Mid-Pleistocene (800-400 ka) records of benthic and planktic foraminfer d18O and d13C, planktic foraminifer based SST, and IRD of IODP Site 306-U1314

Stable carbon and oxygen isotopes from benthic and planktic foraminifers, planktic foraminifer assemblages and ice rafted debris from the North Atlantic Site U1314 (Integrated Ocean Drilling Program Expedition 306) were examined to investigate orbital and millennial-scale climate variability in the North Atlantic and its impact on global circulation focusing on the development of glacial periods during the mid-Pleistocene (ca 800-400 ka). Glacial initiations were characterized by a rapid cooling (6-10 °C in less than 7 kyr) in the mean annual sea surface temperature (SST), increasing benthic d18O values and high benthic d13C values. The continuous increase in benthic d18O suggests a continuous ice sheet growth whereas the positive benthic d13C values indicate that the flow of the Iceland Scotland Overflow water (ISOW) was vigorous. Strong deep water formation in the Norwegian Greenland Sea promoted a high transfer of freshwater from the ocean to the continents. However, low SSTs at Site U1314 suggest a subpolar gyre cooling and freshening that may have reduced deep water formation in the Labrador Sea during glacial initiations. Once the 3.5 per mil threshold in the benthic d18O record was exceeded, ice rafting started and ice sheet growth was punctuated by millennial-scale waning events which returned to the ocean part of the freshwater accumulated on the continents. Ice-rafting events were associated with a rapid reduction in the ISOW (benthic d13C values dropped 0.5-1 per mil) and followed by millennial-scale warmings. The first two millennial-scale warm intervals of each glacial period reached interglacial temperatures and were particularly abrupt (6-10 °C in ~3 kyr). Subsequent millennial-scale warm events were cooler probably because the AMOC was rather reduced as suggested by the low benthic d13C values. These two abrupt warming events that occurred at early glacial periods were also observed in the Antarctic temperature and CO2 records, suggesting a close correlation between both Hemispheres. The comparison of the sea surface proxies with the benthic d18O record (as the Southern sign) indicates the presence of a millennial-scale seesaw pattern similar to that seen during the Last Glacial period.

Carbon and deuterium isotopes and C ratios in gas hydrates of ODP Leg 204 sites

Sediments at the southern summit of Hydrate Ridge display two distinct modes of gas hydrate occurrence. The dominant mode is associated with active venting of gas exsolved from the accretionary prism and leads to high concentrations (15%-40% of pore space) of gas hydrate in seafloor or near-surface sediments at and around the topographic summit of southern Hydrate Ridge. These near-surface gas hydrates are mainly composed of previously buried microbial methane but also contain a significant (10%-15%) component of thermogenic hydrocarbons and are overprinted with microbial methane currently being generated in shallow sediments. Focused migration pathways with high gas saturation (>65%) abutting the base of gas hydrate stability create phase equilibrium conditions that permit the flow of a gas phase through the gas hydrate stability zone. Gas seepage at the summit supports rapid growth of gas hydrates and vigorous anaerobic methane oxidation. The other mode of gas hydrate occurs in slope basins and on the saddle north of the southern summit and consists of lower average concentrations (0.5%-5%) at greater depths (30-200 meters below seafloor [mbsf]) resulting from the buildup of in situ-generated dissolved microbial methane that reaches saturation levels with respect to gas hydrate stability at 30-50 mbsf. Net rates of sulfate reduction in the slope basin and ridge saddle sites estimated from curve fitting of concentration gradients are 2-4 mmol/m**3/yr, and integrated net rates are 20-50 mmol/m**2/yr. Modeled microbial methane production rates are initially 1.5 mmol/m**3/yr in sediments just beneath the sulfate reduction zone but rapidly decrease to rates of <0.1 mmol/m**3/yr at depths >100 mbsf. Integrated net rates of methane production in sediments away from the southern summit of Hydrate Ridge are 25-80 mmol/m**2/yr. Anaerobic methane oxidation is minor or absent in cored sediments away from the summit of southern Hydrate Ridge. Ethane-enriched Structure I gas hydrate solids are buried more rapidly than ethane-depleted dissolved gas in the pore water because of advection from compaction. With subsidence beneath the gas hydrate stability zone, the ethane (mainly of low-temperature thermogenic origin) is released back to the dissolved gas-free gas phases and produces a discontinuous decrease in the C1/C2 vs. depth trend. These ethane fractionation effects may be useful to recognize and estimate levels of gas hydrate occurrence in marine sediments.

