Stable isotope and Magnesium/Calcium ratios of 4 profiles from the equatorial Pacific/Caribbean

This thesis examines the closure history of the Central American Seaway (CAS) and its effect on changes in ocean circulation and climate during the time interval from ~6 - 2.5 Ma. It was accomplished within the DFG Research Unit "Impact of Gateways on Ocean Circulation, Climate and Evolution" at the University of Kiel. Proxy records from Ocean Drilling Program (ODP) Sites 999 and 1000 (Caribbean), and from ODP Sites 1237, 1239 and 1241 (low-latitude east Pacific) are developed and examined. In addition, previously established proxy data from Atlantic Sites 925/926 (Ceara Rise) and 1006 (western Great Bahama Bank) and from two east Pacific sites (851, 1236) are included for interpretations. The main objectives of this study are (1) to acquire a consistent stratigraphic framework for all sites, (2) to reconstruct Pliocene changes in Caribbean and tropical east Pacific upper ocean water masses (i.e. temperature, salinity, thermocline depth), and (3) to identify potential underlying forcing mechanisms.

Comparison of accumulation rates and stable isotope ratios

Since 1979/80, glaciological studies have been carried out at Ekströmisen, Antarctica, including accumulation-stake measurements, snow-pit and shallow-firn-core studies. Snowstratigraphy, chemical properties and stable-isotope ratios (d18O) were investigated. This study focuses on three cores taken between 1982 and 1998. The 1998 core was dated using dielectric profiling, d18O profiles and stake measurements. Accumulation rates showhigh interannual and spatial variability due to the extreme wind influence. No significant trend was found for the last 50 years; during the first half of the 20th century, accumulation decreased. The high spatial and interannual variability, however, means that trends must be interpreted with care. In spite of the highly irregular accumulation distribution, stable-isotope ratios show little spatial variability. The mean annual d18O values of cores B04 and FB0198 agree fairly well for the time period 1955-82 covered by both cores. d18O values have increased during most of the 20th century; since the late 1980s a decrease is observed. This change is not related to air temperature, since mean annual air temperatures at Neumayer show no significant trend over the last two decades.

Stable oxygen and carbon isotope ratios of foraminifera and test results after different sample cleaning procedures from ODP Leg 207 sediments

We report oxygen and carbon stable isotope analyses of foraminifers, primarily planktonic, sampled at low resolution in the Cretaceous and Paleogene sections from Sites 1257, 1258, and 1260. Data from two samples from Site 1259 are also reported. The very low resolution of the data only allows us to detect climate-driven isotopic events on the timescale of more than 500 k.y. A several million-year-long interval of overall increase in planktonic 18O is seen in the Cenomanian at Site 1260. Before and after this interval, foraminifers from Cenomanian and Turonian black shales have d18O values in the range -4.2 per mil to -5.0 per mil, suggestive of upper ocean temperatures higher than modern tropical values. The d18O values of upper ocean dwelling Paleogene planktonics exhibit a long-term increase from the early Eocene to the middle Eocene. During shipboard and postcruise processing, it proved difficult to extract well-preserved foraminifer tests from black shales by conventional techniques. Here, we report results of a test of procedures for cleaning foraminifers in Cretaceous organic-rich mudstone sediments using various combinations of soaking in bleach, Calgon/hydrogen peroxide, or Cascade, accompanied by drying, repeat soaking, or sonication. A procedure that used 100% bleach, no detergent, and no sonication yielded the largest number of clean, whole individual foraminifers with the shortest preparation time. We found no significant difference in d18O or d13C values among sets of multiple samples of the planktonic foraminifer Whiteinella baltica extracted following each cleaning procedure.

