Stable isotope record of foraminifera from sediment core EW9209-1JPC

Stable isotopic measurements of G. sacculifer and C. wuellerstorfi in a core from the western equatorial Atlantic imply that there are parallel, suborbital oscillations in surface water hydrography and deep water circulation occurring during oxygen isotope stages 2 and 3. Low values of G. sacculifer delta18O accompany high values of C. wuellerstorfi delta13C, linking warmer sea surface temperatures (SSTs) in the tropics with increased production of lower North Atlantic Deep Water (NADW). The amplitude of the delta18O oscillations is 0.6 per mil (or 2°-3°C), which is superimposed on a glacial/interglacial amplitude of about 2.1per mil. Using the G. sacculifer delta18O data, we calculate that surface waters were colder during stage 2 than calculated by CLIMAP [1976, 1981]. The longer-period (>2 kyr) oscillations in air temperature recorded in the Greenland and Antarctic ice cores appear to correlate with oscillations in sea surface temperature in the equatorial Atlantic. The magnitude of these oscillations in tropical SST is too large to have resulted from changes in meridional heat transport caused by the global conveyor alone. The apparent synchroneity of equatorial SST and polar air temperature changes, as well as the amplitude of the SST changes at the equator, are consistent with the climate effects expected from changes in the atmosphere's greenhouse gas content (H2Ovapor, CO2, and CH4).

Age model and stable isotope record of DSDP holes 48-401 and 86-577

Early Paleogene warm climates may have been linked to different modes and sources of deepwater formation. Warm polar temperatures of the Paleocene and Eocene may have resulted from either increased atmospheric trace gases or increased heat transport through deep and intermediate waters. The possibility of increasing ocean heat transport through the production of warm saline deep waters (WSDW) in the Tethyan region has generated considerable interest. In addition, General Circulation Model results indicate that deepwater source regions may be highly sensitive to changing basin configurations. To decipher deepwater changes, we examined detailed benthic foraminiferal faunal and isotopic records of the late Paleocene through the early Eocene (~60 to 50 Ma) from two critical regions: the North Atlantic (Bay of Biscay Site 401) and the Pacific (Shatsky Rise Site 577). These records are compared with published data from the Southern Ocean (Maud Rise Site 690, Islas Orcadas Rise Site 702). During the late Paleocene, similar benthic foraminiferal delta18O values were recorded at all four sites. This indicates uniform deepwater temperatures, consistent with a single source of deep water. The highest delta13C values were recorded in the Southern Ocean and were 0.5 per mil more positive than those of the Pacific. We infer that the Southern Ocean was proximal to a source of nutrient-depleted deep water during the late Paleocene. Upper Paleocene Reflector Ab was cut on the western Bermuda Rise by cyclonically circulating bottom water, also suggesting a vigorous source of bottom water in the Southern Ocean. A dramatic negative excursion in both carbon and oxygen isotopes occurred in the latest Paleocene in the Southern Ocean. This is a short-term (<100 kyr), globally synchronous event which also is apparent in both the Atlantic and Pacific records as a carbon isotopic excursion of approximately 1 per mil. Faunal analyses from the North Atlantic and Pacific sites indicate that the largest benthic foraminiferal faunal turnover of the Cenozoic was synchronous with the isotopic excursion, lending support to the hypothesis that the extinctions were caused by a change in deepwater circulation. We speculate that the Southern Ocean deepwater source was reduced or eliminated at the time of the excursion. During the early Eocene, Southern Ocean delta13C values remained enriched relative to the North Atlantic and Pacific. However, the Southern Ocean was also enriched in delta18O relative to these basins. We interpret that these patterns indicate that although the Southern Ocean was proximal to a source of cool, nutrient-depleted water, the intermediate to upper deep water sites of the North Atlantic and Pacific were ventilated by a different source that probably originated in low latitudes, i.e., WSDW.

