Pliocene-Pleistocene oxygen isotope record DSDP Site 586, Ontong Java Plateau, Pacific Ocean i

Oceanographic changes in the western equatorial Pacific during the past 6 Ma are inferred from oxygen isotopic analyses of planktic and benthic foraminifera from Ontong Java Plateau (DSDP Site 586). The taxa are Globigerinoides sacculifer, Pulleniatina, Cibicidoides wuellerstorfi, and Oridorsalis umbonatus. Cooling and ice buildup are indicated by an 18O enrichment of 0.3 per mil in the planktic species near 3.4 Ma. This shift apparently is compensated in the benthic data by a warming of the deep waters by between 1° and 2° C. We suggest that the dominant source of upper deep water supply to the Pacific changed from Antarctic to North Atlantic at that time, the North Atlantic-derived water being warmer. Near 2.8 Ma (approximately) the planktic foraminifera again record an enrichment in 18O (Delta delta18O=0.25 per mil). We suggest ice buildup in the northern hemisphere as the cause, because of subsequent sharp increase in fluctuations of the delta18O signal, that is, instability. The enrichment is magnified in the benthic foraminifera (Delta delta18O = 0.5 per mil) by a cooling of the deep water by 1.5° at the time, presumably signalling a glacial-type reduction of North Atlantic Deep Water (NADW) production. Episodic divergence between the signals of G. sacculifer and Pulleniatina in the Pleistocene apparently reflects periods of increased upwelling in the western equatorial Pacific. The amplitude of ice volume fluctuations cannot be reconstructed from delta18O data alone, unless there are constraints on temperature variations. The increase in amplitude of fluctuation of the benthic and planktic signals during the Pleistocene may be attributed either to an increase in maximum ice volume, or to an increase in the fractionation of continental ice, or a combination of both causes.

Stable isotope record of ODP Sites 108-658 and 108-659

Ocean Drilling Program Site 658, cored below a major upwelling cell offshore Cap Blanc, contains a largely undisturbed hemipelagic sediment section spanning the Brunhes Chron and the early Quaternary and late Pliocene. The companion Site 659 recovered a complete and undisturbed Neogene profile further offshore that serves as a nonupwelling pelagic reference section. Oxygen and carbon isotope ratios in benthic (C. wuellerstorfi and in part Uvigerina sp.) and planktonic foraminifers (G. inflata) provide a climatic record of high resolution for the Brunhes Chron. At Site 658 the record extends back to the early Pleistocene and late Pliocene. The standard oxygen isotope record of the last 730,000 yr is markedly refined by a well-documented high-frequency variation (e.g., by a new "aborted" ice age at stage 13.2 and by Younger-Dryas style climatic setbacks during most terminations). In the late Pliocene, the numerical oxygen isotope stage taxonomy was extended back to stage 137 about 3.3 Ma ago. In comparison with published records, stage 114 at 2.7 Ma represents the first major glaciation event, when 18O was short-term enriched up to a middle Pleistocene glacial d18O level. About 3.17 Ma ago (stage 133), the interglacial oxygen isotope values of C. wuellerstorfi started to increase by 0.5 per mil until 2.7 Ma and then remained largely constant until the Holocene. Based on the d13C difference between C. wuellerstorfi and G. inflata, the dissolved CO2 in the ambient bottom water of Site 658 was dominated by the flux of particulate carbon from the overlying upwelling cell during the last 630,000 yr. In contrast, the advection of (upper) North Atlantic Bottom Water dominated in the control of the local CO2 content during the early Pleistocene and late Pliocene.

