Miocene stable isotope record of ODP Hole 162-982B

Oxygen and carbon isotope records are presented for the benthic foraminifer Cibicidoides wuellerstorfi from upper middle through lower upper Miocene (11.6-8.2 Ma) sediments recovered at intermediate water depth (1134 m) at Ocean Drilling Program Site 982 on Rockall Plateau. Oxygen isotopic values generally lighter than those for the Holocene indicate significantly warmer intermediate waters and/or less global ice volume during the late middle to early late Miocene than at the present. The most depleted oxygen isotope values occurred at around 10.5 Ma. After this time a long-term increase in d18O suggests a gradual increase in global ice volume and/or cooling of intermediate waters during the late Miocene. Comparison of the intermediate depth benthic foraminiferal carbon isotope record from Site 982 and records from various North Atlantic deep sites shows that intermediate waters were generally better ventilated than deep waters between 11.6 and 9.6 Ma. During this time period, increased ventilation of intermediate waters was linked to cooling or the build up of polar ice caps. The Mi events originally proposed by Miller et al. (1991, doi:10.1029/90JB02015) and Wright and Miller (1992, doi:10.2973/odp.proc.sr.120.193.1992) are difficult to identify with certainty in sediments sampled at high resolution (<10**4 year). Comparison of the high-resolution benthic d18O records from ODP Site 982 with the low-resolution benthic d18O record from Monte Gibliscemi (Mediterranean) show that Mi events, if real, may not be of importance as a stratigraphic tool in upper Miocene sedimentary sequences.

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.

Stable isotope record and sediment composition of the subantarctic Pacific

Benthic foraminiferal stable carbon isotope records from the South Atlantic show significant declines toward more "Pacific-like" values at ~7 and ~2.7 Ma, and it has been posited that these shifts may mark steps toward increased CO2 sequestration in the deep Southern Ocean as climate cooled over the late Neogene. We generated new stable isotope records from abyssal subantarctic Pacific cores MV0502-4JC and ELT 25-11. The record from MV0502-4JC suggests that the Southern Ocean remained well mixed and free of vertical or interbasinal d13C gradients following the late Miocene carbon shift (LMCS). According to the records from MV0502-4JC and ELT 25-11, however, cold, low d13C bottom waters developed in the Southern Ocean in the late Pliocene and persisted until ~1.7 Ma. These new data suggest that while conditions in the abyssal Southern Ocean following the LMCS were comparable to the present day, sequestration of respired CO2 may have increased in the deepest parts of the Southern Ocean during the late Pliocene, a critical period for the growth and establishment of the Northern Hemisphere ice sheets.

Mg/Ca and stable isotope record of benthic foraminifera of the Paleocene-Eocene Thermal Maximum

A rapid increase in greenhouse gas levels is thought to have fueled global warming at the Paleocene-Eocene Thermal Maximum (PETM). Foraminiferal magnesium/calcium ratios indicate that bottom waters warmed by 4° to 5°C, similar to tropical and subtropical surface ocean waters, implying no amplification of warming in high-latitude regions of deep-water formation under ice-free conditions. Intermediate waters warmed before the carbon isotope excursion, in association with downwelling in the North Pacific and reduced Southern Ocean convection, supporting changing circulation as the trigger for methane hydrate release. A switch to deep convection in the North Pacific at the PETM onset could have amplified and sustained warming.

