Geochemistry of gas hydrates of DSDP Hole 84-570

During Deep Sea Drilling Project (DSDP) Leg 84 a core 1 m long and 6 cm in diameter of massive gas hydrate was unexpectedly recovered at Site 570 in upper slope sediment of the Middle America Trench offshore of Guatemala. This core contained only 5-7% sediment, the remainder being the solid hydrate composed of gas and water. Samples of the gas hydrate were decomposed under controlled conditions in a closed container maintained at 4°C. Gas pressure increased and asymptotically approached the equilibrium decomposition pressure for an ideal methane hydrate, CH4.5-3/4H2O, of 3930 kPa and approached to this pressure after each time gas was released, until the gas hydrate was completely decomposed. The gas evolved during hydrate decomposition was 99.4% methane, ~0.2% ethane, and ~0.4% CO2. Hydrocarbons from propane to heptane were also present, but in concentrations of less than 100 p.p.m. The carbon-isotopic composition of methane was -41 to -44 per mil, relative to PDB standard. The observed volumetric methane/water ratio was 64 or 67, which indicates that before it was stored and analyzed, the gas hydrate probably had lost methane. The sample material used in the experiments was likely a mixture of methane hydrate and water ice. Formation of this massive gas hydrate probably involved the following processes: (i) upward migration of gas and its accumulation in a zone where conditions favored the growth of gas hydrates, (ii) continued, unusually rapid biological generation of methane, and (iii) release of gas from water solution as pressure decreased due to sea level lowering and tectonic uplift.

Hydrocarbon gases in ODP Leg 104 samples

Geochemical studies at three ODP Leg 104 sites on the Wring Plateau help define the distribution of hydrocarbon gases in sediment of this prominent feature of the Norwegian continental margin. Low levels of hydrocarbon gas were encountered in sediment of the outer part of the plateau, but sediment of the inner part of the plateau is very gassy. The molecular composition of inner plateau gases (>99.9% methane) and the carbon isotopic composition of the methane (avg. = -76 per mil relative to the PDB standard) clearly show that the gas is biogenic. Heavier hydrocarbon gases accompany this methane, and their presence is probably a result of both chemical and microbial low-temperature diagenesis. Although these heavier hydrocarbons were not detected in sediment of the outer part of the plateau during shipboard analyses, subsequent shore-based analyses showed that these compounds are present at very low concentrations. Methane in the gassy sediment of the inner part of the plateau may be present as gas hydrates, judging from sedimentological and inorganic geochemical considerations, but no discernible gas hydrates were recovered during drilling.

Middle Miocene stable carbon and oxygen isotope record of foraminifera of ODP Hole 120-747A

Paleoceanographic variability at southern high latitude Ocean Drilling Program (ODP) Site 747 was investigated in this study through the interval which spans the Middle Miocene Climate Transition (MMCT). Between 15.0 and 12.2 million years ago (Ma), foraminiferal d18O records derived from both benthic (Cibicidoides spp.) and planktonic taxa (Globorotalia praescitula and Globigerina bulloides) reveal a history of changes in water column thermal and salinity structure and a strong imprint of seasonality. Prior to the MMCT, in the interval between 14.35 and 13.9 Ma, G. bulloides displays relatively high d18O values similar to those of G. praescitula, interpreted to indicate weakening of the thermocline and/or increased seasonality with cooler early-spring and/or late-fall temperatures. Following this interval, G. bulloidesd18O values diverge significantly from benthic and G. praescitula values, with G. bulloides values remaining relatively low for at least 600 kyr following the benthic foraminiferal d18O shift during the MMCT at ~13.9 Ma. This divergence in d18O records occurs in direct association with the Mi3 cooling and glaciation event and may suggest: (1) a strengthening of the vertical temperature gradient, with greater cooling of deep waters than surface waters, (2) changes in the depth habitat of G. bulloides, (3) changes in the dominant season of G. bulloides calcification, (4) modification of surface-water d18O values in association with enhanced sea-ice formation, (5) increased surface-water carbonate ion concentration, and/or (6) a significant decrease in surface-water salinity across the MMCT. The first of these possible scenarios is not likely, particularly in light of recent Mg/Ca evidence for significant surface-water cooling in the Southern Ocean associated with the MMCT. Of the remaining possibilities, we favor a change in surface salinity to explain the observed trends in d18O values and hypothesize that surface salinity may have decreased by up to 2 salinity units at ~13.9 Ma. In this scenario, the development of a lower-salinity Antarctic surface layer coincided with regional cooling of both surface and deep waters of the Southern Ocean during the Mi3 glaciation of East Antarctica, and contributed into the dominance of Neogloboquadrina spp. between 13.8 and 13.2 Ma. Additionally, the distinct patterns observed in planktonic foraminiferal d18O records spanning the MMCT correspond with changes in the vertical d13C gradient between planktonic and benthic foraminiferal records and major changes in planktonic foraminiferal assemblages at Site 747, providing further evidence of the environmental significance of this climatic transition.

