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.

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.

(Table 1) Strontium isotope data for marine carbonates of sediment core CRP-3

Strontium isotope stratigraphy was used to date 5 discrete horizons within the CRP-3 drillhole. A single in situ modiolid bivalve fragment at 10.88 mbsf gives an age of 30.9 (±0.8) Ma for the associated sediment. The four remaining well preserved fragments recovered from 29.94-190.31 mbsf are within error of this age, indicating a high sedimentation rate and suggesting little time is missing in disconformities. The diagenetic alteration of carbonate macrofossils by continental fluids (and possibly seawater) is a common feature to 320 mbsf.

Neodymium isotope ratios of fish debris from late Cretaceous black shales

Neodymium isotopes of fish debris from two sites on Demerara Rise, spanning ~4.5 m.y. of deposition from the early Cenomanian to just before ocean anoxic event 2 (OAE2) (Cenomanian-Turonian transition), suggest a circulation-controlled nutrient trap in intermediate waters of the western tropical North Atlantic that could explain continuous deposition of organic-rich black shales for as many as ~15 m.y. (Cenomanian-early Santonian). Unusually low Nd isotopic data (epsilon-Nd(t) ~-11 to ~-16) on Demerara Rise during the Cenomanian are confirmed, but the shallower site generally exhibits higher and more variable values. A scenario in which southwest-flowing Tethyan and/or North Atlantic waters overrode warm, saline Demerara bottom water explains the isotopic differences between sites and could create a dynamic nutrient trap controlled by circulation patterns in the absence of topographic barriers. Nutrient trapping, in turn, would explain the ~15 m.y. deposition of black shales through positive feedbacks between low oxygen and nutrient-rich bottom waters, efficient phosphate recycling, transport of nutrients to the surface, high productivity, and organic carbon export to the seafloor. This nutrient trap and the correlation seen previously between high Nd and organic carbon isotopic values during OAE2 on Demerara Rise suggest that physical oceanographic changes could be components of OAE2, one of the largest perturbations to the global carbon cycle in the past 150 m.y.

Age determination and sedimentology of sediment core Lz1101 from the Melles Lake

A lacustrine sediment core from Store Koldewey, northeast Greenland, was biogeochemically, biologically and sedimentologically investigated in order to reconstruct long- and short-term climatic and environmental variability. The chronology of the uppermost 189 cm of the record is based on ten 14C AMS age determinations of aquatic mosses. The record covers almost the entire Holocene and revealed changes on multidecadal to centennial scales. Dating of the oldest mosses shows that lacustrine biogenic productivity already began at around 11 cal. kyr BP. This age pre-dates the onset of biogenic productivity in other lakes on Store Koldewey by about 2 kyr. In spite of the early onset of biogenic production organic matter accumulation remained low and minerogenic sedimentation dominated. At about 9.5 cal. kyr BP moss, sulphur, organic carbon and biogenic silica content started to increase, indicating that the environment stabilized and the biogenic production in the lake adjusted to more preferable conditions. Subsequently, the biogenic productivity experienced repeated changes and varied both on long- and short-term scales. The long-term trend shows a maximum during the early Holocene thus responding to increased temperatures during the Holocene Thermal Maximum. Superimposed on the long-term trend, biogenic productivity also experienced repeated short-term fluctuations that match partly the NGRIP temperatures. The most pronounced decrease of biogenic productivity occurred at around 8.2 cal. kyr BP. Perennial lake ice coverage resulting from low temperatures is supposed to have caused decreased lacustrine biogenic productivity. From the middle Holocene to the present repeated decreases of productivity occurred that could be related to periods with severe sea-ice conditions of the East Greenland Current. Besides the dependence on air temperature it therefore demonstrates the sensitivity of lacustrine biogenic productivity in coastal high arctic areas to short-term cold spells that are mediated by the currents emanating from the Arctic Ocean. However, the data also emphasize the difficulties associated with the interpretation of lacustrine records.