Stable isotope stratigraphy of ODP Site 167-1014

Late Quaternary oxygen (d18O) and carbon (d13C) isotopic records for the benthic foraminifer Uvigerina and the planktonic foraminifer Globigerina bulloides are presented for the upper 20 meters composite depth sediment sequence of Ocean Drilling Program Site 1014, Tanner Basin, in the outer California Borderland province. The benthic oxygen isotopic record documents a continuous >160-k.y. sequence from marine isotope Stage (MIS) 6 to the present day. The record closely resembles other late Quaternary North Pacific benthic isotope records, as well as the well-dated deep-sea sequence (SPECMAP), and thus provides a detailed chronologic framework. Site 1014 provides a useful record of the California response to climate change as it enters the southern California Border-land. Sedimentation rates are relatively constant and high (~11.5 cm/k.y. ). The planktonic foraminiferal record is well pre-served except during marine isotope Substages 5b and 5d, when normally high G. bulloides abundance is strongly diminished as a result of dissolution. The planktonic oxygen isotopic shift of ~3 per mil between the last glacial maximum and the Holocene suggests a surface water temperature shift of <7°C, similar to estimates from Hole 893A (Leg 146) to the north. Unlike Santa Barbara Basin, G. bulloides d18O values during the last interglacial (MIS 5) at Site 1014 were significantly higher than during the Holocene. In particular, marine isotope Substage 5e (Eemian) was ~0.8 per mil higher. This is unlikely to reflect a cooler Eemian but is instead the result of preferential dissolution of thin-shelled (low d18O) specimens during this interval. In this mid-depth basin, a large benthic d18O shift during Termination I suggests dramatic temperature and salinity changes in response to switches in the source of North Pacific Intermediate Water. Although d13C values of the planktonic foraminifer G. bulloides are in disequilibria with seawater and hence interpretations are limited, the G. bulloides record exhibits several negative d13C excursions found at other sites in the region (Sites 1017 and 893). This indicates a response of G. bulloides d13C to regional surface water processes along the southern California margin. A general increase in benthic carbon isotopic values (-1.75 per mil to -0.75 per mil) in Tanner Basin during the last 200 k.y. is overprinted with smaller fluctuations correlated with climate change. The coolest intervals during the last glacial maximum (MISs 2 and 4) exhibit lower benthic d13C values, which correlate with global 13C shifts. The opposite relationship is exhibited during the last interglacial before 85 ka, when lower benthic d13C values are associated with warmer intervals (marine isotope Substages 5c and 5e) of the last interglacial. These time intervals were also marked by decreased intermediate water ventilation. Increased dissolution and organic accumulation during Substages 5b and 5d are anticorrelated with the benthic d13C record. These results suggest that a delicate balance in intermediate water d13C has existed between the relative influences of global 13C and regional ventilation changes at the 1165-m water depth of Site 1014.

Age models and stable isotope analysis on sediment core Site 199-1218 from the equatorial Pacific

A 13-million-year continuous record of Oligocene climate from the equatorial Pacific reveals a pronounced "heartbeat" in the global carbon cycle and periodicity of glaciations. This heartbeat consists of 405,000-, 127,000-, and 96,000-year eccentricity cycles and 1.2-million-year obliquity cycles in periodically recurring glacial and carbon cycle events. That climate system response to intricate orbital variations suggests a fundamental interaction of the carbon cycle, solar forcing, and glacial events. Box modeling shows that the interaction of the carbon cycle and solar forcing modulates deep ocean acidity as well as the production and burial of global biomass. The pronounced 405,000-year eccentricity cycle is amplified by the long residence time of carbon in the oceans.

Pleistocene stable isotope record of planktonic foraminifera of ODP Site 138-847

We present Pleistocene oxygen and carbon isotope records from two planktonic foraminifer species (Globigerinoides sacculifer and Neogloboquadrina dutertrei) from Ocean Drilling Program Site 847 (0°16'N, 95°19'W; 3334 m water depth). An average sample resolution of 4500 yr was obtained by sampling at an interval of 15 cm through a continuous 35-m section from 0 to 1.15 Ma. Our d18O-based chronology is similar to that derived independently by astronomically tuning the gamma-ray attenuation porosity evaluator (GRAPE) record (Shackleton et al., 1995), though offsets as large as ± 30 k.y. occur on occasion. The surface waters at eastern equatorial Pacific Site 847, 380 km west of the Galapagos, are characterized by strong and constant upwelling, elevated nutrient concentrations, and high productivity. The isotopic composition of G. sacculifer (300-355 µm) reflects conditions in the thin-surface mixed layer, and the composition of N. dutertrei (355-425 µm) monitors the subsurface waters of the permanent shallow (10-40 m) thermocline. The Pleistocene d18O difference (N. dutertrei minus G. sacculifer, Dd18Od-s) averages 0.9 per mil and ranges from 0 per mil to 1.7 per mil. Neglecting species effects and shell size, the average Pleistocene d13C difference (G. sacculifer minus N. dutertrei, Dd13Cs-d) is 0.0 per mil and ranges from -0.5 per mil to 0.5 per mil. The Dd18Od-s and Dd13Cs-d records are used to infer vertical contrasts in upper ocean water temperature and nutrient concentration, though d13C may also be influenced by other factors, such as CO2 gas exchange. Variations in the isotopic differences are often synchronous with glacial/interglacial climate change. Glacial periods are characterized by smaller vertical contrasts in both temperature and nutrient concentration, and by notably greater accumulation rates of N. dutertrei and CaCO3. We attribute these responses to greater upwelling at the equatorial divergence. Superimposed on the glacial/interglacial Dd18Od-s pattern is a long-term trend possibly associated with the advection of Peru Current waters. The temporal fluctuations in the isotopic contrasts are strikingly similar to those observed at Site 851 (Ravelo and Shackleton, this volume), suggesting that the inferred changes in thermal and chemical profiles occurred over a broad region in the equatorial Pacific.