Faunal turnovers in the central Pacific benthic foraminifera during the Paleocene-Eocene thermal maximum

Although it is well known that the Paleocene/Eocene thermal maximum (PETM) coincided with a major benthic foraminiferal extinction event, the detailed pattern of the faunal turnover has not yet been clarified. Our high-resolution benthic foraminiferal and carbon isotope analyses at the low latitude Pacific Ocean Shatsky Rise have revealed the following record of major faunal transitions: (1) An initial turnover which involved the benthic foraminiferal extinction event (BFE). The BFE, marked by a sharp transition from Pre-extinction fauna to Disaster fauna represented by small-sized Bolivina gracilis, expresses the onset of the PETM and the abrupt extinction of about 30% of taxa. This faunal transition lasted about 45-74 kyr after the initiation of the PETM and was followed by: (2) the appearance of Opportunistic fauna represented by Quadrimorphina profunda, which existed for about 74-91 kyr after the initiation of the PETM. These two faunas, which appeared after the extinction event, are characterized by low diversity and dwarfism, possibly due to lowered oxygen condition and decreased surface productivity. The second pronounced turnover involved the gradual recovery from Opportunistic Fauna to the establishment of Recovery fauna, which coincided with the recovery about 83-91 kyr after its initiation.

Stable carbon and oxygen isotope ratios of benthic foraminifera from Paleocene to Oligocene sediments

Benthic oxygen and carbon isotopic results from a depth transect on Maud Rise, Antarctica, provide the first evidence for Warm Saline Deep Water (WSDW) in the Paleogene oceans. Distinct reversals occur in the oxygen isotopic gradient between the shallower Hole 689B (Eocene depth ~1400 m; present-day depth 2080 m) and the deeper Hole 690B (Eocene depth ~2250 m; present-day depth 2914 m). The isotopic reversals, well developed by at least 46 Ma (middle middle Eocene), existed for much of the remaining Paleogene. We do not consider these reversals to be artifacts of differential diagenesis between the two sites or to have resulted from other potentially complicating factors. This being so, the results show that deep waters at Hole 690B were significantly warmer than deep waters at the shallower Hole 689B. A progressive decrease and eventual reversal in benthic to planktonic delta18O gradients in Hole 690B, demonstrate that the deeper waters became warmer relative to Antarctic surface waters during the Eocene. The warmer deep waters of the Paleogene are inferred to have been produced at middle to low latitudes, probably in the Tethyan region which contained extensive shallow-water platforms, ideal sites for the formation of high salinity water through evaporative processes. The ocean during the Eocene, and perhaps the Paleocene, is inferred to have been two-layered, consisting of warm, saline deep waters formed at low latitudes and overlain by cooler waters formed at high latitudes. This thermospheric ocean, dominated by halothermal circulation we name Proteus. The Neogene and modern psychrospheric ocean Oceanus is dominated by thermohaline circulation of deep waters largely formed at high latitudes. An intermediate condition existed during the Oligocene, with a three-layered ocean that consisted of cold, dense deep waters formed in the Antarctic (Proto-AABW), overlain by warm, saline deep waters from low latitudes, and in turn overlain by cool waters formed in the polar regions. This we name Proto-oceanus which combined both halothermal and thermohaline processes. The sequence of high latitude, major, climatic change inferred from the oxygen isotopic records is as follows: generally cooler earlier Paleocene; warming during the late Paleocene; climax of Cenozoic warmth during the early Eocene and continuing into the early middle Eocene; cooling mainly in a series of steps during the remainder of the Paleogene. Superimposed upon this Paleogene pattern, the Paleocene/Eocene boundary is marked by a brief but distinct warming that involved deep to surface waters and a reduction in surface to deep carbon and oxygen isotopic gradients. This event coincided with major extinctions among the deep-sea benthic foraminifers as shown by Thomas (1990 doi:10.2973/odp.proc.sr.113.123.1990). Salinity has played a major role in deep ocean circulation, and thus paleotemperatures cannot be inferred directly from the oxygen isotopic composition of Paleogene benthic foraminifers without first accounting for the salinity effect.