Age determination and stable isotope record of sediment cores at 9°S in the Indian Ocean

A continuous 10-m-long section consisting of roughly two thirds Ethmodiscus rex (a diatom) and one third mixed planktonic foraminifera was identified in a core from 3800 m depth at 9°S on the Indian Ocean's 90°E Ridge. Radiocarbon dates place the onset of deposition of this layer at >30,000 years B.P. and its termination at close to 11,000 years B.P. However, precise dating of the foraminifera from the Ethmodiscus layer itself proved to be impossible owing to the presence of secondary calcite presumably precipitated from the pore waters. During the Holocene, high calcium carbonate content ooze free of diatoms was deposited at this locale. As the site currently lies beneath the pathway taken by upper ocean waters entering the Indian Ocean from the Pacific (via the Indonesian Straits), it appears that during glacial time, thermocline waters moving along this same path provided the silica and other nutrients required by these diatoms.

Planktonic foraminifer assemblages and stable oxygen and carbon isotope record of sediment core MD07-3076Q

We report high-resolution planktonic foraminifer census counts and stable oxygen and carbon isotope measurements of the planktonic foraminifera G. bulloides and N. pachyderma s. from sediment core MD07-3076Q for the last deglaciation, the last glacial maximum and Marine Isotope Stage 3. These data provide insights into the marine cycling of carbon and frontal dynamics in the sub-Antarctic Atlantic during the last 68 ka.

Age model and stable isotope record of eastern equatorial Pacific sediment cores

Six deep sea cores from the eastern equatorial Pacific (EEP) were analyzed for planktonic foraminifera and stable isotopes in order to reconstruct sea surface temperatures (SST) for the last 40 ka. South of the Equatorial Front the abundance of Globorotalia inflata increased, and SST decreased by >5°C (core ODP846B), creating a stronger SST meridional gradient and advection of the Peru Current than present for the ~16-35 ka interval. A sharper SST meridional gradient forced stronger Choco jet events and a moisture increase in western Colombia, which supplied, through the San Juan River and the south-flowing equatorial and the Peru-Chile countercurrents, abundant hemipelagic quartz over the northern Peru basin (core TR163-31B). The Choco jet, and its associated mesoscale convective cells, provoked an increase in snow precipitation over the Central Cordillera of Colombia and the advance of the Murillo glacier. In synchrony with the intensified Choco jet events, the "dry island" effect over the Eastern Cordillera of Colombia intensified, and the level of Fuquene Lake dropped.

Stable foraminifer isotope composition and age of ODP Sites 184-1147 and 184-1148, South China Sea

Sites 1147 (18°50.11'N, 116°33.28'E; water depth = 3246 m) and 1148 (18°50.17'N, 116°33.94'E; water depth = 3294 m) are located on the lowermost continental slope off southern China near the continent/ocean crust boundary of the South China Sea Basin. Site 1147 is located upslope ~0.45 nmi west of Site 1148. Three advanced piston corer holes at Site 1147 and two extended core barrel holes at Site 1148 were cored and combined into a composite (spliced) stratigraphic section, which provided a relatively continuous profile for the lower Oligocene to Holocene (Wang, Prell, Blum, et al., 2000, doi:10.2973/odp.proc.ir.184.2000; Jian, et al., 2001, doi:10.1007/BF02907088) for studying stratigraphy and paleoceanography. A total of 1047 planktonic foraminifers stable isotope measurements were performed on 975 samples covering the upper 409.58 meters composite depth (mcd) at ~42-cm intervals (Tables T1, T2), and a total of 1864 benthic foraminifers measurements were performed on 1650 samples in the upper 837.11 mcd at ~51-cm intervals (Tables T3, T4). We significantly improved the time resolution of the benthic stable isotope record in the upper 476.68 mcd by reducing the average sample spacing to ~29 cm. This translates into an average sampling resolution of ~16 k.y. for the Miocene sequence and ~8 k.y. for the Pliocene-Holocene interval, assuming a change in sedimentation rates from ~1.8 to ~3.5 cm/k.y., as suggested by shipboard stratigraphy. These data sets provide the basis for upcoming studies to establish an oxygen isotope stratigraphy and examine the Neogene evolution of deep and surface water signatures (temperature, salinity, and nutrients) in the South China Sea.