Radiocarbon ages and stable isotope measurements on sediment cores of the subarctic Pacific and its marginal seas

Under modern conditions only North Pacific Intermediate Water is formed in the northwest Pacific Ocean. This situation might have changed in the past. Recent studies with general circulation models indicate a switch to deep-water formation in the northwest Pacific during Heinrich Stadial 1 (17.5-15.0 ka) of the last glacial termination. Reconstructions of past ventilation changes based on paleoceanographic proxy records are still insufficient to test whether a deglacial mode of deep-water formation in the North Pacific Ocean existed. Here we present deglacial ventilation records based on radiocarbon-derived ventilation ages in combination with epibenthic stable carbon isotopes from the northwest Pacific including the Okhotsk Sea and Bering Sea, the two potential source regions for past North Pacific ventilation changes. Evidence for most rigorous ventilation of the intermediate-depth North Pacific occurred during Heinrich Stadial 1 and the Younger Dryas, simultaneous to significant reductions in Atlantic Meridional Overturning Circulation. Concurrent changes in d13C and ventilation ages point to the Okhotsk Sea as driver of millennial-scale changes in North Pacific Intermediate Water ventilation during the last deglaciation. Our records additionally indicate that changes in the d13C intermediate-water (700-1750 m water depth) signature and radiocarbon-derived ventilation ages are in antiphase to those of the deep North Pacific Ocean (>2100 m water depth) during the last glacial termination. Thus, intermediate- and deep-water masses of the northwest Pacific have a differing ventilation history during the last deglaciation.

Middle Eocene bulk sediment, benthic and planktic foraminiferal stable isotope values, and relative weight percent CaCO3 content from ODP Site 207-1260

Major ice sheets were permanently established on Antarctica approximately 34 million years ago, close to the Eocene/ Oligocene boundary, at the same time as a permanent deepening of the calcite compensation depth in the world's oceans. Until recently, it was thought that Northern Hemisphere glaciation began much later, between 11 and 5million years ago. This view has been challenged, however, by records of ice rafting at high northern latitudes during the Eocene epoch and by estimates of global ice volume that exceed the storage capacity of Antarctica at the same time as a temporary deepening of the calcite compensation depth 41.6 million years ago. Here we test the hypothesis that large ice sheets were present in both hemispheres 41.6 million years ago using marine sediment records of oxygen and carbon isotope values and of calcium carbonate content from the equatorial Atlantic Ocean. These records allow, at most, an ice budget that can easily be accommodated on Antarctica, indicating that large ice sheets were not present in the Northern Hemisphere. The records also reveal a brief interval shortly before the temporary deepening of the calcite compensation depth during which the calcite compensation depth shoaled, ocean temperatures increased and carbon isotope values decreased in the equatorial Atlantic. The nature of these changes around 41.6 million years ago implies common links, in terms of carbon cycling, with events at the Eocene/Oligocene boundary and with the 'hyperthermals' of the Early Eocene climate optimum. Our findings help to resolve the apparent discrepancy between the geological records of Northern Hemisphere glaciation and model results that indicate that the threshold for continental glaciation was crossed earlier in the Southern Hemisphere than in the Northern Hemisphere.