Stable isotope ratios of benthic foraminifera in mid-Pleitsocene sediments of ODP Site 108-664 in the equatorial Atlantic

Five delta13C records from the deep ocean, extending back to 1.3 Ma, were examined in order to constrain changes in mean ocean carbon isotope composition and thermohaline circulation over the 41- to 100-ka climate transition. These data show that significant perturbations in mean ocean carbon chemistry were associated with the mid-Pleistocene climate transition. Notable features of the last 1.3 Myr are (1) a pronounced ~0.3? decrease in mean ocean delta13C between 0.9 and 1.0 Myr, followed by a return to pre-1.0 Ma values by 400 ka B.P., which we propose was due to the onetime addition of isotopically depleted terrestrial carbon to the ocean, possibly associated with an increase in global aridity (and decrease in the size of the biosphere) across the 41- to 100-ka transition; (2) no change in the Atlantic-Pacific (A-P) delta13C gradient over the last 1.3 Myr, suggesting no change in mean ocean nutrient content accompanied the addition of light carbon; and (3) stronger vertical nutrient fractionation in the North Atlantic in the middle Pleistocene between sites 607 and 552, suggesting weaker North Atlantic Deep Water formation at this time relative to the early and late Pleistocene. We also find evidence for a more pronounced deep recirculation gyre in the western North Atlantic basin in the early Brunhes, as evidenced by "aging" of deep northern basin water (site 607) relative to deep water in the equatorial Atlantic (site 664).

Extractable hydrocarbon and carbon isotope geochemistry of Lower Cretaceous sediments of the Exmouth Plateau

The organic geochemical character of rocks selected from Aptian, Valanginian, and Berriasian clay stone and siltstone sequences encountered in Ocean Drilling Program (ODP) Holes 762C and 763C on the Exmouth Plateau was determined by means of a variety of analytical procedures. These sequences represent distal portions of the Mesozoic Barrow delta, in which petroleum source rocks and reservoirs exist on the Australian continent. The organic matter at the ODP sites is thermally immature type III material. Biomarker hydrocarbon compositions are dominated by long-chain, waxy n-alkanes and by C29 steranes, which reflect the land-plant origin of organic matter. Organic carbon d13C values ranged from -26 per mil to -28 per mil, consistent with a C3 land-plant source. Kerogen pyrolysate compositions and hopane isomerization ratios revealed progressively larger contributions of recycled organic matter as the depth of the deltaic sedimentary layers became greater.

Density and stable oxygen isotope profiles of four snow pits from Berkner Island, Filchner-Ronne Ice Shelf, Antarctica

The ice cap on Berkner Island is grounded on bedrock within the Filchner-Ronne Ice Shelf and is, therefore, expected to be a well-suited place to retrieve long-term ice-core records reflecting the environmental situation of the Weddell Sea region. Shallow firn cores were drilled to 11 m at the two main summits of Berkner Island and analysed in high depth resolution for electrical d.c. conductivity (ECM), stable isotopes, chloride, sulphate, nitrate and methane-sulphonate (MSA). From the annual layering of dD and non-sea-salt (nss) sulphate, a mean annual snow accumulation of 26.6 cm water at the north dome and 17.4 cm water at the south dome are obtained. As a result of ineffective wind scouring indicated by a relatively low near-surface snow density, regular annual cycles are found for all species at least in the upper 4-5 m. Post depositional changes are responsible for a substantial decrease of the seasonal dD and nitrate amplitude as well as for considerable migration of the MSA signal operating below a depth of 3-4 m. The mean chemical and isotopic firn properties at the south dome correspond to the situation on the Filchner-Ronne Ice shelf at a comparable distance to the coast, whereas the north dome is found to be more influenced by maritime air masses. Persistent high sea-salt levels in winter snow at Berkner Island heavily obscure the determination of nss sulphate probably due to sulphate fractionation in the Antartic sea-salt aerosols. Estimated time-scales predict ages at 400 m depth to be ca. 2000 years for the north and ca. 3000 years for the south dome. Pleistocene ice is expected in the bottom 200 and 300 m, respectively.