Isotopic composition of the fine fraction of ODP Site 114-704

Ocean Drilling Program Site 704 in the subantarctic South Atlantic was drilled to investigate the response of the Southern Ocean to climatic and Oceanographic developments during the late Neogene. Stable oxygen and carbon isotopes of fine-fraction (<63 µm) carbonate were analyzed to supplement similar analyses of benthic and planktonic foraminifers. The fine fraction is generally composed primarily of coccoliths, and isotopic analyses of the fine fraction were made to complement the foraminiferal analyses. The isotopic curves thus generated suggest paleoceanographic changes not recognizable by the use of benthic and planktonic foraminifers alone. The global Chron 6 carbon isotope shift, found at 253-244 mbsf (6.39-6.0 Ma) at Site 704 in the planktonic and benthic record, is seen in the fine-fraction d13C record as a gradual decrease from 255 mbsf (6.44 Ma) to 210 mbsf (4.24 Ma). At 170 mbsf, mean d18O values of Neogloboquadrina pachyderma increase by 0.6 per mil-0.7 per mil (Hodell and Ciesielski, 1991, doi:10.2973/odp.proc.sr.114.150.1991), reflecting decreased temperature and increased continental ice volume. Accumulation rates increase by 3.3 times above this depth (which corresponds to an age of 2.5 Ma), suggesting increased upwelling and biologic productivity. Carbon isotopic values of fine-fraction carbonate decrease by about 1.5 per mil at 2.6 Ma; however, no change is recorded in the d13C of N. pachyderma. The fine-fraction d13C shift slightly precedes an average l per mil decrease in d13C in benthic foraminifers. The cause of the benthic d13C shift (most likely due to a change in deep water circulation; Hodell and Ciesielski, 1991) is probably not directly related to the fine-fraction shift. The fine-fraction shift is most likely caused by (1) a change in the upwelling to productivity ratio at this site, with increased upwelling bringing lighter carbon to surface waters, more productivity, and higher sedimentation rates and (2) a change in the particle composition of the fine fraction. The increased upwelling is probably due to a northward migration of the Antarctic Polar Front to a position nearer Site 704.

Isotopic record across the Aptian/Albian boundary of ODP Hole 171-1049C

Geochemical analyses of extraordinarily well preserved late Aptian-early Albian foraminifera from Blake Nose (Ocean Drilling Program Site 1049) reveal rapid shifts of d18O, d13C, and 87Sr/88Sr in the subtropical North Atlantic that may be linked to a major planktic foraminifer extinction event across the Aptian/Albian boundary. The abruptness of the observed geochemical shifts and their coincidence with a sharp lithologic contact is explained as an artifact of a previously undetected hiatus of 0.8-1.4 million years at the boundary contact, but the values before and after the hiatus indicate that major oceanographic changes occurred at this time. 87Sr/88Sr increase by ~0.000200, d13C values decrease by 1.5 per mil to 2.2 per mil, and d18O values decrease by ~1.0 per mil (planktics) to 0.5 per mil (benthics) across the hiatus. Further, both 87Sr/88Sr ratios and d18O values during the Albian are anomalously high. The 87Sr/88Sr values deviate from known patterns to such a degree that an explanation requires either the presence of inter-basin differences in seawater 87Sr/88Sr during the Albian or revision of the seawater curve. For d18O, planktic values in some Aptian samples likely reflect a diagenetic overprint, but preservation is excellent in the rest of the section. In well preserved material, benthic foraminiferal values are largely between 0.5 and 0.0 per mil and planktic samples are largely between 0.0 per mil to -1.0 per mil, with a brief excursion to -2.0 per mil during OAE 1b. Using standard assumptions for Cretaceous isotopic paleotemperature calculations, the d18O values suggest bottom water temperatures (at ~1000 -1500 m) of 8-10°C and surface temperatures of 10-14°C, which are 4-6°C and 10-16°C cooler, respectively, than present-day conditions at the same latitude. The cool subtropical sea surface temperature estimates are especially problematic because other paleoclimate proxy data for the mid-Cretaceous and climate model predictions suggest that subtropical sea surface temperatures should have been the same as or warmer than at present. Because of their exquisite preservation, whole scale alteration of the analyzed foraminifera is an untenable explanation. Our proposed solution is a high evaporative fractionation factor in the early Albian North Atlantic that resulted in surface waters with higher d18O values at elevated salinities than commonly cited in Cretaceous studies. A high fractionation factor is consistent with high rates of vapor export and a vigorous hydrological cycle and, like the Sr isotopes, implies limited connectivity among the individual basins of the Early Cretaceous proto-Atlantic ocean.