Occurrence and isotopic composition (d18O, d13C) of benthic foraminifera in sediments from DSDP Leg 72

Changes in the vertical water mass structure of the Vema Channel during the Pliocene have been inferred from benthic foraminiferal assemblages and stable isotopic analyses from three sites of DSDP Leg 72 (South Atlantic). Faunal and isotopic results from Sites 516A and 518 suggest that a major change occurred in deep-water circulation patterns in the late Pliocene near 3.2 Ma. Benthic oxygen isotopic records from Sites 516A and 518 show a characteristic increase in d18O values near 3.2 Ma. This has been documented in numerous Pliocene isotopic records. The magnitude of the oxygen isotopic enrichment near 3.2 Ma appears to increase with water depth from an average enrichment of 0.34 per mil in Site 516A (1313 m) to an average enrichment of 0.58 per mil in Site 518 (3944 m). We suggest that this enrichment resulted partly from a change in deep-water circulation patterns which included a decrease in bottom-water temperatures. Planktonic d18O values near 3.2 Ma show no evidence of an enrichment which would be indicative of an increase in global ice volume. On the contrary, d18O values in Sites 517 and 518 become more depleted near 3.2 Ma, indicating a surface-water warming perhaps due to a change in the strength and/or position of the Brazil Current. An increase in the relative abundance of the benthic foraminifer Nuttalides umbonifera, which is associated with Antarctic Bottom Water (AABW) in the modern ocean, coincides with the benthic 18O enrichment in Site 518. At 3.2 Ma, oxygen and carbon isotopic gradients between Sites 518 (3944 m) and 516A (1313 m) show a marked increase such that Site 518 becomes enriched in 18O and depleted in 13C relative to Site 516A. This enrichment in d18O is interpreted as partly representing a temperature decrease at Site 518; the depletion in d13C indicates a corrosive water mass which is high in metabolic CO2. We suggest that benthic foraminiferal and stable isotopic changes in Site 518 resulted from a pulse-like increase in the formation of AABW near 3.2 Ma. The cause of this circulation event may have been linked to global cooling and/or the final closure of the Central American Seaway.

Natural remanent magnetization (NRM) from ODP Site 1263 covering magnetochron C20r and C21n and high-resolution bulk carbon isotope (d13C) records from Sites 702 and 1263

To explore cause and consequences of past climate change, very accurate age models such as those provided by the astronomical timescale (ATS) are needed. Beyond 40 million years the accuracy of the ATS critically depends on the correctness of orbital models and radioisotopic dating techniques. Discrepancies in the age dating of sedimentary successions and the lack of suitable records spanning the middle Eocene have prevented development of a continuous astronomically calibrated geological timescale for the entire Cenozoic Era. We now solve this problem by constructing an independent astrochronological stratigraphy based on Earth's stable 405 kyr eccentricity cycle between 41 and 48 million years ago (Ma) with new data from deep-sea sedimentary sequences in the South Atlantic Ocean. This new link completes the Paleogene astronomical timescale and confirms the intercalibration of radioisotopic and astronomical dating methods back through the Paleocene-Eocene Thermal Maximum (PETM, 55.930 Ma) and the Cretaceous-Paleogene boundary (66.022 Ma). Coupling of the Paleogene 405 kyr cyclostratigraphic frameworks across the middle Eocene further paves the way for extending the ATS into the Mesozoic.

Miocene Mediterranean Nd, Sr, C and O isotope composition

Isotopic compositions of marine sediments and fossils have been investigated from northern basins of the Mediterranean to help constrain local oceanographic and climatic changes adjacent to the uplifting Alps. Stable C and O isotope compositions of benthic and planktonic foraminifera from the Umbria-Marche region (UMC) have an offset characteristic for their habitats and the changes in composition mimic global changes, suggesting that the regional conditions of climate and the carbon cycle were controlled by global changes. The radiogenic isotope composition of these fossil assemblages allows recognition of three distinct periods. In the first period, from 25 to 19 Ma, high epsilon-Nd values and low 87Sr/86Sr of sediments and fossils support intense tectonism and volcanism, related to the opening of the western Mediterranean. In the second period, from 19 to 13 Ma the 87Sr/86Sr ratio of Mediterranean (UMC) deviate from the global ocean, which is compatible with rapid uplift of the hinterland and intense influx of Sr from Mesozoic carbonates of the western Apennines. This local control on the seawater was driven by a humid and warm climate and indicates restricted exchange of water with the global ocean. Generally, the epsilon-Nd values of the fossils are very similar to those of Indian Ocean water, with brief periods of a decrease in the epsilon-Nd values coinciding with volcanic events and maybe sea level variation at 15.2 Ma. In the third period, from 13 to 10 Ma the fossils have 87Sr/86Sr similar to those of Miocene seawater while their epsilon-Nd values change considerably with time. This indicates fluctuating influence of the Atlantic versus the Paratethys and/or locally evolved seawater in the Mediterranean driven by global sea level changes. Other investigated localities near the Alps and from the ODP 900 site are compatible with this oceanographic interpretation. However, in the late early Miocene, enhanced local control, reflecting erosion of old crustal silicate rocks near the Alps, results in higher 87Sr/86Sr.