Down-core sedimentary Sr-Nd isotope records from two Cape Basin sediment cores in the South Atlantic: GeoB3603-2 (Meteor cruise M34/1) and MD02-2594 (Marion Dufresne cruise MD128)

We report down-core sedimentary Nd isotope (epsilon Nd) records from two South Atlantic sediment cores, MD02-2594 and GeoB3603-2, located on the western South African continental margin. The core sites are positioned downstream of the present-day flow path of North Atlantic Deep Water (NADW) and close to the Southern Ocean, which makes them suitable for reconstructing past variability in NADW circulation over the last glacial cycle. The Fe-Mn leachates epsilon Nd records show a coherent decreasing trend from glacial radiogenic values towards less radiogenic values during the Holocene. This trend is confirmed by epsilon Nd in fish debris and mixed planktonic foraminifera, albeit with an offset during the Holocene to lower values relative to the leachates, matching the present-day composition of NADW in the Cape Basin. We interpret the epsilon Nd changes as reflecting the glacial shoaling of Southern Ocean waters to shallower depths combined with the admixing of southward flowing Northern Component Water (NCW). A compilation of Atlantic epsilon Nd records reveals increasing radiogenic isotope signatures towards the south and with increasing depth. This signal is most prominent during the Last Glacial Maximum (LGM) and of similar amplitude across the Atlantic basin, suggesting continuous deep water production in the North Atlantic and export to the South Atlantic and the Southern Ocean. The amplitude of the epsilon Nd change from the LGM to Holocene is largest in the southernmost cores, implying a greater sensitivity to the deglacial strengthening of NADW at these sites. This signal impacted most prominently the South Atlantic deep and bottom water layers that were particularly deprived of NCW during the LGM. The epsilon Nd variations correlate with changes in 231Pa/230Th ratios and benthic d13C across the deglacial transition. Together with the contrasting 231Pa/230Th: epsilon Nd pattern of the North and South Atlantic, this indicates a progressive reorganization of the AMOC to full strength during the Holocene.

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 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.

Age models and sea-surface paleotemperature reconstruction of sediment cores from the eastern equatorial Atlantic

Based on the faunal record of planktonic foraminifers in three long gravity sediment cores from the eastern equatorial Atlantic, the sea-surface temperature history ove the last 750,000 years was studied at a resolution of 3,000 to 10,000 years. Detailed oxygen-isotope and paleomagnetic stratigraphy helped to identify the following major faunal events: Globorotaloides hexagonus and Globorotalia tumida flexuosa became extinct in the eastern tropical Atlantic at the isotope stage 4/5 boundary, now dated at 68,000 years B.P. The persistent occurrence of the pink variety of Globigerinoides ruber started during the late stage 12 at 410,000 years B.P. CARTUNE-age. This datum may provide an easily detectible faunal stratigraphic marker for the mid-Brunhes Chron. The updated scheme of the Ericson zones helped the recognition of a hiatus at the northwestern slope of the Sierra Leone Basin covering oxygen-isotope stages 10 to 12. Classifying the planktonic foraminifer counts into six faunal assemblages, according to the factor analysis derived model of Pflaumann (1985), the tropical and the tropical-upwelling communities account for 57 % at Site 16415, and 86 % at Site 13519, respectively of the variance of the faunal record. A largely continuous paleotemperature record for both winter and summer seasons was obtained from the top of the Sierra Leone Rise with the winter temperatures ranging between 20 and 25 °C, and the summer ones between 24 and 30 °C. The record of cores from greater water depths is frequently interrupted by samples with no-analogue faunal communities and/or poor preservation. Based on the seasonality signal, during cold periods the termal equator shifted to a geographically mnore asymmetrical northern position. Dissolution altering the faunal communities becomes stronger with greater water depth, the estimated mean minimum loss of specimens increases from 70 % to 80 % between 2,860 and 3,850 water depth although some species will be more susceptible than others. Enhanced dissolution occured during stage 4 but also during cold phases in the warm stage 7 and 9. Correlations between the Foraminiferal Dissolution Index and the estimated sea-surface temperatures are significant. Foraminiferal flux rates, negatively correlated to the flux rates of organic carbon and of diatoms, may be a result of enhanced dissolution during cold stages, destroying still more of the faunal signal than indicated by the calculated minimum loss. The fluctuations of the oxygen-isotope curves and the hibernal sea-surfave temperatures are fairly coherent. During warm oxygen-isotope stages the temperature maxima lag often by 5 to 15 ka behind the respective sotope minima. During cold stages, sea-surface temperature changes are partly out of phase and contain additional fluctuations.