Stable isotope and trace element geochemistry of carbonate sediments at DSDP Holes 87-577 and 6-47.2

Detailed analyses of well-preserved carbonate samples from across the Cretaceous/Tertiary boundary in Hole 577 have revealed a significant decline in the d13C values of calcareous nannoplankton from the Maestrichtian to the Danian Age accompanied by a substantial reduction in carbonate accumulation rates. Benthic foraminifers, however, do not exhibit a shift in carbon composition similar to that recorded by the calcareous nannoplankton, but actually increase slightly over the same time interval. These results are similar to the earlier findings at two North Pacific Deep Sea Drilling Project locations, Sites 47.2 and 465, and are considered to represent a dramatic decrease in oceanic phytoplankton production associated with the catastrophic Cretaceous/Tertiary boundary extinctions. In addition, the change in carbon composition of calcareous nannoplankton across the Cretaceous/Tertiary boundary at Hole 577 is accompanied by only minor changes in the oxygen isotope trends of both calcareous nannoplankton and benthic foraminifers, suggesting that temperature variations in the North Pacific from the late Maestrichtian to the early Danian Age were insignificant.

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.

Neogen carbonate and stable isotope record of ODP Hole 120-751A

Lower Miocene through upper Pleistocene benthic foraminifer assemblage records from Ocean Drilling Program Site 751 on the Southern Kerguelen Plateau (57°44'S, water depth 1634 m) were combined with benthic and planktonic foraminifer oxygen and carbon isotope records and high-resolution CaCO3 data from the same site. Implications for the Neogene productivity and paleoceanography of the southern Indian Ocean are discussed. We used distinctive features of the Miocene d18O and d13C curves for stratigraphic correlation. Coinciding with a lower middle Miocene hiatus from 14.2 to 13.4 Ma, there was a rapid increase in benthic d18O values by 1.2 per mil. This distinct increase occurs in middle Miocene benthic foraminifer oxygen isotope curves from all oceans. No major change, however, in benthic foraminifer faunal composition occurred in this period of growth of the Antarctic ice cap and cooling of deep ocean waters (14.9-14.2 Ma). A drastic change in benthic foraminifer faunas coincided with a hiatus from 8.4 to 5.9 Ma. Shortly after this hiatus, in the latest Miocene, the CaCO3 content of the sediments dropped from 75% to 0%. From that time ( 5.8 Ma) through the early Pliocene, Site 751 has been situated beneath a high biogenic siliceous productivity zone. Carbonate contents of upper Pliocene and Pleistocene sediments vary between 20% and 70%. The benthic foraminifer faunas in the uppermost Pliocene and lower Pleistocene reflect strong bottom current conditions, in contrast to those in the upper Pleistocene, which indicate calm sedimentation and high food supply. High d13C values of planktonic foraminifers compared with low values of benthic foraminifers suggest high primary productivity in the late Pleistocene. The changes in productivity were probably a result of latitudinal migration and meandering of the Polar Frontal Zone.

Stable isotope ratios of foraminifera and sea surface temperature estimation of sediment core W2804A-14

