Stable carbon and oxygen isotopes of foraminifera fand carbon content of ODP Leg 107 holes

High-resolution bio- and chemostratigraphy of an earliest Pliocene section from ODP Site 652 indicates that postflood paleoceanographic conditions in the Tyrrhenian Sea can be sub-divided into two discrete intervals. The first is manifested by an acme of Sphaeroidinellopsis spp., increasing carbonate contents, and a progressive decrease upsection in both the d13C and dl8O values of the planktonic foraminifera. The lower part of the acme interval contains unusual surface-to-bottom water isotope gradients suggesting a stratification of two water masses. Normal gradients in the upper part of the acme interval suggest a well-mixed water body. Between the end of the acme interval and the MP11/MP12 boundary, denoted by the first occurrence (F.O.) of Globorotalia margaritae, a migrational first appearance, there was a catastrophic collapse of the gradient marking an onset of the second post-flood interval. The disintegration of habitable conditions is suggested by a sharp decrease in carbonate content and the disappearance of the benthonic assemblage, which is subsequently replaced predominantly by Uvigerinapygmea, indicative of cold, low-oxygenated bottom waters. The introduction of benthonic species denoting well-oxygenated bottom conditions occurs within the lower MP12 zone. Superimposed on these overall trends are shorter term, warm-cold cycles, which are interpreted as orbitally induced, climatic fluctuations. Correlative studies of the less complete earliest Pliocene sections from ODP Holes 653B and 654A confirm these interpretations. A scenario derived from an integration of all the stratigraphic data indicates that normal paleoceanographic conditions were operating in the Tyrrhenian Sea only approximately 250,000 yr after the cessation of Messinian evaporative conditions at the Miocene/Pliocene boundary. The post-flood interval is marked by an initial period of gradual infilling, the Sphaeroidinellopsis spp. acme interval, followed by a disintegration of oceanographic conditions and a second recovery period. A sudden influx of cold, deep Atlantic waters into the Tyrrhenian Sea, resulting from a major tectonic break in the Gibraltar sill, may have caused this catastrophic reversal in the orderly recovery of normal paleoceanographic conditions in the post-flood period.

Foraminiferal study of ODP Hole 189-1171

Sequence boundary ages determined in shallow-water sediments obtained from ODP (Ocean Drilling Program) Leg 189 Site 1171 (South Tasman Rise) compare well with other stratigraphic records (New Jersey, United States, and northwestern Europe) and d18O increases from deep-sea records, indicating that significant (>10 m) eustatic changes occurred during the early to middle Eocene (51-42 Ma). Sequence boundaries were identified and dated using lithology, bio- and magnetostratigraphy, water-depth changes, CaCO3 content, and physical properties (e.g., photospectrometry). They are characterized by a sharp bioturbated surface, low CaCO3 content, and an abrupt increase in glauconite above the surface. Foraminiferal biofacies and planktonic/benthic foraminiferal ratios were used to estimate water-depth changes. Ages of six sequence boundaries (50.9, 49.2, 48.5-47.8, 47.1, 44.5, and 42.6 Ma) from Site 1171 correlate well to the timings of d18O increases and sequence boundaries identified from other Eocene studies. The synchronous nature of sequence boundary development from globally distal sites and d18O increases indicates a global control and that glacioeustasy was operating in this supposedly ice-free world. This is supported by previous modeling studies and atmospheric pCO2 estimates showing that the first time pCO2 levels decreased below a threshold that would support the development of an Antarctic ice sheet occurred at ca. 51 Ma. Estimates of sea-level amplitudes range from ~20 m for the early Eocene (51-49 Ma) and ~25 m to ~45 m for the middle Eocene (48-42 Ma) using constraints established for Oligocene d18O records.