Simulated change in atmospheric CO2 and D14C around 14.6 kyr BP, at the onset of the northern hemispheric warming into the Bølling/Allerød

One of the most abrupt and yet unexplained past rises in atmospheric CO2 (10 p.p.m.v. in two centuries) occurred in quasi-synchrony with abrupt northern hemispheric warming into the Bølling/Allerød, 14,600 years ago. Here we use a U/Th-dated record of atmospheric D14C from Tahiti corals to provide an independent and precise age control for this CO2 rise. We also use model simulations to show that the release of old (nearly 14C-free) carbon can explain these changes in CO2 and D14C. The D14C record provides an independent constraint on the amount of carbon released (125 Pg C). We suggest, in line with observations of atmospheric CH4 and terrigenous biomarkers, that thawing permafrost in high northern latitudes could have been the source of carbon, possibly with contribution from flooding of the Siberian continental shelf during meltwater pulse 1A. Our findings highlight the potential of the permafrost carbon reservoir to modulate abrupt climate changes via greenhouse-gas feedbacks.

Mineralogy and stable oxygen isotope ratios of the Cretaceous-Tertiary boundary

Results of detailed mineralogical, chemical, and oxygen isotope analyses of the clay minerals and zeolites from two Cretaceous-Tertiary (K/T) boundary regions, Stevns Klint, Denmark, and Deep Sea Drilling Project (DSDP) Hole 465A in the north central Pacific Ocean, are presented. In the central part of the Stevns Klint K/T boundary layer, the only clay mineral detected by x-ray diffraction is a pure smectite with > 95 percent expandable layers. No detrital clay minerals or quartz were observed in the clay size fraction in these beds, whereas the clay minerals above and below the boundary layer are illite and mixed-layer smectite-illite of detrital origin as well as quartz. The mineralogical purity of the clay fraction, the presence of smectite only at the boundary, and the d18O value of the smectite (27.2 ± 0.2 per mil) suggest that it formed in situ by alteration of glass. Formation from impact rather than from volcanic glass is supported by its major element chemistry. The high content of iridium and other siderophile elements is not due to the cessation of calcium carbonate deposition and resulting slow sedimentation rates. At DSDP Hole 465A, the principal clay mineral in the boundary zone (80 to 143 centimeters) is a mixed-layer smectite-illite with >=90 percent expandable layers, accompanied by some detrital quartz and small amounts of a euhedral authigenic zeolite (clinoptilolite). The mixed-layer smectite-illite from the interval 118 to 120 centimeters in the zone of high iridium abundance has a very low rare earth element content; the negative cerium anomaly indicates formation in the marine environment. This conclusion is corroborated by the d18O value of this clay mineral (27.1 ± 0.2 per mil). Thus, this mixed-layer smectite-illite formed possibly from the same glass as the K/T boundary smectite at Stevns Klint, Denmark.

An early Eocene carbon cycle perturbation at in the Southern Alps

At least two transient events of extreme global warming occurred superimposed on the long-term latest Paleocene and early Eocene warming trend in the Paleocene-Eocene thermal maximum (PETM) (or ETM1 ~55.5 Ma) and the Elmo (or ETM2 ?53.6 Ma). Other than warmth, the best known PETM is characterized by (1) significant injection of 13C-depleted carbon into the ocean-atmosphere system, (2) deep-sea carbonate dissolution, (3) strong biotic responses, and (4) perturbations of the hydrological cycle. Documentation of the other documented and suspected "hyperthermals" is, as yet, insufficient to assess whether they are similar in nature to the PETM. Here we present and discuss biomagnetostratigraphic data and geochemical records across two lower Eocene successions deposited on a continental margin of the western Tethys: the Farra and Possagno sections in the Venetian pre-Alps. We recognize four negative carbon isotope excursions within chron C24. Three of these shifts correlate to known or suspected hyperthermals: the PETM, the Eocene thermal maximum 2 (~53.6 Ma), and the informally named "X event" (~52.5 Ma). The fourth excursion lies within a reverse subchron and occurred between the latter two. In the Farra section, the X event is marked by a ~0.6 per mil negative carbon isotope excursion and carbonate dissolution. Furthermore, the event exhibits responses among calcareous nannofossils, planktic foraminifera, and dinoflagellates that are similar to, though less intense than, those observed across the PETM. Sedimentological and quantitative micropaleontological data from the Farra section also suggest increased weathering and runoff as well as sea surface eutrophication during this event.