High-resolution isotope stratigraphy of ODP Site 184-1144

Narrow-spaced oxygen and carbon stable isotope records of the planktonic foraminifer Globigerinoides ruber (white) were obtained at Ocean Drilling Program Leg 184 Site 1144 to establish a first record of high-resolution Pleistocene monsoon variability on orbital to centennial timescales in the northern South China Sea. The new records extend from the Holocene back to marine isotope Stage (MIS) 34 (1.1 Ma). Sedimentation rates average 0.56 m/k.y. for the upper Matuyama and Brunhes Chrons and increase to 1.8 m/k.y. over the last 100 k.y. Stable isotope records thus reach an average time resolution of 270-500 yr for the last 375 k.y. and 570 yr further back to 700 ka. On the other hand, major stratigraphic gaps were identified for peak warm Stages 5.5, 7.5 (down to 8.4), 11.3, and 15.5. These gaps probably resulted from short-lasting events of contour current erosion induced by short-term enhanced incursions of Upper Pacific Deep Water near the end of glacial terminations. A further major hiatus extends from MIS 34 to MIS 73(?). The long-term variations in monsoon climate were largely dominated by the 100-k.y. eccentricity cycle. Planktonic delta13C values culminated near 30, 480, and 1035 ka and reflect an overlying 450-k.y. eccentricity cycle of minimum nutrient concentrations in the surface ocean. Superimposed on the orbital variations, millennial-scale cycles were prominent throughout the last 700 k.y., mainly controlled by short-term changes in monsoon-driven precipitation and freshwater input from mainland China. During the last 110 k.y. these short-lasting oscillations closely match the record of 1500-yr Dansgaard-Oeschger climate cycles in the Greenland ice core record.

Stable oxygen isotope ratios of marine barite from Cenozoic sediments

We report new data on oxygen isotopes in marine sulfate (delta18O[SO4]), measured in marine barite (BaSO4), over the Cenozoic. The delta18O[SO4] varies by 6x over the Cenozoic, with major peaks 3, 15, 30 and 55 Ma. The delta18O[SO4] does not co-vary with the delta18O[SO4], emphasizing that different processes control the oxygen and sulfur isotopic composition of sulfate. This indicates that temporal changes in the delta18O[SO4] over the Cenozoic must reflect changes in the isotopic fractionation associated with the sulfide reoxidation pathway. This suggests that variations in the aerial extent of different types of organic-rich sediments may have a significant impact on the biogeochemical sulfur cycle and emphasizes that the sulfur cycle is less sensitive to net organic carbon burial than to changes in the conditions of that organic carbon burial. The delta18O[SO4] also does not co-vary with the d18O measured in benthic foraminifera, emphasizing that oxygen isotopes in water and sulfate remain out of equilibrium over the lifetime of sulfate in the ocean. A simple box model was used to explore dynamics of the marine sulfur cycle with respect to both oxygen and sulfur isotopes over the Cenozoic. We interpret variability in the delta18O[SO4] to reflect changes in the aerial distribution of conditions within organic-rich sediments, from periods with more localized, organic-rich sediments, to periods with more diffuse organic carbon burial. While these changes may not impact the net organic carbon burial, they will greatly affect the way that sulfur is processed within organic-rich sediments, impacting the sulfide reoxidation pathway and thus the delta18O[SO4]. Our qualitative interpretation of the record suggests that sulfate concentrations were probably lower earlier in the Cenozoic.

Organic carbon and humic substances contents, carbon isotope composition and peroxidase activity in sediments from DSDP Sites 15-147 and 75-532

Sediment samples from the Cariaco Trench (DSDP Leg 15) and the Walvis Ridge (DSDP Leg 75) ranging in age from Holocene to Upper Miocene (approximately 8 million years BP) and in depth from 5 to 258 m were extracted with basic sodium pyrophosphate and the extract analyzed for enzymic activity. Since no dehydrogenase, alkaline phosphatase or esterase activity was found, it is estimated from these data that the maximum bacterial population does not exceed 1000 cells per gram dry sediment. Peroxidase activity was, however, found in most samples: this showed marked dependence on the humic substance concentration (expressed as percent of the organic carbon content) and increased with depth at a rate of 33 units per meter. To explain this observation, we favor an hypothesis based on the presence of active humic-enzyme association. The humic substances absorb and stabilize peroxidase which is liberated throughout the sediment column by lysis of cells. The association of the enzyme with the humic substances protects it from biodegradation and denaturation. This hypothesis agrees with laboratory experiments which show the enhanced stability of humic-enzyme complexes towards degradation by biological, chemical and thermal effects.