Pore-water chemistry at DSDP Leg 70 Holes

Geological and geophysical data collected during Deep Sea Drilling Project (DSDP) Leg 70 indicate that hydrothermal solutions are upwelling through the sediments of the mounds hydrothermal field (Sites 506, 507, and 509) and downwelling in the low heat-flow zone to the south (Site 508). Pore-water data are compatible with these conclusions. Pore waters at mounds sites are enriched in Ca and depleted in Mg relative to both seawater and Site 508 pore waters. These anomalies are believed to reflect prior reaction of the interstitial waters with basement rocks. The mounds solutions are also enriched in iron, which is probably hydrothermal and en route to forming nontronite. Concentrations of Si and NH3 in mounds pore water increase upcore as a result of the addition of dissolving biogenic debris to ascending hydrothermal solutions. Some low heat-flow pore-water samples (Site 508) are enriched in Ca and depleted in Mg. These anomalies likely reflect the presence of pockets of hydrothermal solutions in areas otherwise dominated by downwelling bottom water.

Composition of organic matter from water, suspended matter, and bottom sediments of Nha Trang Bay, South China Sea

This research has been carried out in the Nha Trang Bay (Southern Vietnam, South China Sea) at a section from the estuary of the Cai River to the marine part of the bay, as well as in the area of coral reefs. River- and sea waters, suspended matter, and bottom sediments are studies. Data on dissolved organic carbon and total nitrogen in water are obtained. Organic carbon concentration is estimated in suspended matter; organic carbon and molecular and group compositions of n-alkanes are determined in bottom sediments. Molecular and group compositions of n-alkanes in bottom sediments of the landfill made it possible to identify three types of organic matter (OM): marine, mixed, and mainly of terrigenous origin. All these types of OM are closely related to specificity of sedimentation and hydrodynamics of waters in this area.

Isotopic composition and Strontium/Calcium ratios of foraminifera of ODP Holes 113-689B and 113-690C

Oxygen and carbon isotopic ratios were measured from Maestrichtian benthic and planktonic foraminifer species and bulk carbonate samples from ODP Sites 689 and 690, drilled on the Maud Rise during Leg 113. Careful scanning electron microscope observations reveal that test calcite in some intervals was diagenetically altered, although Sr/Ca and isotopic ratios of these tests do not appear to have been modified significantly. Foraminifer d18O values at both sites document a cooling trend during early Maestrichtian time, a rapid drop in water temperatures at the time of the first appearance of Abathomphalus mayaroensis in the high southern latitude regions (about 69.9 Ma), and lower water temperatures during late Maestrichtian time. d13C values record a depletion in 13C in the latest early Maestrichtian time beginning at about 72.2 Ma, just prior to the sharp late Maestrichtian increase in d18O values. These trends are similar to those previously reported for well-preserved benthic foraminifer species from Seymour Island, in the Antarctic Peninsula. Paleotemperature estimates are also comparable to those at Seymour Island and suggest temperate climatic conditions in Antarctica and that bottom waters in the southern South Atlantic region were of Antarctic origin. Benthic and planktonic foraminifer 613C values fluctuate sympathetically and are higher in upper Maestrichtian sediments than in the lower Maestrichtian sequence.

Gas content, composition of gas hydrate and volumetric gas/water ratios of ODP and DSDP sites

Gas hydrate samples were recovered from four sites (Sites 994, 995, 996, and 997) along the crest of the Blake Ridge during Ocean Drilling Program (ODP) Leg 164. At Site 996, an area of active gas venting, pockmarks, and chemosynthetic communities, vein-like gas hydrate was recovered from less than 1 meter below seafloor (mbsf) and intermittently through the maximum cored depth of 63 mbsf. In contrast, massive gas hydrate, probably fault filling and/or stratigraphically controlled, was recovered from depths of 260 mbsf at Site 994, and from 331 mbsf at Site 997. Downhole-logging data, along with geochemical and core temperature profiles, indicate that gas hydrate at Sites 994, 995, and 997 occurs from about 180 to 450 mbsf and is dispersed in sediment as 5- to 30-m-thick zones of up to about 15% bulk volume gas hydrate. Selected gas hydrate samples were placed in a sealed chamber and allowed to dissociate. Evolved gas to water volumetric ratios measured on seven samples from Site 996 ranged from 20 to 143 mL gas/mL water to 154 mL gas/mL water in one sample from Site 994, and to 139 mL gas/mL water in one sample from Site 997, which can be compared to the theoretical maximum gas to water ratio of 216. These ratios are minimum gas/water ratios for gas hydrate because of partial dissociation during core recovery and potential contamination with pore waters. Nonetheless, the maximum measured volumetric ratio indicates that at least 71% of the cages in this gas hydrate were filled with gas molecules. When corrections for pore-water contamination are made, these volumetric ratios range from 29 to 204, suggesting that cages in some natural gas hydrate are nearly filled. Methane comprises the bulk of the evolved gas from all sites (98.4%-99.9% methane and 0%-1.5% CO2). Site 996 hydrate contained little CO2 (0%-0.56%). Ethane concentrations differed significantly from Site 996, where they ranged from 720 to 1010 parts per million by volume (ppmv), to Sites 994 and 997, which contained much less ethane (up to 86 ppmv). Up to 19 ppmv propane and other higher homologues were noted; however, these gases are likely contaminants derived from sediment in some hydrate samples. CO2 concentrations are less in gas hydrate than in the surrounding sediment, likely an artifact of core depressurization, which released CO2 derived from dissolved organic carbon (DIC) into sediment. The isotopic composition of methane from gas hydrate ranges from d13C of -62.5 per mil to -70.7 per mil and dD of -175 per mil to -200 per mil and is identical to the isotopic composition of methane from surrounding sediment. Methane of this isotopic composition is mainly microbial in origin and likely produced by bacterial reduction of bicarbonate. The hydrocarbon gases here are likely the products of early microbial diagenesis. The isotopic composition of CO2 from gas hydrate ranges from d13C of -5.7 per mil to -6.9 per mil, about 15 per mil lighter than CO2 derived from nearby sediment.