Carbon isotopically based estimates of CO2 levels have been generated from a record of the photosynthetic fractionation of 13C (epsilon p) in a central equatorial Pacific sediment core that spans the last ~255 ka. Contents of 13C in phytoplanktonic biomass were determined by analysis of C37 alkadienones. These compounds are exclusive products of Prymnesiophyte algae which at present grow most abundantly at depths of 70-90 m in the central equatorial Pacific. A record of the isotopic compostion of dissolved CO2 was constructed from isotopic analyses of the planktonic foraminifera Neogloboquadrina dutertrei, which calcifies at 70-90 m in the same region. Values of epsilon p, derived by comparison of the organic and inorganic delta values, were transformed to yield concentrations of dissolved CO2 (c e) based on a new, site-specific calibration of the relationship between epsilon p and c e. The calibration was based on reassessment of existing epsilon p versus c e data, which support a physiologically based model in which epsilon p is inversely related to c e. Values of PCO2, the partial pressure of CO2 that would be in equilibrium with the estimated concentrations of dissolved CO2, were calculated using Henry's law and the temperature determined from the alkenone-unsaturation index UK 37. Uncertainties in these values arise mainly from uncertainties about the appropriateness (particularly over time) of the site-specific relationship between epsilon p and 1/c e. These are discussed in detail and it is concluded that the observed record of epsilon p most probably reflects significant variations in Delta pCO2, the ocean-atmosphere disequilibrium, which appears to have ranged from ~110 µatm during glacial intervals (ocean > atmosphere) to ~60 µatm during interglacials. Fluxes of CO2 to the atmosphere would thus have been significantly larger during glacial intervals. If this were characteristic of large areas of the equatorial Pacific, then greater glacial sinks for the equatorially evaded CO2 must have existed elsewhere. Statistical analysis of air-sea pCO2 differences and other parameters revealed significant (p < 0.01) inverse correlations of Delta pCO2 with sea surface temperature and with the mass accumulation rate of opal. The former suggests response to the strength of upwelling, the latter may indicate either drawdown of CO2 by siliceous phytoplankton or variation of [CO2]/[Si(OH)4] ratios in upwelling waters.

Benthic stable-isotope records of ODP Site 208-1262, South Atlantic

The Late Paleocene and Early Eocene were characterised by warm greenhouse climates, punctuated by a series of rapid warming and ocean acidification events known as "hyperthermals", thought to have been paced or triggered by orbital cycles. While these hyperthermals, such as the Paleocene Eocene Thermal Maximum (PETM), have been studied in great detail, the background low-amplitude cycles seen in carbon and oxygen-isotope records throughout the Paleocene-Eocene have hitherto not been resolved. Here we present a 7.7 million year (myr) long, high-resolution, orbitally-tuned, benthic foraminiferal stable-isotope record spanning the late Paleocene and early Eocene interval (~52.5 - 60.5 Ma) from Ocean Drilling Program (ODP) Site 1262, South Atlantic. This high resolution (~2-4 kyr) record allows the changing character and phasing of orbitally-modulated cycles to be studied in unprecedented detail as it reflects the long-term trend in carbon cycle and climate over this interval. The main pacemaker in the benthic oxygen-isotope (d18O) and carbon-isotope (d13C) records from ODP Site 1262, are the long (405 kyr) and short (100 kyr) eccentricity cycles, and precession (21 kyr). Obliquity (41 kyr) is almost absent throughout the section except for a few brief intervals where it has a relatively weak influence. During the course of the Early Paleogene record, and particularly in the latest Paleocene, eccentricity-paced negative carbon-isotope excursions (d13C, CIEs) and coeval negative oxygen-isotope (d18O) excursions correspond to low carbonate (CaCO3) and coarse fraction (%CF) values due to increased carbonate dissolution, suggesting shoaling of the lysocline and accompanied changes in the global exogenic carbon cycle. These negative CIEs and d18O events coincide with maxima in eccentricity, with changes in d18O leading changes in d13C by ~6 (±5) kyr in the 405-kyr band and by ~3 (±1) kyr in the higher frequency 100-kyr band on average. However, these phase lags are not constant, with the lag in the 405-kyr band extending from ~4 (±5) kyr to ~21 (±2) kyr from the late Paleocene to the early Eocene, suggesting a progressively weaker coupling of climate and the carbon-cycle with time. The higher amplitude 405-kyr cycles in the latest Paleocene are associated with changes in bottom water temperature of 2-4ºC, while the most prominent 100 kyr-paced cycles can be accompanied by changes of up to 1.5ºC. Comparison of the 1262 record with a lower resolution, but orbitally-tuned benthic record for Site 1209 in the Pacific allows for verification of key features of the benthic isotope records which are global in scale including a key warming step at 57.7 Ma.