Measurements of trace metal abundances and isotopes in carbonate sediments, Exuma, Bahamas

In order to validate the use of 238U/235U as a paleoredox proxy in carbonates, we examined the incorporation and early diagenetic evolution of U isotopes in shallow Bahamian carbonate sediments. Our sample set consists of a variety of primary precipitates that represent a range of carbonate producing organisms and components that were important in the past (scleractinian corals, calcareous green and red algae, ooids, and mollusks). In addition, four short push cores were taken in different depositional environments to assess the impact of early diagenesis and pore water chemistry on the U isotopic composition of bulk carbonates. We find that U concentrations are much higher in bulk carbonate sediments (avg. 4.1 ppm) than in primary precipitates (avg. 1.5 ppm). In almost all cases, the lowest bulk sediment U concentrations were as high as or higher than the highest concentrations found in primary precipitates. This is consistent with authigenic accumulation of reduced U(IV) during early diagenesis. The extent of this process appears sensitive to pore water H2S, and thus indirectly to organic matter content. d238/235U values were very close to seawater values in all of the primary precipitates, suggesting that these carbonate components could be used to reconstruct changes in seawater U geochemistry. However, d238/235U of bulk sediments from the push cores was 0.2-0.4 per mil heavier than seawater (and primary precipitates). These results indicate that authigenic accumulation of U under open-system sulfidic pore water conditions commonly found in carbonate sediments strongly affects the bulk U concentrations and 238U/235U ratios. We also report the occurrence of dolomite in a tidal pond core which contains low 234U/238U and 238U/235U ratios and discuss the possibility that the dolomitization process may result in sediments depleted in 238U. From this initial exploration, it is clear that 238U/235U variations in ancient carbonate sediments could be driven by changes in global average seawater, by spatial and temporal variations in the local deposition environment, or subsequent diagenesis. To cope with such effects, proxies for syndepositional pore water redox conditions (e.g., organic matter content, iron speciation, and trace metal distributions) and careful consideration of possible post-deposition alteration will be required to avoid spurious interpretation of 238U/235U data from ancient carbonate sediments.

Major nannofossils, carbon and oxygen isotopes and carbon composition of ODP leg 194 site survey gravity cores

Biostratigraphic, sedimentologic, and geochemical analyses of hemipelagic periplatform sediments from shallow gravity cores taken during the Ocean Drilling Program Leg 194 site survey reveal that, despite the strong currents and almost infilled intraplatform bathymetric depressions, recent sedimentation at the location of the Leg 194 drill sites recorded glacial-interglacial cycles. Sediment analyses included determination of sediment type, carbonate content, bulk stable oxygen isotope composition, and calcareous nannofossil zones. Glacial periods, identified by elevated bulk d18O, are characterized by darker sediment color, coarser grain size, and lower carbonate content, whereas interglacial periods yield lighter-colored, finer, and carbonate-rich sediments. These data from the shallowmost few meters of Marion Plateau sediments complement the subsurface information of Leg 194 holes, in which the top few meters have not been analyzed in such a high-resolution fashion. In addition, these gravity cores are more likely to have recovered the sediments closest to the sediment/water interface as compared to the hydraulic piston cores collected during Leg 194.