Organic matter, isotopic composition of calcite veins in basement basalt and pore water at DSDP Leg 78A Holes

Sediments of the Barbados Ridge complex, cored on DSDP Leg 78A, contain low concentrations of acid-insoluble carbon (0.05-0.25%) and nitrogen (C/N 1.5-5) and dispersed C1-C6 hydrocarbons (100-800 ppb). The concentrations of organic carbon and 13C in organic carbon decrease with depth, whereas the concentration of dispersed hydrocarbons increases slightly with depth. These trends may reflect the slow oxidation of organic matter, with selective removal of 13C and slow conversion of the residual organic matter to hydrocarbons. Very minor indications of nitrogen gas were observed at about 250 meters sub-bottom at two of the drilling sites. Basement basalts have calcite veins with d13C values in the range of 2.0 to 3.2 per mil and d18O-SMOW values ranging from 28.5 to +30.6 per mil. Interstitial waters have d18O-SMOW of 0.2 to -3.5 per mil and dD-SMOW of -2 to -15 per mil. The oxygen isotopic composition of the calcite veins in the basement basalts gives estimated equilibrium fractionation temperatures in the range of 11 to 24°C, assuming precipitation from water with d18O-SMOW in the range of +0.1 to -1.0 per mil. This suggests that basalt alteration and precipitation of vein calcite occurred in contact either with warmer Campanian seawater or, later, with pore water, after burial to depths of 200- 300 meters. Pore waters from all three sites are depleted in deuterium and 18O, and dissolved sulfate is enriched in 34S at Sites 541 and 542, but not at Site 543.

Miocene to Pleistocene planktonic foraminifer biostratigraphy of ODP Leg 135 sites

