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.

North Atlantic late Miocene stable-isotope stratigraphy, biostratigraphy, and magnetostratigraphy

Upper Miocene foraminiferal nannofossil ooze and chalk from DSDP Hole 552A in the northeast Atlantic Ocean have been closely sampled for biostratigraphic, paleomagnetic, and stable-isotopic studies. Sampling at 10-cm intervals resulted in an uppermost Miocene isotope stratigraphy with a 1000- to 3000-yr. resolution. Covariance in benthic (Planulina wuellerstorfi) and planktonic (Globigerina bulloides) foraminiferal d18O records is taken as evidence for variability in continental ice volume. Our best estimate is that glacial maxima occurred at -5.0 and ~ 5.5 Ma and lasted no more than 20,000 yrs. These events probably lowered sea level by 60 m below the latest Miocene average. There is little oxygen-isotope evidence, however, for a prolonged glaciation during the last 2 m.y. of the late Miocene. High- and low-frequency variability in the d13C record of foraminifers is useful for correlation among North Atlantic DSDP Sites 408, 410, 522, 610, and 611, and for correlation with sites in other oceans. Similar d13C changes are seen in P. wuellerstorfi and G. bulloides, but the amplitude of the signal is always greater in G. bulloides. Variability in d13C common to both species probably reflects variability in the d13C of total CO2 in seawater. Major long-term features in the d13C record include a latest Miocene maximum (P. wuellerstorfi = 1.5 per mil ) in paleomagnetic Chron 7, an abrupt decrease in d13C at -6.2 Ma, and a slight increase at -5.5 Ma. The decrease in d13C at -6.2 Ma, which has been paleomagnetically dated only twice before, occurs in the upper reversed part of Chronozone 6 at Holes 552A and 611C, in excellent agreement with earlier studies. Cycles in d13C with a period of ~ 10 4 yrs. are interpreted as changes in seawater chemistry, which may have resulted from orbitally induced variability in continental biomass. Samples of P. wuellerstorfi younger than 6 Ma from throughout the North Atlantic have d13C near lo, on average ~ l per mil greater than samples of the same age in the Pacific Ocean. Thus, there is no evidence for cessation of North Atlantic Deep Water production resulting from the Messinian "salinity crisis." Biostratigraphic results indicate continuous sedimentation during the late Miocene after about -6.5 Ma at Hole 552A. Nannofossil biostratigraphy is complicated by the scarcity of low-latitude marker species, but middle and late Miocene Zones NN7 through NN11 are recognized. A hiatus is present at -6.5 Ma, on the basis of simultaneous first occurrences of Amaurolithusprimus, Amaurolithus delicatus, Amaurolithus amplificus, and Scyphosphaera globulata. The frequency and duration of older hiatuses increase downsection in Hole 552A, as suggested by calcareous nannofossil biostratigraphy and magnetostratigraphy. Paleomagnetic results at Hole 552A indicate a systematic pattern of inclination changes. Chronozone 6 was readily identified because of its characteristic nannoflora (sequential occurrences of species assigned to the genus Amaurolithus) and the d13C decrease in foraminifers, but its lower reversed interval is condensed. Only the lower normal interval of Chronozone 5 was recognized at Hole 552A; the upper normal interval and the lowest Gilbert sediment are not recognized, owing to low intensity of magnetization and to coring disturbance. Interpreting magnetic reversals below Chronozone 6 was difficult because of hiatuses, but a lower normally magnetized interval is probably Chronozone 7. Correlation between DSDP Hole 552A and other North Atlantic sites is demonstrated using coiling direction changes in the planktonic foraminifer Neogloboquadrina. At most sites this genus changed its coiling preference from dominantly right to dominantly left during the late Miocene. At Hole 552A this event probably occurred about 7 m.y. ago. At the same time, P. wuellerstorfi had maximum d13C values. A similar d13C maximum and coiling change occurred together in Chron 7 at Hole 611C, and at Hole 610E. In sediment younger than -5.5 Ma, the coiling of small Neogloboquadrina species is random, but the larger species N. atlantica retains preferential left coiling.