Mineralogy, lithology and stable isotope composition of diagenetic siliceous rocks from ODP Leg 129 sites

Ocean Drilling Program Leg 129 recovered chert, porcellanite, and radiolarite from Middle Jurassic to lower Miocene strata from the western Pacific that formed by different processes and within distinct host rocks. These cherts and porcellanites formed by (1) replacement of chalk or limestone, (2) silicification and in-situ silica phase-transformation of bedded clay-bearing biosiliceous deposits, (3) high-temperature silicification adjacent to volcanic flows or sills, and (4) silica phase-transformation of mixed biosiliceous-volcaniclastic sediments. Petrologic and O-isotopic studies highlight the key importance of permeability and time in controlling the formation of dense cherts and porcellanites. The formation of dense, vitreous cherts apparently requires the local addition and concentration of silica. The influence of permeability is shown by two examples, in which: (1) fragments of originally identical radiolarite that were differentially isolated from pore-water circulation by cement-filled fractures were silicified to different degrees, and (2) by the development of secondary porosity during the opal-CT to quartz inversion within conditions of negligible permeability. The importance of time is shown by the presence of quartz chert below, but not above, a Paleogene hiatus at Site 802, indicating that between 30 and 52 m.y. was required for the formation of quartz chert within calcareous-siliceous sediments. The oxygen-isotopic composition for all Leg 129 carbonate- and Fe/Mn-oxide-free whole-rock samples of chert and porcellanite range widely from d18O = 27.8 per mil to 39.8 per mil vs. V-SMOW. Opal-CT samples are consistently richer in 18O (34.1 per mil to 39.3 per mil) than quartz subsamples (27.8 per mil to 35.7 per mil). Using the O-isotopic fractionation expression for quartz-water of Knauth and Epstein (1976) and assuming d18Opore water = -1.0 per mil, model temperatures of formation are 7°-26°C for carbonate-replacement quartz cherts, 22°-25°C for bedded quartz cherts, and 32°-34°C for thermal quartz cherts. Large variations in O-isotopic composition exist at the same burial depth between co-existing silica phases in the same sample and within the same phase in adjacent lithologies. For example, quartz has a wide range of isotopic compositions within a single breccia sample; d18O = 33.4 per mil and 28.0 per mil for early and late stages of fracture-filling cementation, and 31.6 per mil and 30.2 per mil for microcrystalline quartz precipitation within enclosed chert and radiolarite fragments. Similarly, opal-CT d101 spacing varies across lithologic or diagenetic boundaries within single samples. Co-occurring opal-CT and chalcedonic quartz in shallowly buried chert and porcellanite from Sites 800 and 801 have an 8.7 per mil difference in d18O, suggesting that pore waters in the Pigafetta Basin underwent a Tertiary shift to strongly 18O-depleted values due to alteration of underlying Aptian to Albian-Cenomanian volcaniclastic deposits after opal-CT precipitation, but prior to precipitation of microfossil-filling chalcedony.