Diverse and well-preserved planktonic foraminifers were recovered from six sites (834-839) drilled in the Lau Basin. Planktonic faunas from the Tongan Platform sites varied from those of the Lau Basin sites by being less well preserved (Site 840) to being very poorly preserved and very sparse (Site 841); at Site 841 most samples were barren. All sites penetrated a volcaniclastic sequence in which thick ash beds were encountered; foraminifer populations within the ash beds were often very small, making it difficult to obtain biostratigraphic data. No hiatuses were encountered in the upper Miocene to Pleistocene sections of the Lau Basin, but a possible break occurs at Site 840 on the Tongan Platform. Site 834 penetrated through a Quaternary-Pliocene sequence overlying basaltic basement, and topmost Miocene (Zone N17B) sediments interbedded within the volcanic sequence. Site 835 penetrated into the lower Pliocene (Zones N19 to N19-20). Site 836 penetrated the shortest section, with Zone N22 {Globorotalia (Truncorotalia) crassaformis hessi Subzone) directly overlying basalts. Site 837 penetrated into the basal part of Zone N22 (Globigerinoides quadrilobatus fistulosus Subzone) overlying basalt. Site 838 failed to encounter basalts, with the oldest sediment being from Zone N22 (Globigerinoides quadrilobatus fistulosus Subzone). Site 839, within the same basin as Site 838, located Zone N22 (Globigerinoides quadrilobatus fistulosus Subzone) sediments directly overlying igneous basement. Site 840 penetrated into the upper Miocene Zone N17A without encountering any major unconformity. Site 841, studied mainly from core-catcher samples, penetrated a Quaternary to questionable upper Miocene sequence that was in fault contact with middle Miocene (Zones N8 to N9) sediments. For the Lau Basin sites, reworking was encountered only in Sites 834 and 835. Site 834 was drilled adjacent to the Lau Ridge, on which are developed numerous reef al and shallow-water environments, where erosional conditions could have been expected during sea-level lowstands. Site 835 was drilled in a narrow basin that has been remote from these erosional influences; slumping and erosion of material from the adjacent basin slopes appears to have been the source of the reworking. For the Tongan Platform sites, reworking was observed only in the lower part of the upper Miocene section at Site 841, where late Eocene larger foraminifers are present in conglomerates and grits. The presence of Globorotalia (Globorotalia) multicamerata and small specimens of Sphaeroidinellopsis spp. in the Pleistocene of Site 840 may indicate reworking, but this is not clear. Unit I, which marks a reduction in volcanic activity in the Lau Basin, ranges in age from the lower part of Zone N22 (Globigerinoides quadrilobatus fistulosus Subzone) at Sites 834 and 835, to within Zone N22 (Globorotalia crassaformis hessi Subzone) at Sites 836 to 838, and within the upper part of Zone N22 (Bolliella praeadamsi Subzone) at Site 839. Units II and III are generally represented by thick to very thick ash beds, which generally contain low-diversity and often poorly preserved assemblages. Igneous sources seem to have remained important contributors of sediment up to the present day.

Elemental abundance and water content at DSDP Leg 86 Holes

X-ray fluorescence analyses of 1143 samples from Site 576 (32°21.4'N, 164°16.5'E) and 539 samples from Site 578 (33°55.6'N, 151°37.7'E) for the elements Na, Mg, Al, Si, P, K, Ca, Ti, Mn, Fe, Ba, and S show consistent trends from Si-rich surficial deposits to dark brown clays rich in Mn, Fe, P, and Ti in early Cenozoic sections. These data sets form the basis for a detailed paleogeochemical stratigraphy of North Pacific "red" clays.

Diffusion transport of water in basalts

Studying diffusive transport in porous rocks is of fundamental importance in understanding a variety of geochemical processes including: element transfer, primary mineral dissolution kinetics and precipitation of secondary phases. Here we report new findings on the relationship between diffusive transport and textural characteristics of the pore systems on the example of mid-oceanic ridge basalts having different degree of alteration but very similar bulk pore volume. Diffusion processes in porous basalts were studied in situ using H2O -> D2O exchange experiments. The effective diffusion coefficients of water molecules increase systematically from 5.05*10**-11 to 1.19*10**-10 m**2/s for fresh and moderately altered basalts and from 2.40*10**-11 to 6.72*10**-11 m**2/s for completely altered basalt as temperature increases from 5 to 50 °C. The activation energy of the diffusion process increases from 12.29 ± 0.71 kJ/mol for fresh and moderately altered basalts to 14.3 ± 1.33 kJ/mol for completely altered basalt. The results indicate that neither the bulk porosity nor the degree of alteration can be used as proxies for the efficiency of element transport during MORB-water interaction. The formation of secondary phases that replace primary minerals and fill the pore space in the rock leads to the formation of tiny pores and phases with large specific surface area. These factors might have a dominant control on the transport properties of altered basaltic rocks.

Quaternary radiolarians and plamktonic foraminifera from the mouth of the Gulf of California

I recovered well-preserved radiolarian assemblages from the Quaternary sediments drilled at all four sites at the mouth of the Gulf of California during Leg 65. The sites, with positions and water depths averaged for all hole locations per site, are Site 482 - 22°47.4'N, 107°59.6'W; water depth, 3022 meters. Site 483 - 22°53.0'N, 108°44.8' W; water depth, 3070 meters. Site 484 - 23°11.2'N, 108°23.6'W; water depth, 2887 meters. Site 485 - 22°44.9'N, 107°54.2'W; water depth, 2981 meters. The nearly 200 taxa I identified are listed alphabetically in the systematic reference list. The only reliable radiolarian biostratigraphic datum determined for the Quaternary sedimentary section is the highest occurrence of Axoprunum angelinum (Hays) at Sites 483, 484, and 485.