Sedimentology, planktonic foraminifera distribution and stable isotope composition during marine isotope stage 3 of ODP Site 172-1060 in the West Atlantic

We have studied Ocean Drilling Program Site 1060 on the Blake Outer Ridge, which lies beneath the Gulf Stream. We focus on marine isotope stage 3, 60-25 thousand years before present (ka). Sea surface temperatures (SSTs) inferred both from foraminiferal fauna and alkenone ratios, as well as counts of iceberg melt-out debris and benthic stable isotope analyses, enable our record to be interpreted in terms of regional hydrographic changes as well as changing thermohaline circulation (THC). The observed SST record is consistent with the air temperature record from the Greenland ice cores. However, Site 1060 exhibits important differences in detail compared with the ice core record, and when compared to other sites within the North Atlantic, significant longitudinal differences emerge. At Site 1060 in the western Atlantic, all Greenland stadials (GS) whether associated with Heinrich events (HEs) or not, show a similar small amplitude of cooling; mean faunal-based SSTaug during GS is only 1.5°C colder than during Greenland interstadials (GIS). In addition, during GS the coldest SSTs are limited to apparently brief events. This is in contrast to several eastern Atlantic sites where HE stadials exhibit coolings that are enhanced by 2°C compared to other GS and where cold conditions are not restricted to cold pulses but cover 2 ka-long intervals. Furthermore, Site 1060 SSTs remained warm right through each interstadial, in contrast to the sustained and uniform cooling trend through interstadials that is consistently observed in Greenland, indicated by measurements of delta18O in ice.

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.

Stable isotope ratios of planktonic foraminifera from the West Equatorial Pacific

Differential dissolution affects the isotopic composition of different species of planktonic foraminifera in different ways. In the two species studied here in cores from Ontong Java Plateau, the less resistant species, Globigerinoides sacculifer, is more readily affected at a shallower depth than the more resistant species, Pulleniatina obliquiloculata (2.9 versus 3.4 km), but shows a smaller and less predictable response to partial dissolution (0.2 to 0.3 per mil versus 0.6 to 0.7 per mil). Comparison of isotopic values from the last glacial period with those from the late Holocene indicates that the apparent dissolution effect is considerably reduced during the last glacial, presumably due to reduced dissolution intensity during glacial time. A change in the level of the lysocline of about 400 m is suggested. In the published isotope records from Pacific cores V28-238 and V28-239, the dissolution-generated difference in delta18O (noted previously by Shackleton and Opdyke [1976]) is seen to describe a mid-Brunhes dissolution maximum, between 300 and 500 thousand years ago. This mid-Brunhes dissolution excursion is well known from the Pacific and the Indian Ocean.

Stable isotope record of benthic foraminifera in late Pleistocene sediments

Variations in the contribution of North Atlantic Deep Water (NADW), relative to North Pacific Deep Water (NPDW), to the Southern Ocean, are assessed by comparing delta13C records from the mid-depth North Atlantic, deep Southern Ocean, and deep equatorial Pacific Ocean. In general, the relative contribution of NADW was greater during interglaciations than glaciations of the past 550,000 years. An increase in the NADW flux to the Southern Ocean since the last glaciation was proposed to have resulted in higher atmospheric CO2 in the Holocene (Broecker and Peng, 1989, doi:10.1029/GB003i003p00215). Glacial-interglacial variations in the proportion of NADW in the Southern Ocean may have also influenced atmospheric CO2 levels over the past 550,000 years. The greatest relative flux of NADW to the Southern Ocean occurred during interglacial stage 11. Faunal data suggest that the North Atlantic polar front and southern Indian Ocean subtropical convergence zone were located farthest poleward during stage 11. Warmth in these locations and a strong southward flux of NADW during stage 11 may be causally linked by the NADW formation process/warm water return route (Gordon, 1986, doi:10.1029/JC091iC04p05037). Time series analysis indicates that delta13C variations in the deep Southern Ocean occur at the same frequencies as the Earth's orbital variations and are coherent and in phase with delta18O. At most, 50% of the glacial-interglacial delta13C amplitude in the Southern Ocean is due changes in the contribution of NADW. The remainder is probably due to mean ocean delta13C changes.