Stable isotopes and calcium carbonate at DSDP Holes 85-574 and 85-574A

Detailed stable isotopic and calcium carbonate records (with a sampling resolution of 3000 yr.) from the middle Miocene section of hydraulic piston corer (HPC) Hole 574A provide a sequence that records the major shift in the oxygen isotopic composition of the world's oceans that occurred at about 14 Ma. The data suggest that this transition was rapid and spans about 30,000 yr. of sediment deposition. In intervals before and after the shift, the mean d18O values are characterized by a constant mean with a high degree of variability. The degree of variability in both the d18O and d13C records is comparable to that observed for the Pliocene and earliest Pleistocene and does not show a significant change before or after the major shift in the d18O record. Whereas the oxygen isotopic record is characterized by relatively stable mean values before and after the middle Miocene event, the d13C record shows a number of significant offsets in the mean value separated by intervals of high-frequency variations. Time and frequency domain analysis of all records from Hole 574A indicate that the frequency components shown to be related to orbital changes in the Pleistocene record are also present in the middle Miocene. The high variability observed in the Site 574 isotopic records places important constraints on models describing the role of formation of the Antarctic ice sheet during the middle Miocene climatic transitions. Thus, HPC Hole 574A provides a valuable sequence for detailed study of climatic variability during an important time in the Earth's history, although we cannot provide a definitive explanation of the major oxygen isotopic event of the middle Miocene.

Geochemistry and Mg-isotopes of carbonate sediments and porefluids of ODP Site 130-807

Deep-sea pore fluids are potential archives of ancient seawater chemistry. However, the primary signal recorded in pore fluids is often overprinted by diagenetic processes. Recent studies have suggested that depth profiles of Mg concentration in deep-sea carbonate pore fluids are best explained by a rapid rise in seawater Mg over the last 10-20 Myr. To explore this possibility we measured the Mg isotopic composition of pore fluids and carbonate sediments from Ocean Drilling Program (ODP) site 807. Whereas the concentration of Mg in the pore fluid declines with depth, the isotopic composition of Mg in the pore fluid increases from -0.78 per mil near the sediment-water interface to -0.15 per mil at 778 mbsf. The Mg isotopic composition of the sediment, with few important exceptions, does not change with depth and has an average d26Mg value of -4.72 per mil. We reproduce the observed changes in sediment and pore-fluid Mg isotope values using a numerical model that incorporates Mg, Ca and Sr cycling and satisfies existing pore-fluid Ca isotope and Sr data. Our model shows that the observed trends in magnesium concentrations and isotopes are best explained as a combination of two processes: a secular rise in the seawater Mg over the Neogene and the recrystallization of low-Mg biogenic carbonate to a higher-Mg diagenetic calcite. These results indicate that burial recrystallization will add Mg to pelagic carbonate sediments, leading to an overestimation of paleo-temperatures from measured Mg/Ca ratios. The Mg isotopic composition of foraminiferal calcite appears to be only slightly altered by recrystallization making it possible to reconstruct the Mg isotopic composition of seawater through time.

Geochemistry and isotopes at DSDP Site 68-503

Nodules occur in the siliceous calcareous ooze and siliceous marl at Site 503 in the eastern equatorial Pacific. They are present below a depth of about 11 meters throughout the green-colored reduced part of the section down to 228 meters, although they are most abundant between 30 and 85 meters. They are cylindrical or barrel-shaped, up to 70 mm long, and usually have an axial channel through them or are hollow. They appear to have formed around and/or within burrows. XRD studies and microprobe analyses show that they are homogeneous and consist of calcian rhododrosite and minor calcite; Mn is present to the extent of about 30%. Isotopic analyses of the carbonate give carbon values which range from -1.2 per mil to -3.8 per mil, and oxygen isotope compositions vary from +4.0 per mil to +6.0 per mil. These values are different from those for marine-derived carbonates as exemplified by the soft sediment filling of a burrow: d13C, -0.26 per mil; d18O, +1.05 per mil. The carbon isotope data indicate that carbonate derived (possibly indirectly) from seawater was mixed with some produced by organic diagenesis to form the nodules. The d18O values suggest that although they formed near the sediment surface, some modification or the introduction of additional diagenetic carbonate occurred during burial.