Benthic foraminiferal carbon isotopic records and the development of abyssal circulation at DSDP Sites 9-77, 12-119, 30-289, 82-563 and 94-608

The North Atlantic at present is ventilated by overflow of the Denmark Strait, Iceland-Faeroe Ridge, Faeroe Bank Channel, and Wyville-Thompson Ridge. The evolution of Cenozoic abyssal circulation of this region was related to tectonic opening and subsidence of these sills. We used d13C records of the benthic foraminifer Cibicidoides to decipher the timing of tectonically controlled changes in bottom-water circulation in the eastern basins (Biscay and Iberian) of the northern North Atlantic. Records from Site 608 (Kings Trough, northeastern North Atlantic) show that from about 24 to 15 Ma (early to early middle Miocene), d13C values in the Kings Trough area were depleted relative to western North Atlantic values and were more similar to Pacific d13C values. This reflects less ventilation of the Kings Trough region as compared to the well-oxygenated western North Atlantic. Comparison of Oligocene d13C records from Site 119 (Bay of Biscay) with western North Atlantic records suggests that the eastern basin was also relatively isolated prior to 24 Ma. At about 15 Ma, d13C values at Site 608 attained values similar to the western North Atlantic, indicating increased eastern basin ventilation in the middle Miocene. This increased advection into the eastern basin predated a major d18O increase which occurred at about 14.6 Ma. Subsidence estimates of the Greenland-Scotland Ridge indicate that the deepening of the Iceland-Faeroe Ridge was coincident with the marked change in eastern basin deep-water ventilation.

Oxygen- and carbon-isotopes of Globigerina bulloides and Neogloboquadrina pachyderma at DSDP Holes 80-548 and 80-549A

Oxygen- and carbon-isotope analyses have been performed on the Quaternary planktonic foraminifers of Sites 548 and 549 (DSDP Leg 80) to investigate major water mass changes that occurred in the northeastern Atlantic at different glacial-interglacial cycles and to compare them with the well-defined picture of 18,000 yr. ago. Oxygen-isotope stratigraphy also provides a chronological framework for the more important data on the fauna and flora. Although bioturbation and sedimentary gaps obliterate the climatic and stratigraphic record, general trends in the oceanographic history can be deduced from the isotopic data. Isotopic stratigraphy has tentatively been delineated down to isotopic Stage 16 at Site 548 and in Hole 549A. This stratigraphy fits well with that deduced from benthic foraminiferal d18O changes and with bioclimatic zonations based on foraminiferal associations at Site 549. Variations in the geographic extension and in the flux of the Gulf Stream subtropical waters are inferred from both d18O and d13C changes. Maximal fluxes occurred during the late Pliocene. Northward extension of subtropical waters increased through the various interglacial phases of the early Pleistocene and decreased through the late Pleistocene interglacial phases. Conversely, glacial maxima were more intense after Stage 16. Isotopic Stages 12 and 16 mark times of important change in water mass circulation. Oxygen- and carbon-isotope analyses have been performed on the Quaternary planktonic foraminifers of Sites 548 and 549 (DSDP Leg 80) to investigate major water mass changes that occurred in the northeastern Atlantic at different glacial-interglacial cycles and to compare them with the well-defined picture of 18,000 yr. ago. Oxygen-isotope stratigraphy also provides a chronological framework for the more important data on the fauna and flora. Although bioturbation and sedimentary gaps obliterate the climatic and stratigraphic record, general trends in the oceanographic history can be deduced from the isotopic data. Isotopic stratigraphy has tentatively been delineated down to isotopic Stage 16 at Site 548 and in Hole 549A. This stratigraphy fits well with that deduced from benthic foraminiferal d18O changes and with bioclimatic zonations based on foraminiferal associations at Site 549. Variations in the geographic extension and in the flux of the Gulf Stream subtropical waters are inferred from both d18O and d13C changes. Maximal fluxes occurred during the late Pliocene. Northward extension of subtropical waters increased through the various interglacial phases of the early Pleistocene and decreased through the late Pleistocene interglacial phases. Conversely, glacial maxima were more intense after Stage 16. Isotopic Stages 12 and 16 mark times of important change in water mass circulation.