Nannofossil and stable isotope record across the Paleocene/Eocene Thermal Maximum in ODP Hole 183-1135A

The Paleocene/Eocene Thermal Maximum (PETM, ca. 55 Ma) is an abrupt, profound perturbation of climate and the carbon cycle associated with a massive injection of isotopically light carbon into the ocean-atmosphere system. As such, it provides an analogue for understanding the interplay between phytoplankton and climate under modern anthropogenic global-warming conditions. However, the accompanying enhanced dissolution poses uncertainty on the reconstruction of the affected ecology and productivity. We present a high-resolution record of bulk isotopes and nannofossil absolute abundance from Ocean Drilling Program (ODP) Site 1135 on the Kerguelen Plateau, Southern Indian Ocean to quantitatively constrain for the first time the influence of dissolution on paleoecological reconstruction. Our bulk-carbonate isotope record closely resembles that of the classic PETM site at ODP Site 690 on the opposite side of the Antarctic continent, and its correlation with those from ODP Sites 690, 1262 and 1263 records allows recognition of 14 precessional cycles upsection from the onset of the carbon isotopic excursion (CIE). This, together with a full range of common Discoasteraraneus and an abundance crossover between Fasciculithus and Zygrhablithusbijugatus, indicates the presence of the PETM at Site 1135, a poorly known record with calcareous fossils throughout the interval. The strong correlation between the absolute abundances of Chiasmolithus and coccolith assemblages reveals a dominant paleoecological signal in the poorly preserved fossil assemblages, while the influence of dissolution is only strong during the CIE. This suggests that r-selected taxa can preserve faithful ecological information even in the severely-altered assemblages studied here, and therefore provide a strong case for the application of nannofossils to paleoecological studies in better-preserved PETM sections. The inferred nannoplankton productivity drops abruptly at the CIE onset, but rapidly increases after the CIE peak, both of which may be driven by nutrient availability related to ocean stratification and vertical mixing due to changed sea-surface temperatures.

Benthic foraminiferal biofacies and stable isotopic record of St. Stephens Quarry, Alabama