Stable isotope ratios in shells of marine organisms

Oxygen and carbon isotope analyses have been carried out on calcareous skeletons of important recent groups of organisms. Annual temperature ranges and distinct developmental stages can be reconstructed from single shells with the aid of the micro-sampling technique made possible by modern mass-spectrometers. This is in contrast to the results of earlier studies which used bulk sampIes. The skeletons analysed are from Bermuda, the Philippines, the Persian Gulf and the continental margin off Peru. In these environments, seasonal salinity ranges and thus annual variations in the isotopic composition of the water are small. In addition, environmental parameters are weIl documented in these areas. The recognition of seasonal isotopic variations is dependant on the type of calcification. Shells built up by carbonate deposition at the margin, such as molluscs, are suitable for isotopic studies. Analysis is more difficult where chambers are added at the margin of the shell but where older chambers are simultaneously covered by a thin veneer of carbonate e. g. in rotaliid foraminifera. Organisms such as calcareous algae or echinoderms that thicken existing calcareous parts as weIl as growing in length and breadth are the most difficult to analyse. All organisms analysed show temperature related oxygen-isotope fractionation. The most recent groups fractionate oxygen isotopes in accordance with established d18O temperature relationships (Tab. 18, Fig. 42). These groups are deep-sea foraminifera, planktonic foraminifera, serpulids, brachiopods, bryozoa, almost all molluscs, sea urchins, and fish (otoliths). A second group of organisms including the calcareous algae Padina, Acetabularia, and Penicillus, as weIl as barnacles, cause enrichment of the heavy isotope 18O. Finally, the calcareous algae Amphiroa, Cymopolia and Halimeda, the larger foraminifera, corals, starfish, and holothurians cause enrichment of the lighter isotope 16O. Organisms causing non-equilibrium fractionation also record seasonal temperature variations within their skeletons which are reflected in stable-oxygen-isotope patterns. With the exception of the green algae Halimeda and Penicillus, all organisms analysed show lower d13C values than calculated equilibrium values (Tab. 18, Fig. 42). Especially enriched with the lighter isotope 12C are animals such as hermatypic corals and larger foraminifera which exist in symbiosis with other organisms, but also ahermatypic corals, starfish, and holothurians. With increasing age of the organisms, seven different d13C trends were observed within the skeletons. 1) No d13C variations are observed in deep-sea foraminifera presumably due to relatively stable environmental conditions. 2) Lower d13C values occur in miliolid larger foraminifera and are possibly related to increased growth with increasing age of the foraminifera. 3) Higher values are found in planktonic foraminifera and rotaliid larger foraminifera and can be explained by a slowing down of growth with increasing age. 4) A sudden change to lower d13C values at a distinct shell size occurs in molluscs and is possibly caused by the first reproductive event. 5) A low-high-Iow cycle in calcareous algae is possibly caused by variations in the stage of calcification or growth. 6) A positive correlation between d18O and d13C values is found in some hermatypic corals, all ahermatypic corals, in the septa of Nautilus and in the otoliths of fish. In hermatypic corals from tropical areas, this correlation is the result of the inverse relationship between temperature and light caused by summer cloud cover; in other groups it is inferred to be due to metabolic processes. 7) A negative correlation between d18O and d13C values found in hermatypic corals from the subtropics is explained by the sympathetic relationship between temperature and light in these latitudes. These trends show that the carbon isotope fractionation is controlled by the biology of the respective carbonate producing organisms. Thus, the carbon isotope distribution can provide information on the symbiont-host relationship, on metabolic processes and calcification and growth stages during ontogenesis of calcareous marine organisms.

Gas composition, concentration and stable isotope ratios (Table 2, 3, 4)

The deployment of CCS (carbon capture and storage) at industrial scale implies the development of effective monitoring tools. Noble gases are tracers usually proposed to track CO2. This methodology, combined with the geochemistry of carbon isotopes, has been tested on available analogues. At first, gases from natural analogues were sampled in the Colorado Plateau and in the French carbogaseous provinces, in both well-confined and leaking-sites. Second, we performed a 2-years tracing experience on an underground natural gas storage, sampling gas each month during injection and withdrawal periods. In natural analogues, the geochemical fingerprints are dependent on the containment criterion and on the geological context, giving tools to detect a leakage of deep-CO2 toward surface. This study also provides information on the origin of CO2, as well as residence time of fluids within the crust and clues on the physico-chemical processes occurring during the geological story. The study on the industrial analogue demonstrates the feasibility of using noble gases as tracers of CO2. Withdrawn gases follow geochemical trends coherent with mixing processes between injected gas end-members. Physico-chemical processes revealed by the tracing occur at transient state. These two complementary studies proved the interest of geochemical monitoring to survey the CO2 behaviour, and gave information on its use.