Stable carbon isotope compositions and concentrations of biphytanes from IODP Hole 311-U1327C and 311-U1328B

We have investigated the distributions and carbon isotopic compositions of archaeal membrane lipids in gas-hydrate-bearing sediments collected from the northern Cascadia Margin offshore from Vancouver Island (Sites U1327 and U1328) by the R/V JOIDES Resolution during IODP Expedition 311. Archaeal lipid biomarkers, including glycerol dialkyl glycerol tetraethers (GDGTs), tend to become abundant below 100 mbsf (meters below sea floor). Tricyclic biphytane (BP[3]; which is a robust biomarker derived from GDGT), crenarchaeol, and other BPs exhibit d13C values of ca. -20 per mil, and become abundant between 130 and 230 mbsf at Site U1328. In this depth range, concentrations of ammonium and phosphate in interstitial waters also increase, suggesting that a larger population and higher activity of heterotrophic community consisting of crenarchaeota and other archaea decompose the sedimentary organic matter, thereby liberating ammonium and phosphate. Such crenarchaeotic activity can produce other metabolic products such as molecular hydrogen by fermentation of organic matter during diagenesis. Furthermore, near the organic matter decomposition zone (130 to 230 mbsf), a probable methanogen biomarker (13C-depleted BP[1] with d13C values as low as -48.8 per mil) becomes abundant, indicating that methanogens utilize these diagenetic products. The molecular and isotopic distributions of archaeal lipid biomarkers indicate that the archaeal community plays an important role in the biogeochemical cycles of deep-sea sediments, including both methanogenesis and nutrient recycling.

Late Pleistocene oxygen isotope record of biognic silica

We determined the isotopic composition of oxygen in marine diatoms in eight deep-sea cores recovered from the Atlantic sector of the Southern Ocean. The analytical reproducibility and core-to-core consistency of the isotopic signal suggests that diatom delta18O can be used as a new paleocenographic tool to reconstruct past variations in surface water characteristics and to generate 18O -isotope-based stratigraphy for the Southern Ocean. The data indicate that diatom delta18O reflects sea surface temperature and seawater isotopic composition and that diatoms retain their isotopic signal on timescales of a least 430 ka. The delta18O analyses of different diatom assemblages reveal that the isotopic signal is free of species effects and that the common Antarctic species have the same water-opal fractionation. The transition from the last glacial maximum (LGM) to the Holocene is fully recorded in high sedimentation rate cores. An 18O enrichment during the LGM, a post-LGM meltwater spike and an input of meltwater during the late Holocene are the main isotopic features observed in down core records. The origin of this meltwater was very likely melting icebergs and/or continental ice or by melting sea ice that had accumulated snow. The most pronounced meltwater effects are recorded in cores that are associated with the Weddel gyre. Our results provide the basis for extending isotope studies to oceanic regions devoid of carbonate; further, isotopic stratigraphies may be constructed for records and regions where they were previously not possible.

Helium isotope concentrations and ratios in sediments from ODP Hole 130-806B

We have determined the helium abundance and isotopic composition of seafloor carbonate sediments from the flanks of the Ontong Java Plateau, western equatorial Pacific Ocean (ODP Site 806). These results provide a two million year record of the burial flux of extraterrestrial 3He, which we believe is a proxy for the terrestrial accretion rate of interplanetary dust particles. The 3He burial flux prior to ~700 ka was relatively low, ~0.5 pcc/cm**2/kyr, but from 700 ka to the present, the burial flux gradually increased to a value of ~1.0 pcc/cm**2/kyr. 100 kyr periodicity in the 3He burial flux is apparent over the last 700 kyr and correlates with the oxygen isotope record of global climate, with high 3He burial fluxes associated with interglacial periods. This periodicity and phase are consistent with previous 3He measurements in North Atlantic sediments. Although 100 kyr periodicity in 3He burial flux is in agreement with recent predictions of the accretion rate of interplanetary dust based on a model of the orbital evolution of asteroidal debris, the measurements and predictions differ by one half cycle in phase. Nevertheless, our observations suggest the terrestrial accretion rate of interplanetary dust is controlled by orbital eccentricity and/or inclination relative to the solar-system invariable plane. Such control is a necessary but not sufficient condition for the hypothesis of that variations in extraterrestrial dust accretion modulates terrestrial climate with a 100 kyr period. We also identify several brief (<25 kyr) intervals of strongly enhanced 3He burial, possibly related to random and transient fluctuations in the accretion rate of asteroidal or cometary dust particles.