Alkenone stable carbon isotopes, planktic foraminfera stable carbon isotopes, alkenone unsaturation indices and calculated sea surface temperatures and atmospheric pCO2 for ODP Site 165-999

Temperature reconstructions indicate that the Pliocene was ~3 °C warmer globally than today, and several recent reconstructions of Pliocene atmospheric CO2 indicate that it was above pre-industrial levels and similar to those likely to be seen this century. However, many of these reconstructions have been of relatively low temporal resolution, meaning that these records may have failed to capture variations associated with the 41 Kyr glacial-interglacial cycles thought to operate in the Pliocene. Here we present a new, high temporal resolution alkenone carbon isotope based record of pCO2 spanning 2.8 to 3.3 million years ago from ODP Site 999. Our record is of high enough resolution (~19 Kyrs) to resolve glacial-interglacial changes beyond the intrinsic uncertainty of the proxy method. The record suggests that Pliocene CO2 levels were relatively stable, exhibiting variation less than 55 ppm. We perform sensitivity studies to investigate the possible effect of changing sea surface temperature, which highlights the importance of accurate and precise SST reconstructions for alkenone palaeobarometry, but demonstrate that these uncertainties do not affect our conclusions of relatively stable pCO2 levels during this interval.

(Table 3) Reduced inorganic sulphur, d34S and nickel content of ODP Leg 165 sites

Leg 165 of the Ocean Drilling Program afforded a unique opportunity to investigate organic and inorganic geochemistry across a wide gradient of sediment compositions and corresponding chemical pathways. The solid fractions at Sites 998, 999, 1000, and 1001 reveal varying proportions of reactive carbonate species, a labile volcanic ash fraction occurring in discrete layers and as a dispersed component, and detrital fluxes that derive from continental weathering. The relative proportions and reactivities of these end-members strongly dictate the character of the diagenetic profiles observed during the pore-water work of Leg 165. In addition, alteration of the well-characterized basaltic basement at Site 1001 has provided a strong signal that is reflected in many of the dissolved components. The relative effects of basement alteration and diagenesis within the sediment column are discussed in terms of downcore relationships for dissolved calcium and magnesium. With the exception of Site 1002 in the Cariaco Basin, the sediments encountered during Leg 165 were uniformly deficient in organic carbon (typically <0.1 wt%). Consequently, rates of organic oxidation were generally low and dominated by suboxic pathways with subordinate levels of bacterial sulfate reduction and methanogenesis. The low rates of organic remineralization are supported by modeled rates of sulfate reduction. Site 1000 provided an exception to the generally low levels of microbially mediated redox cycling. At this site the sediment is slightly more enriched in organic phases, and externally derived thermogenic hydrocarbons appear to aid in driving enhanced levels of redox diagenesis at great depths below the seafloor. The entrapment of these volatiles corresponds with a permeability seal defined by a pronounced Miocene minimum in calcium carbonate concentration recognized throughout the basin and with a dramatic downcore increase in the magnitude of limestone lithification. The latter has been tentatively linked to increases in alkalinity associated with microbial oxidation of organic matter and gaseous hydrocarbons. Recognition and quantification of previously unconstrained large volumes and frequencies of Eocene and Miocene silicic volcanic ash within the Caribbean Basin is one of the major findings of Leg 165. High frequencies of volcanic ash layers manifest as varied but often dominant controls on pore-water chemistry. Sulfur isotope results are presented that speak to secondary metal and sulfur enrichments observed in ash layers sampled during Leg 165. Ultimately, a better mechanistic understanding of these processes and the extent to which they have varied spatially and temporally may bear on the global mass balances for a range of major and minor dissolved components of seawater.

Age and chemical composition of apatites from five DSDP and ODP Sites in the Pacific, Atlantic and Indian Oceans

Since studies on deep-sea cores were carried out in the early 1990s it has been known that ambient temperature may have a marked affect on apatite fission track annealing. Due to sluggish annealing kinetics, this effect cannot be quantified by laboratory annealing experiments. The unknown amount of low-temperature annealing remains one of the main uncertainties for extracting thermal histories from fission track data, particularly for samples which experienced slow cooling in shallow crustal levels. To further elucidate these uncertainties, we studied volcanogenic sediments from five deep-sea drill cores, that were exposed to maximum temperatures between ~10° and 70°C over geological time scales of ~15-120 Ma. Mean track lengths (MTL) and etch pit diameters (Dpar) of all samples were measured, and the chemical composition of each grain analyzed for age and track length measurements was determined by electron microprobe analysis. Thermal histories of the sampled sites were independently reconstructed, based on vitrinite reflectance measurements and/or 1D numerical modelling. These reconstructions were used to test the most widely used annealing models for their ability to predict low-temperature annealing. Our results show that long-term exposure to temperatures below the temperature range of the nominal apatite fission track partial annealing zone results in track shortening ranging between 4 and 11%. Both chlorine content and Dpar values explain the downhole annealing patterns equally well. Low chlorine apatite from one drill core revealed a systematic relation between Si-content and Dpar value. The question whether Si-substitution in apatite has direct and systematic effects on annealing properties however, cannot be addressed by our data. For samples, which remained at temperatures <30°C, and which are low in chlorine, the Laslett et al. [Laslett G., Green P., Duddy I. and Gleadow A. (1987) Thermal annealing of fission tracks in apatite. Chem. Geol. 65, 1-13] annealing model predicts MTL up to 0.6 µm longer than those actually measured, whereas for apatites with intermediate to high chlorine content, which experienced temperatures >30°C, the predictions of the Laslett et al. (1987) model agree with the measured MTL data within error levels. With few exceptions, predictions by the Ketcham et al. [Ketcham R., Donelick R. and Carlson W. (1999) Variability of apatite fission-track annealing kinetics. III: Extrapolation to geological time scales. Am. Mineral. 84/9, 1235-1255] annealing model are consistent with the measured data for samples which remained at temperatures below ~30°C. For samples which experienced maximum temperatures between ~30 and 70°C, and which are rich in chlorine, the Ketcham et al. (1999) model overestimates track annealing.