High-resolution planktic stable isotope and trace element record of ODP Hole 161-976

Multi-decadal to centennial planktic d18O and Mg/Ca records were generated at ODP976 in the Alboran Sea. The site is in the flow path of Atlantic inflow waters entering the Mediterranean and captured North Atlantic signals through the surface inflow and the atmosphere. The records reveal similar climatic oscillations during the last two glacial-to-interglacial transitions, albeit with a different temporal pacing. Glacial termination 1 (T1) was marked by Heinrich event 1 (H1), post-H1 Bolling/Allerod (B/A) warming and Younger Dryas (YD) cooling. During T2 the H11 d18O anomaly was twice as high and lasted 30% longer than during H1. The post-H11 warming marked the start of MIS5e while the subsequent YD-style cooling occurred during early MIS5e. The post-H11 temperature increase at ODP976 matched the sudden Asian Monsoon Termination II at 129 ka BP. Extending the 230Th-dated speleothem timescale to ODP976 suggests glacial conditions in the Northeast Atlantic region were terminated abruptly and interglacial warmth was reached in less than a millennium. The early-MIS5e cooling and freshening at ODP976 coincided with similar changes at North Atlantic sites suggesting this was a basin-wide event. By analogy with T1 we argue that this was a YD-type event that was shifted into the early stages of the last interglacial period. This scenario is consistent with evidence from northern North Atlantic and Nordic Sea sites that the continuing disintegration of the large Saalian Stage (MIS6) ice sheet in Eurasia delayed the advection of warm North Atlantic waters and full-strength convective overturn until later stages of MIS5e.

Stable isotope ratios and geochemical composition of authigenic carbonates from ODP Sites 186-1150 and 186-1151

Several carbonaceous layers or fragments were recovered from sediments of Sites 1150 and 1151 on the deep-sea terrace of the Japan Trench during Leg 186. The X-ray diffraction analysis (XRD) data indicate that these are predominantly dolomitic. In this study, carbon and oxygen isotopes of these carbonates recovered at Sites 1150 and 1151 are presented. The oxygen isotope ratios of the dolomites analyzed range from +0.4 per mil to +4.1 per mil vs. Peedee formation belemnite (PDB) and those of calcites from +0.6 per mil to +2.8 per mil PDB. The isotopic composition of carbon varies from -7.0 per mil to +12.3 per mil PDB in dolomite and from -13.4 per mil to -24.1 per mil PDB in calcite. The wide range of carbon isotopic compositions indicates that the carbonate samples were formed by the decomposition of organic matter through reactions such as oxidation, sulfate reduction, and methane formation during diagenesis.

Stable isotope and geochemical record of ODP Hole 124-769A

Deep marine late Pleistocene sediments from Ocean Drilling Program Sulu Sea Site 769 contain a high-resolution record of paleoceanographic change in this strongly monsoonal climatic setting in the tropical western Pacific. Detailed time series of planktonic foraminifer (G.ruber; white variety) d18O, d13C, and bulk CaCO3 mass accumulation rate (MAR) were generated, spanning the last 750 k.y. Sedimentation rates in this portion of the record average 8.5 cm/k.y., and vary from 4 to 16 cm/k.y. Cross spectral analysis of the d18O and d13C time-series demonstrate that each contains increased variance at the primary orbital periodicities. The d18O record shows strong variability in the precessional-band and closely correlates with the SPECMAP d18O record and other high-resolution records. The dominance of a 23-k.y cycle in the d18O record agrees with other studies of the monsoon system in the Indian Ocean that have documented the importance of precessional insolation as a monsoon-forcing mechanism. In addition, d13C is strongly coherent, with d18O at a period of 41 k.y (obliquity), suggesting a connection between surface water CO2 chemistry in the Sulu Sea and high- latitude climatic change. The d18O and d13C time-series both contain increased spectral variance at a period of 30 k.y. Although the source of 30-k.y. variability is unknown, other studies have documented late Pleistocene Pacific Oceanographic variability with a period of 30 k.y. Major- and trace-metal analyses were performed on a second, less-detailed sample series to independently assess paleoproductivity changes and bottom-water conditions through time. Glacial periods are generally times of increased calcium carbonate and copper accumulation. The positive association between these independent indicators of paleoproductivity suggests an increase in productivity in the basin during most glacial episodes. Changing bottom-water redox conditions were also assessed using the geochemical data. Low concentrations of molybdenum throughout the record demonstrate that bottom waters at this site were never anoxic during the last 750 k.y. The bioturbated character of the sediments agrees with this interpretation.