C and H geochemistry of altered oceanic crus of ODP/IODP Hole 1256D

Carbon and hydrogen concentrations and isotopic compositions were measured in 19 samples from altered oceanic crust cored in ODP/IODP Hole 1256D through lavas, dikes down to the gabbroic rocks. Bulk water content varies from 0.32 to 2.14 wt% with dD values from -64per mil to -25per mil. All samples are enriched in water relative to fresh basalts. The dD values are interpreted in terms of mixing between magmatic water and another source that can be either secondary hydrous minerals and/or H contained in organic compounds such as hydrocarbons. Total CO2, extracted by step-heating technique, ranges between 564 and 2823 ppm with d13C values from -14.9per mil to -26.6per mil. As for water, these altered samples are enriched in carbon relative to fresh basalts. The carbon isotope compositions are interpreted in terms of a mixing between two components: (1) a carbonate with d13C = -4.5per mil and (2) an organic compound with d13C = -26.6per mil. A mixing model calculation indicates that, for most samples (17 of 19), more than 75% of the total C occurs as organic compounds while carbonates represent less than 25%. This result is also supported by independent estimates of carbonate content from CO2 yield after H3PO4 attack. A comparison between the carbon concentration in our samples, seawater DIC (Dissolved Inorganic Carbon) and DOC (Dissolved Organic Carbon), and hydrothermal fluids suggests that CO2 degassed from magmatic reservoirs is the main source of organic C addition to the crust during the alteration process. A reduction step of dissolved CO2 is thus required, and can be either biologically mediated or not. Abiotic processes are necessary for the deeper part of the crust (>1000 mbsf) because alteration temperatures are greater than any hyperthermophilic living organism (i.e. T > 110 °C). Even if not required, we cannot rule out the contribution of microbial activity in the low-temperature alteration zones. We propose a two-step model for carbon cycling during crustal alteration: (1) when "fresh" oceanic crust forms at or close to ridge axis, alteration starts with hot hydrothermal fluids enriched in magmatic CO2, leading to the formation of organic compounds during Fischer-Tropsch-type reactions; (2) when the crust moves away from the ridge axis, these interactions with hot hydrothermal fluids decrease and are replaced by seawater interactions with carbonate precipitation in fractures. Taking into account this organic carbon, we estimate C isotope composition of mean altered oceanic crust at ? -4.7per mil, similar to the d13C of the C degassed from the mantle at ridge axis, and discuss the global carbon budget. The total flux of C stored in the altered oceanic crust, as carbonate and organic compound, is 2.9 ± 0.4 * 10**12 molC/yr.

Sulphate and d34S in pore waters and d13C, d18O and mineral composition of carbonate nodules from ODP Leg 188 sites

Carbon and oxygen isotopic compositions of authigenic carbonate nodules or layers reflect the diagenetic conditions at the time of nodule growth. The shallowest samples of carbonate nodules and dissolved inorganic carbon of pore water samples beneath the sulfate reduction zone (0-160 meters below seafloor [mbsf]) at Site 1165 have extremely negative d13C values (-50 per mil and -62 per mil, respectively). These negative d13C values indicate nodule formation in association with anaerobic methane oxidation coupled with sulfate reduction. The 34S of residual sulfate at Site 1165 shows only minor 34S enrichment (+6 per mil), even with complete sulfate reduction. This small degree of apparent 34S enrichment is due to extreme "open-system" sulfate reduction, with sulfate abundantly resupplied by diffusion from overlying seawater. Ten calcite nodules from Site 1165 contain minor quartz and feldspar and have d13C values ranging from -49.7 per mil to -8.2 per mil. The nodules with the most negative d13C values currently are at depths of 273 to 350 mbsf and must have precipitated from carbonate largely derived from subsurface anaerobic methane oxidation. The processes of sulfate reduction coupled with methane oxidation in sediments of Hole 1165B are indicated by characteristic concentration and isotopic (d34S and d13C) profiles of dissolved sulfate and bicarbonate. Three siderite nodules from Site 1166 contain feldspar and mica and one has significant carbonate-apatite. The siderite has d13C values ranging from -15.3 per mil to -7.6 per mil. These siderite nodules probably represent early diagenetic carbonate precipitation during microbial methanogenesis.

