and Nevianipora sp., have low to intermediate magnesian calcite skeletons (1.5-10.0 and 0.9-6.4 molar percentage [mol%] MgCO3, respectively), but a considerable number include marine cements. The cheilostome Adeonellopsis spp. are biminerallic, principally aragonite, with some high magnesian calcite (HMC) (6.6-12.1 mol% MgCO3). The HMC fraction of Adeonellopsis has lower d13C and similar d18O values compared with the aragonite fraction. Reexamination of modern bryozoan isotopic composition shows that skeletons of Adeonellopsis spp. and Nevianipora sp. form close to oxygen isotopic equilibrium with their ambient water. Therefore, changes in glacial-interglacial oceanographic conditions are preserved in the oxygen isotopic profiles. The bryozoan oxygen isotopic profiles are correlated well with marine isotope Stages 1-8 in Holes 1129C and 1132B and to Stages 1-4(?) in Hole 1131A. The horizons of the bryozoan mounds that yield skeletons with heavier oxygen isotopic values can be correlated with isotope Stages 2, 4(?), 6, and 8 in Hole 1129C; Stages 2 and 4(?) in Hole 1131A; and Stages 2, 4, 6, and 8 in Hole 1132B. These results provide supporting evidence for a model for bryozoan mound formation, in which the mounds were formed during intensified upwelling and increased trophic resources during glacial periods.

Stable foraminifer isotope composition of ODP Site 184-1143, South China Sea

Site 1143 is located at 9°21.72'N, 113°17.11'E, at a water depth of 2772 m within a basin on the southern continental margin of the South China Sea. Three holes were cored at the site and combined into a composite (spliced) stratigraphic section that documents complete recovery for the upper 190.85 meters composite depth, the interval of advanced piston coring (Wang, Prell, Blum, et al., 2000, doi:10.2973/odp.proc.ir.184.2000; Wang et al., 2001, doi:10.1007/BF02907085). The early Pliocene to Holocene sediment sequence provided abundant and well-preserved calcareous microfossils and offered an excellent opportunity to establish foraminiferal stable isotope records. Here, we present benthic and planktonic d18O and d13C records that cover the last 5 m.y. These data sets will provide an important basis for upcoming studies to generate an orbitally tuned oxygen isotope stratigraphy and examine long- and short-term changes in deep and surface water mass signatures (temperature, salinity, and nutrients) with an average sample spacing of ~2.9 k.y. for the benthic and ~2.6 k.y. for the planktonic records.

Chemical and isotope composition of poor fluid from gas-hydrate samples of ODP Site 146-892

Although the presence of extensive gas hydrate on the Cascadia margin, offshore from the western U.S. and Canada, has been inferred from marine seismic records and pore water chemistry, solid gas hydrate has only been found at one location. At Ocean Drilling Program (ODP) Site 892, offshore from central Oregon, gas hydrate was recovered close to the sediment-water interface at 2-19 m below the seafloor (mbsf) at 670 m water depth. The gas hydrate occurs as elongated platy crystals or crystal aggregates, mostly disseminated irregularly, with higher concentrations occurring in discrete zones, thin layers, and/or veinlets parallel or oblique to the bedding. A 2- to 3-cm thick massive gas hydrate layer, parallel to bedding, was recovered at ~17 mbsf. Gas from a sample of this layer was composed of both CH4 and H2S. This sample is the first mixed-gas hydrate of CH4-H2S documented in ODP; it also contains ethane and minor amounts of CO2. Measured temperatures of the recovered core ranged from 2 to -1.8°C and are 6 to 8 degrees lower than in-situ temperatures. These temperature anomalies were caused by the partial dissociation of the CH4-H2S hydrate during recovery without a pressure core sampler. During this dissociation, toxic levels of H2S (delta34S, +27.4?) were released. The delta13C values of the CH4 in the gas hydrate, -64.5 to -67.5? (PDB), together with deltaD values of -197 to -199? (SMOW) indicate a primarily microbial source for the CH4. The delta18O value of the hydrate H2O is +2.9? (SMOW), comparable with the experimental fractionation factor for sea-ice. The unusual composition (CH4-H2S) and depth distribution (2-19 mbsf) of this gas hydrate indicate mixing between a methane-rich fluid with a pore fluid enriched in sulfide; at this site the former is advecting along an inclined fault into the active sulfate reduction zone. The facts that the CH4-H2S hydrate is primarily confined to the present day active sulfate reduction zone (2-19 mbsf), and that from here down to the BSR depth (19-68 mbsf) the gas hydrate inferred to exist is a >=99% CH4 hydrate, suggest that the mixing of CH4 and H2S is a geologically young process. Because the existence of a mixed CH4-H2S hydrate is indicative of moderate to intense advection of a methane-rich fluid into a near surface active sulfate reduction zone, tectonically active (faulted) margins with organic-rich sediments and moderate to high sedimentation rates are the most likely regions of occurrence. The extension of such a mixed hydrate below the sulfate reduction zone should reflect the time-span of methane advection into the sulfate reduction zone.

(Supplementary Table 1) Proportions of methane (C1) to ethane (C2) and the stable isotope composition of methane (d13CCH4) of gas and oil collected by gas bubble sampler during cruise M 114 in the southern Gulf of Mexico

Hydrocarbon seepage is a widespread process at the continental margins of the Gulf of Mexico. We used a multidisciplinary approach, including multibeam mapping and visual seafloor observations with different underwater vehicles to study the extent and character of complex hydrocarbon seepage in the Bay of Campeche, southern Gulf of Mexico. Our observations showed that seafloor asphalt deposits previously only known from the Chapopote Knoll also occur at numerous other knolls and ridges in water depths from 1230 to 3150 m. In particular the deeper sites (Chapopopte and Mictlan knolls) were characterized by asphalt deposits accompanied by extrusion of liquid oil in form of whips or sheets, and in some places (Tsanyao Yang, Mictlan, and Chapopote knolls) by gas emission and the presence of gas hydrates in addition. Molecular and stable carbon isotopic compositions of gaseous hydrocarbons suggest their primarily thermogenic origin. Relatively fresh asphalt structures were settled by chemosynthetic communities including bacterial mats and vestimentiferan tube worms, whereas older flows appeared largely inert and devoid of corals and anemones at the deep sites. The gas hydrates at Tsanyao Yang and Mictlan Knolls were covered by a 5-to-10 cm-thick reaction zone composed of authigenic carbonates, detritus, and microbial mats, and were densely colonized by 1-2 m-long tube worms, bivalves, snails, and shrimps. This study increased knowledge on the occurrences and dimensions of asphalt fields and associated gas hydrates at the Campeche Knolls. The extent of all discovered seepage structure areas indicates that emission of complex hydrocarbons is a widespread, thus important feature of the southern Gulf of Mexico.