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.

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.

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.

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 record of planktic foraminifera sampled by plankton haul and in surface sediments off North-West Africa

Foraminifera shells from modern sediments document the hydrography of the coastal upwelling region off Northwest-Africa (12-35° N) through the stable isotopic composition of their shells. Oxygen isotopes in planktonic foraminifers reflect sea surface temperatures (SST) during the main growing season of the differnt species: Globigerinoides ruber (pink and white) and G. sacculifer delineate the temperatures of the summer, Globorotalia inflata and Pulleniatina obliquiloculata those of the winter. Oxygen isotopes on Globigerina bulloides document temperature ranges of the upwelling seasons. d18O values in planktonic foraminifera from plankton hauls resemble those from the surface sediment samples, if the time of the plankton collection is identical with that of the main growing season of the species. The combined isotopic record of G. ruber (white) and G. inflata clearly reveals the latitudinal variations of the annual mean SST. The deviation of the d18O values from both species from their common mean is a scale for the seasonality, i.e. the maximum temperature range within one year. Thus in the summer upwelling region (north of 25° N) seasonality is relatively low, while it becomes high in the winter upwelling region south of 20° N. Furthermore, the winter upwelling region is characterized by relatively high d18O values - indicating low temperatures - in G. bulloides, the region of summer upwelling by relatively low d180 values compared with the constructed annual mean SST. Generally, carbon isotopes from the plankton hauls coincide with those from sediment surface samples. The enrichment of 13C isotopes in foraminifers from areas with high primary production can be caused by the removal of 12C from the total dissolved inorganic carbon during phytoplankton blooms. It is found that carbon isotopes from plankton hauls off Northwest-Africa are relatively enriched in 13C compared with samples from the western Atlantic Ocean. Also shells of G. ruber (pink and white) from upwelling regions are enriched in the heavier isotope compared with regions without upwelling. In the sediment, the enrichement of 13C due to high primary production can only be seen in G. bulloides from the high fertile upwelling region south of 20° N. North of this latitude values are relatively low. An enrichment of 12C is observed in shells of G. ruber (pink), G. inflata and P. obliquiloculata from summer-winter- and perennial upwelling regions respectively. Northern water masses can be distinguished from their southern counterparts by relatively high oxygen and carbon values in the "living" (=stained) benthic foraminifera Uvigerina sp. and Hoeglundina elegans. A tongue of the Mediterranean Outflow water can be identified far to the south (20° N) by 13C-enriched shells of these benthic foraminifera. A zone of erosion (15-25° N, 300-600 m) with a subrecent sediment surface can be mapped with the help of oxygen isotopes in "dead" benthic specimens. Comparison of d18O values in aragonitic and calcitic benthic foraminifers does not show a differential influence of temperature on the isotopic composition in the carbonate. However, carbon isotopes reflect slightly differences under the influence of temperature.