We integrate upper Eocene-lower Oligocene lithostratigraphic, magnetostratigraphic, biostratigraphic, stable isotopic, benthic foraminiferal faunal, downhole log, and sequence stratigraphic studies from the Alabama St. Stephens Quarry (SSQ) core hole, linking global ice volume, sea level, and temperature changes through the greenhouse to icehouse transition of the Cenozoic. We show that the SSQ succession is dissected by hiatuses associated with sequence boundaries. Three previously reported sequence boundaries are well dated here: North Twistwood Creek-Cocoa (35.4-35.9 Ma), Mint Spring-Red Bluff (33.0 Ma), and Bucatunna-Chickasawhay (the mid-Oligocene fall, ca. 30.2 Ma). In addition, we document three previously undetected or controversial sequences: mid-Pachuta (33.9-35.0 Ma), Shubuta-Bumpnose (lowermost Oligocene, ca. 33.6 Ma), and Byram-Glendon (30.5-31.7 Ma). An ~0.9 per mil d18O increase in the SSQ core hole is correlated to the global earliest Oligocene (Oi1) event using magnetobiostratigraphy; this increase is associated with the Shubuta-Bumpnose contact, an erosional surface, and a biofacies shift in the core hole, providing a first-order correlation between ice growth and a sequence boundary that indicates a sea-level fall. The d18O increase is associated with a eustatic fall of ~55 m, indicating that ~0.4 per mil of the increase at Oi1 time was due to temperature. Maximum d18O values of Oi1 occur above the sequence boundary, requiring that deposition resumed during the lowest eustatic lowstand. A precursor d18O increase of 0.5 per mil (33.8 Ma, midchron C13r) at SSQ correlates with a 0.5 per mil increase in the deep Pacific Ocean; the lack of evidence for a sea-level change with the precursor suggests that this was primarily a cooling event, not an ice-volume event. Eocene-Oligocene shelf water temperatures of ~17-19 °C at SSQ are similar to modern values for 100 m water depth in this region. Our study establishes the relationships among ice volume, d18O, and sequences: a latest Eocene cooling event was followed by an earliest Oligocene ice volume and cooling event that lowered sea level and formed a sequence boundary during the early stages of eustatic fall.

Chemical and mineral compositions of sedimentary deposits and magmatic rocks from DSDP Legs 41, 45, 48, and 49

This collective monography by a group of lithologists from the Geological Institute of the USSR Academy of Sciences summarizes materials of the Deep-Sea Drilling Project from the Atlantic Ocean. It gives results of processing materials on the sequences drilled during DSDP Legs 41, 45, 48 and 49. These studies were based on lithological-facial analysis combined with detailed mineralogical-petrographic description. Its chapters give a number of ideas on formation of the Earth sedimentary cover, which can be used for compilation of regional and global schemes of ocean paleogeography, reconstruction of history of some structures in the World Ocean, correlation between sedimentary processes on continents and in oceans, estimation of perspectives for oil and gas fields and ore formation.

Pliocene stable oxygen and carbon isotope record of benthic foraminifera from ODP Site 138-846 in the eastern equatorial Pacific

Oxygen and carbon isotope ratios were measured in benthic foraminifers from the entire Pliocene and latest Miocene sections of Site 846, a 180-m section, at a sampling interval of 10 cm. This provides a temporal resolution of about 2500 yr. The documented continuity of the record is excellent. Using the time scale that was developed on the basis of orbital tuning of GRAPE density records, we observed a fairly constant phase relationship between delta18O and variations in the obliquity of Earth's rotational axis. A new numbering scheme for Pliocene isotope stages is proposed. This high-resolution delta18O record clarifies several interesting aspects of late Neogene climatic evolution, including a "glacial" event that may have caused the final Messinian desiccation of the Mediterranean Sea; one or more "interglacial" events that might have caused refilling of the Mediterranean; a well-resolved couplet of glacial events at about the age of the Sidujfall Subchron; interglacial extremes in the early part of the Gauss that could have resulted from either significant deglaciation on Antarctica or from warming of deep water; and a gradual ramp of increasingly extreme "glacial" events, starting at about the Kaena Subchron and culminating with delta18O stage 100 in the earliest Matuyama.

Glacial-interglacial record of ODP Site 181-1119 in the Canterbury Bright, Southwest Pacific Ocean