Dissolved inorganic carbon isotopes in pore waters of ODP Leg 204 sediments

Isotopic characterization of carbon in the dissolved inorganic carbon (DIC) pool is fundamental for a wide array of scientific studies directly related to gas hydrate research. In order to generate integrated and internally consistent data of d13C of DIC in pore waters from Hydrate Ridge, we used the modern continuous flow technology of a GasBench II automated sampler interfaced to a gas source stable isotope mass spectrometer for the rapid determination (~80 samples/day) of d13C DIC in small-volume water samples. The overall precision of this technique is conservatively estimated to be better than ±0.15 per mil (1 sigma), which is similar to the precision of methods in current use. Here we present the data generated from Ocean Drilling Program Leg 204 pore water samples.

Stable isotope record of the Okhotsk Sea

Stable isotope data on benthic foraminifera from more than 30 cores on the northern Emperor Seamounts and in the Okhotsk Sea are synthesized in paleohydrographic profiles spanning the depth range 1000-4000 m. Holocene (core-top) benthic foraminiferal d18O and d13C data are calibrated to modern hydrographic properties through measurements of d13C of SumCO2 and d18O of seawater. Cibicidoides stable isotope ratios are close to the d13C and equilibrium d18O of seawater, whereas Uvigerina d18O and d13C are variably offset from Cibicidoides. Glacial maximum d13C of Cibicidoides displays a different vertical profile than that of the Holocene. When results are adjusted by +0.32 per mil to account for the secular change in d13C during the last glacial maximum, the data coincide with the modern seawater and foraminiferal curves deeper than ~2 km. However, at shallower depths d13C gradually increases by as much as 1 per mil above the modern value. Furthermore, above 2 km the benthic d18O decreases by ~0.5 per mil. These results are consistent with a benthic front at ~2 km in the North Pacific (see Herguera et al., 1992), but they differ from interpretations based on trace metal data which indicate a source of nutrient-depleted deep water during glaciation. The isotopic data suggest that during glaciation there was a better ventilated watermass at intermediate depths in the far northwestern Pacific, it was relatively fresher than deep waters there, and deep waters were as nutrient-rich as today.

Calibration and application of B/Ca, Cd/Ca, and d11B in Neogloboquadrina pachyderma (sinistral)

The North Atlantic and Norwegian Sea are prominent sinks of atmospheric CO2 today, but their roles in the past remain poorly constrained. In this study, we attempt to use B/Ca and d11B ratios in the planktonic foraminifera Neogloboquadrina pachyderma (sinistral variety) to reconstruct subsurface water pH and pCO2 changes in the polar North Atlantic during the last deglaciation. Comparison of core-top results with nearby hydrographic data shows that B/Ca in N. pachyderma (s) is mainly controlled by seawater [B(OH)4]?/[HCO3]? with a roughly constant partition coefficient (KD =([B/Ca]of CaCO3)/([B(OH)4]-/[HCO3]-)of seawater) of 1.48 ± 0.15 * 10**-3 (2sigma), and d11B in this species is offset below d11B of the borate in seawater by 3.38 ± 0.71 per mil (2sigma). These values represent our best estimates with the sparse available hydrographic data close to our core-tops. More culturing and sediment trap work is needed to improve our understanding of boron incorporation into N. pachyderma (s). Application of a constant KD of 1.48 * 10**-3 to high resolution N. pachyderma (s) B/Ca records from two adjacent cores off Iceland shows that subsurface pCO2 at the habitat depth of N. pachyderma (s) (~50 m) generally followed the atmospheric CO2 trend but with negative offsets of ~10-50 ppmv during 19-10 ka. These B/Ca-based reconstructions are supported by independent estimates from low-resolution d11B measurements in the same cores. We also calibrate and apply Cd/Ca in N. pachyderma (s) to reconstruct nutrient levels for the same down cores. Like today's North Atlantic, past subsurface pCO2 variability off Iceland was significantly correlated with nutrient changes that might be linked to surface nutrient utilization and mixing within the upper water column. Because surface pCO2 (at 0 m water depth) is always lower than at deeper depths and if the application of a constant KD is valid, our results suggest that the polar North Atlantic has remained a CO2 sink during the calcification seasons of N. pachyderma (s) over the last deglaciation.