Stable oxygen and carbon isotope record of benthic foraminifera in Pliocene sediments of the Californian margin

New benthic foraminiferal stable isotopic records of northeast Pacific intermediate water (ODP Site 1014, 1177 m) and mid-depth water (ODP Site 1018, 2476 m) were compared to isotopic records of deep water in the tropical Pacific (ODP Site 849, 3851 m) for the reconstruction of vertical profiles of nutrient and physical properties from the Early Pliocene to the Early Pleistocene (approx. 5-1.4 Ma). Our data indicate that, for the entire interval, there was enhanced north Pacific intermediate water ventilation relative to today, and a similar to modern circulation pattern with northward flowing Pacific Bottom Water (PBW) beneath its southward flowing return flow. However, the core of maximally aged return flow resided as deep as ~2500 m (as compared to ~1500 m today), probably due to the strengthened intermediate water flow. Less apparent aging of deep water along its path before 2.7 Ma indicates that thermohaline overturning may have been more rapid in the warm period of the Early Pliocene. In addition, prior to 2.7 Ma, foraminiferal oxygen isotopic values at mid-depth sites are higher than at deep sites (a reversed vertical gradient relative to today) in both the Atlantic and Pacific Oceans. We suggest that NADW was warmer and more saline than today and that it influenced mid-depth waters throughout the Atlantic and Pacific Oceans. Enhanced Pliocene formation of warmer/saltier intermediate water in the north Pacific, and deep water in the north Atlantic, may have been a result of higher than modern high/mid-latitude sea surface temperatures, evaporation, and salinity.

Middle Miocene stable carbon and oxygen isotope record of ODP Holes 130-805B and 130-806B

Bulk carbon isotope records are an effective chemostratigraphic tool for the middle Miocene because of the large and systematic variation in first-order d13C signals. Bulk d13C measurements support the presence of a hiatus at 305 mbsf in Hole 805B (latest middle Miocene), provisionally located while on board ship using biostratigraphic and magnetostratigraphic events. Records at Holes 805B and 806B show the middle Miocene Monterey carbon isotope excursion although the record at Hole 806B is apparently more stratigraphically continuous. Detailed analysis of multispecies foraminiferal carbon isotope records during the middle Miocene ("Monterey excursion") segment at Hole 806B support the assertion that this carbon isotope excursion comprises mainly between-reservoir effects. The benthic d18O data increase after 15.3 Ma, which we suggest corresponds to the mid-Miocene cooling step/ice volume increase of other authors. Planktonic foraminiferal d18O evidence exists for steepening of the thermocline at 17.4 Ma. A second-order d13C excursion superimposed at 13.8 Ma on the first-order Monterey excursion is associated with a second-order negative d18O excursion.

Sable isotope record and sediment composition of Cretaceous samples of Deremara Rise

We estimate tropical Atlantic upper ocean temperatures using oxygen isotope and Mg/Ca ratios in well-preserved planktonic foraminifera extracted from Albian through Santonian black shales recovered during Ocean Drilling Program Leg 207 (North Atlantic Demerara Rise). On the basis of a range of plausible assumptions regarding seawater composition at the time the data support temperatures between 33° and 42°C. In our low-resolution data set spanning ~84-100 Ma a local temperature maximum occurs in the late Turonian, and a possible minimum occurs in the mid to early late Cenomanian. The relation between single species foraminiferal d18O and Mg/Ca suggests that the ratio of magnesium to calcium in the Turonian-Coniacian ocean may have been lower than in the Albian-Cenomanian ocean, perhaps coincident with an ocean 87Sr/86Sr minimum. The carbon isotopic compositions of distinct marine algal biomarkers were measured in the same sediment samples. The d13C values of phytane, combined with foraminiferal d13C and inferred temperatures, were used to estimate atmospheric carbon dioxide concentrations through this interval. Estimates of atmospheric CO2 concentrations range between 600 and 2400 ppmv. Within the uncertainty in the various proxies, there is only a weak overall correspondence between higher (lower) tropical temperatures and more (less) atmospheric CO2. The GENESIS climate model underpredicts tropical Atlantic temperatures inferred from ODP Leg 207 foraminiferal d18O and Mg/Ca when we specify approximate CO2 concentrations estimated from the biomarker isotopes in the same samples. Possible errors in the temperature and CO2 estimates and possible deficiencies in the model are discussed. The potential for and effects of substantially higher atmospheric methane during Cretaceous anoxic events, perhaps derived from high fluxes from the oxygen minimum zone, are considered in light of recent work that shows a quadratic relation between increased methane flux and atmospheric CH4 concentrations. With 50 ppm CH4, GENESIS sea surface temperatures approximate the minimum upper ocean temperatures inferred from proxy data when CO2 concentrations specified to the model are near those inferred using the phytane d13C proxy. However, atmospheric CO2 concentrations of 3500 ppm or more are still required in the model in order to reproduce inferred maximum temperatures.