Ocean Drilling Program (ODP) Site 1119 is located at water depth 395 m near the subtropical front (STF; here represented by the Southland Front), just downslope from the shelf edge of eastern South Island, New Zealand. The upper 86.19 metres composite depth (mcd) of Site 1119 sediment was deposited at an average sedimentation rate of 34 cm/kyr during Marine Isotope Stages (MIS) 1-8 (0-252 ka), and is underlain across a ~25 kyr intra-MIS 8 unconformity by MIS 8.5-11 (277-367 ka) and older sediment deposited at ~14 cm/kyr. A time scale is assigned to Site 1119 using radiocarbon dates for the period back to ~39 ka, and, prior to then, by matching its climatic record with that of the Vostok ice core, which it closely resembles. Four palaeoceanographic proxy measures for surface water masses vary together with the sandy-muddy, glacial-interglacial (G/I) cyclicity at the site. Interglacial intervals are characterised by heavy delta13C, high colour reflectance (a proxy for carbonate content), low Q-ray (a proxy for clay content) and light delta18O; conversely, glacial intervals exhibit light delta13C, low reflectance, high Q-ray and heavy delta18O signatures. Early interglacial intervals are represented by silty clays with 10-105-cm-thick beds of sharp-based (Chondrites-burrowed), shelly, graded, fine sand. The sands are rich in foraminifera, and were deposited distant from the shoreline under the influence of longitudinal flow in relatively deep water. Glacial intervals comprise mostly micaceous silty clay, though with some thin (2-10 cm thick) sands present also at peak cold periods, and contain the cold-water scallop Zygochlamys delicatula. Interglacial sandy intervals are characterised by relatively low sedimentation rates of 5-32 cm/kyr; cold climate intervals MIS 10, 6 and 2 have successively higher sedimentation rates of 45, 69 and 140 cm/kyr. Counter-intuitively,and forced by the bathymetric control of a laterally-moving shoreline during G/I and I/G transitions, the 1119 core records a southeasterly (seaward) movement of the STF during early glacial periods, accompanied by the incursion of subtropical water (STW) above the site, and northwesterly (landward) movement during late glacial and interglacial times, resulting in a dominant influence then of subantarctic surface water (SAW). The history of passage of these different water masses at the site is clearly delineated by their characteristic delta13C values. The intervals of thin, graded sands-muds which occur within MIS 2-3, 6, 7.4 and 10 indicate the onset at times of peak cold of intermittent bottom currents caused by strengthened and expanded frontal flows along the STF, which at such times lay near Site 1119 in close proximity to seaward-encroaching subantarctic waters within the Bounty gyre. In common with other nearby Southern Hemisphere records, the cold period which represents the last glacial maximum lasted between ~23-18 ka at Site 1119, during which time the STF and Subantarctic Front (SAF) probably merged into a single intense frontal zone around the head of the adjacent Bounty Trough.

Late Quaternary carbonate and isotope stratigraphy of DSDP Site 90-594 east of South Island, New Zealand

The late Quaternary sequence off eastern South Island, New Zealand, consists of ~100 m of alternating bluish gray pelagic oozes and greenish gray hemipelagic oozes that extend uninterruptedly back to the Brunhes/Matuyama boundary (0.73 m.y.). A very high resolution (~2400 yr.) record of sediment texture, calcium carbonate content, and planktonic and benthic foraminiferal oxygen and carbon isotope composition demonstrates an in-phase cyclical fluctuation between the sedimentary parameters that closely correspond to the pelagic-hemipelagic sedimentation cycles and the isotope composition. Pelagic oozes, formed during interglacial periods of high eustatic sea level, are characterized by calcareous microfossils, relative enrichment in sand and clay sizes, high carbonate contents, reduced delta18O values, and increased delta13C values. Hemipelagic oozes, associated with glacial episodes and lowered eustatic sea level, include common terrigenous material and siliceous microfossils, are enriched in silt sizes, have low carbonate contents, high delta18O values, and low delta13C values. The history of alpine glaciations and associated erosion of the South Island of New Zealand, as expressed by the appearance of hemipelagic oozes, can be correlated directly with the major fluctuations of Northern Hemisphere ice sheets as expressed by the influence of eustatic sea-level changes on the oxygen isotope composition of both planktonic and benthic foraminifers. This high-accumulation-rate record contains conspicuous intervals of highfrequency, high-amplitude isotope variability including the presence of multiple glacial/interglacial intervals within single isotope stages, and offers one of the best sections cored to date for detailed study of the evolution and history of climate change over the last 0.75 m.y.