Lithology, stage, organic carbon, d13C, hydrocarbons and fatty acids at DSDP Hole 93-603B

Organic-matter-rich Upper Cretaceous claystones from DSDP Hole 603B, lower continental rise, had organic carbon values ranging from 1.7 to 13.7%, C/N ratios from 32 to 72, and d13C values from -23.5 to -27.1 per mil. Lipid class maxima for the unbound alkanes (C29 and C31), unbound fatty acids (C28 and C30), and bound fatty acids (C24, C26 , and C28) and the strong odd-carbon and even-carbon preferences, respectively, suggested that the organic matter in these sediments was partially the result of input from continental plant waxes. Transport of the organic-matter-rich sediments to the deep sea from the near-shore environment probably resulted from turbiditic flow under oxygen-stressed conditions.

(Table 1) Calcite, siderite, and stable isotopes d13C and d18O at DSDP Hole 93-603B

Diagenesis of the fine-grained, feldspathic sandstones in the Lower Cretaceous submarine fan complex cored in DSDP Hole 603B can be considered to have occurred in three stages: (1) replacement of matrix and framework grains by pyrite, siderite, phillipsite (?), and particularly by ferroan calcite; (2) dissolution of ferroan calcite and feldspars to produce secondary macroporosity; and (3) development of sparse feldspar and quartz overgrowths, and authigenic modification of remnant matrix. Only ferroan calcite is a volumetrically important diagenetic mineral phase (up to 50 vol.%). Matrix in thin sandstone turbidite deposits has been extensively replaced by ferroan calcite. Carbon stable isotope data suggest that organic diagenesis had only a minor influence on calcite precipitation. Oxygen stable isotope data indicate that the minimum average calcite precipitation temperature was 40° C. Preliminary calculations show that steadystate diffusion of Ca+ + from the dissolution of nannoplankton skeletal material in the interbedded pelagic marls to the associated sandstones is a feasible transport mechanism. A thick sandstone unit from 1234-1263 m sub-bottom is extensively replaced by calcite near the upper and lower contacts. Farther into the sand body away from the contacts, the sandstone has good secondary porosity resulting from the dissolution of ferroan calcite that partially replaced matrix and framework grains. The central portion of the thick sand appears to be a channel with high-energy clean sand. We believe that the channel provided a conduit for focused flow of diagenetic compactional fluids responsible for dissolution. Focused flow may be the result of the earlier lithification of the pelagic limestones and thin-bedded sandstones which, then formed vertical permeability barriers. Calcite dissolution has occurred and may still be occurring at temperatures less than 65°C.

Carbon isotopic record of CO2 from the Holocene of the Dome C ice core

Reconstructions of atmospheric CO2 concentrations based on Antarctic ice cores reveal significant changes during the Holocene epoch, but the processes responsible for these changes in CO2 concentrations have not been unambiguously identified. Distinct characteristics in the carbon isotope signatures of the major carbon reservoirs (ocean, biosphere, sediments and atmosphere) constrain variations in the CO2 fluxes between those reservoirs. Here we present a highly resolved atmospheric d13C record for the past 11,000 years from measurements on atmospheric CO2 trapped in an Antarctic ice core. From mass-balance inverse model calculations performed with a simplified carbon cycle model, we show that the decrease in atmospheric CO2 of about 5 parts per million by volume (p.p.m.v.) and the increase in d13C of about 0.25% during the early Holocene is most probably the result of a combination of carbon uptake of about 290 gigatonnes of carbon by the land biosphere and carbon release from the ocean in response to carbonate compensation of the terrestrial uptake during the termination of the last ice age. The 20 p.p.m.v. increase of atmospheric CO2 and the small decrease in d13C of about 0.05% during the later Holocene can mostly be explained by contributions from carbonate compensation of earlier land-biosphere uptake and coral reef formation, with only a minor contribution from a small decrease of the land-biosphere carbon inventory.