Response of marine palynomorphs to Neogene climate cooling in the Iceland Sea, ODP Hole 151-907A

The present study on ODP Leg 151 Hole 907A combines a detailed analysis of marine palynomorphs (dinoflagellate cysts, prasinophytes, and acritarchs) and a low-resolution alkenone-based sea-surface temperature (SST) record for the interval between 14.5 and 2.5 Ma, and allows to investigate the relationship between palynomorph assemblages and the paleoenvironmental evolution of the Iceland Sea. A high marine productivity is indicated in the Middle Miocene, and palynomorphs and SSTs both mirror the subsequent long-term Neogene climate deterioration. The diverse Middle Miocene palynomorph assemblages clearly diminish towards the impoverished assemblages of the Late Pliocene; parallel with a somewhat gradual decrease of SSTs being as high as 20 °C at ~13.5 Ma to around 8 °C at ~3 Ma. Superimposed, palynomorph assemblages not only reflect Middle to Late Miocene climate variability partly coinciding with the short-lived global Miocene isotope events (Mi-events), but also the initiation of a proto-thermohaline circulation across the Middle Miocene Climate Transition, which led to increased meridionality in the Nordic Seas. Last occurrences of species cluster during three events in the Late Miocene to Early Pliocene and are ascribed to the progressive strengthening and freshening of the proto-East Greenland Current towards modern conditions. A significant high latitude cooling between 6.5 and 6 Ma is depicted by the supraregional "Decahedrella event" coeval with lowest Miocene productivity and a SST decline. In the Early Pliocene, a transient warming is accompanied by surface water stratification and increased productivity that likely reflects a high latitude response to the global biogenic bloom. The succeeding crash in palynomorph accumulation, and a subsequent interval virtually barren of marine palynomorphs may be attributed to enhanced bottom water oxygenation and substantial sea ice cover, and indicates that conditions seriously affecting marine productivity in the Iceland Sea were already established well before the marked expansion of the Greenland Ice Sheet at 3.3 Ma.

Diagenesis of siliceous particles in ODP Hole 114-699A

A number of neogenic opaline structures, not previously reported in the literature, as well as other neogenic phases are described from four Oligocene to Pliocene biosiliceous sediment samples from Hole 699A. The possible influence of microbes on the formation or the morphology of some of them is discussed. The samples, which are early Pliocene, early to middle Miocene, and late Oligocene (two) in age, were histologically fixed aboard ship upon retrieval. Investigations of the samples used SEM (with Edax/Tracor) and XRD methods. Diagenesis has affected all four samples, but the most extensive development of neoformed structures occurs in the Miocene and uppermost Oligocene samples, where microbial filaments (0.05 to 10 ?m long), microbial colonies, and siliceous microhemispheroids (0.2 to 0.7 µm diameter) were observed. The latter encrust filaments, diatoms, and detrital grains to varying degrees. Other neoformed structures include (1) flakes formed by coalesced microhemispheroids, some of which are guided by short, stubby filaments, which occur only in the Miocene and uppermost Oligocene samples, and (2) flakes characterized by smooth or microfissured surfaces, which grow on diatom frustules and in pore spaces and have a more widespread distribution. The XRD data indicate possible cristobalite formation in the Miocene and uppermost Oligocene samples; we believe that the neoformed opaline structures (encrusted filaments and microhemispheroids) may represent an early phase of opal-CT. The timing of neoformation of most of these features appears to have been fairly recent, continuing even at the time of sampling. There appears to be no direct correlation of this incipient, lower Miocene-uppermost Oligocene diagenetic layer and the pore-water chemistry profiles; a massive increase in shear strength in these sediments, however, may indicate some cementation. Smectite was identified by XRD as the most prominent clay mineral in these generally clay-poor sediments. Honeycombed minerals with filamentous edges, which could correspond to smectite, were observed with SEM in the pore spaces.