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.

Alkenone and boron based Oligocene pCO2 records

The Pliocene period is the most recent time when the Earth was globally significantly (~3°C) warmer than today. However, the existing pCO2 data for the Pliocene are sparse and there is little agreement between the various techniques used to reconstruct palaeo-pCO2. Moreover, the temporal resolution of the published records does not allow a robust assessment of the role of declining pCO2 in the intensification of the Northern Hemisphere Glaciation (INHG) and a direct comparison to other proxy records are lacking. For the first time, we use a combination of foraminiferal (delta11B) and organic biomarker (alkenone-derived carbon isotopes) proxies to determine the concentration of atmospheric CO2 over the past 5 Ma. Both proxy records show that during the warm Pliocene pCO2 was between 330 and 400 ppm, i.e. similar to today. The decrease to values similar to pre-industrial times (275-285 ppm) occurred between 3.2 Ma and 2.8 Ma - coincident with the INHG and affirming the link between global climate, the cryosphere and pCO2.

Planktonic foraminiferal preservation in Plio/Pleistocene sediments from the western equatorial Atlantic and Caribbean

Records of mean sortable silt and planktonic foraminiferal preservation from the Ceará Rise (western equatorial Atlantic) and from the Caribbean are presented to analyze the Pliocene (3.5-2.2 Ma) to Pleistocene (1.6-0.3 Ma) evolution of near-bottom current strength and the carbonate corrosiveness of deep water. During the mid-Pleistocene climate transition (~1 Ma) a drastic decrease in glacial bottom current strength and an increase in carbonate corrosiveness is registered, demonstrating a substantial decrease in the glacial contribution of the Lower North Atlantic Deep Water (LNADW) to the Atlantic Ocean. Also, an increased sensitivity to eccentricity orbital forcing is registered after the MPT. By contrast, carbonate preservation increases considerably in the deep Caribbean in response to a strong and persistent stable contribution of Upper North Atlantic Deep Water (UNADW). We found evidence for the strongest and most stable circulation within the LNADW cell during the Northern Hemisphere cooling period between ~3.2 and 2.75 Ma. This is in agreement with the 'superconveyor model' which postulates that the highest NADW production took place prior to ~2.7 Ma. A considerable decrease in bottom current strength and planktonic foraminiferal preservation is observed synchronous with the first occurrence of large-scale continental ice sheets in the Northern Hemisphere. This documents the final termination of the 'superconveyor' at ca. 2.75 Ma. However, our data do not support a 'superconveyor' in the interval between 3.5 and 3.2 Ma when high-amplitude fluctuations in bottom current flow and preservation in planktonic foraminifera are observed. Because of the great sensitivity of NADW production to changes in surface water salinity, we assume that the high-amplitude fluctuations of LNADW circulation prior to ~3.2 Ma are linked to changes in the Atlantic salinity budget. After 2.75 Ma they are primarily controlled by ice-sheet forcing. In contrast to the stepwise deterioration of planktonic foraminiferal preservation in the western deep Atlantic, a trend toward better preservation from the Pliocene to Pleistocene is observed in the deep Caribbean. This indicates a long-term increase in the contribution of UNADW to the Atlantic Ocean.

Stable oxygen isotope and Mg/Ca ratios of planktonic foraminifera from the Caribbean and North Atlantic

Variations in the strength of the North Atlantic Ocean thermohaline circulation have been linked to rapid climate changes during the last glacial cycle through oscillations in North Atlantic Deep Water formation and northward oceanic heat flux. The strength of the thermohaline circulation depends on the supply of warm, salty water to the North Atlantic, which, after losing heat to the atmosphere, produces the dense water masses that sink to great depths and circulate back south. Here we analyse two Caribbean Sea sediment cores, combining Mg/Ca palaeothermometry with measurements of oxygen isotopes in foraminiferal calcite in order to reconstruct tropical Atlantic surface salinity during the last glacial cycle. We find that Caribbean salinity oscillated between saltier conditions during the cold oxygen isotope stages 2, 4 and 6, and lower salinities during the warm stages 3 and 5, covarying with the strength of North Atlantic Deep Water formation. At the initiation of the Bølling/Allerød warm interval, Caribbean surface salinity decreased abruptly, suggesting that the advection of salty tropical waters into the North Atlantic amplified thermohaline circulation and contributed to high-latitude warming.

Summary of boron isotope and Mg/Ca data

Biological productivity and carbon export in the equatorial Atlantic are thought to have been dramatically higher during the last glacial period than during the Holocene. Here we reconstruct the pH and CO2 content of surface waters from the eastern equatorial Atlantic Ocean over the past ~30 k.y. using the boron isotope composition of Globigerinoides ruber (a mixed-layer-dwelling planktic foraminifera). Our new record, combined with previously published data, indicates that during the last glacial, in contrast to today, a strong west to east gradient existed in the extent of air:sea equilibrium with respect to pCO2 (DeltapCO2), with the eastern equatorial Atlantic acting as a significant source of CO2 (+100 µatm) while the western Atlantic remained close to equilibrium (+25 µatm). This pattern suggests that a fivefold increase in the upwelling rate of deeper waters drove increased Atlantic productivity and large-scale regional cooling during the last glacial, but the higher than modern DeltapCO2 in the east indicates that export production did not keep up with enhanced upwelling of nutrients. However, the downstream decline of DeltapCO2 provides evidence that the unused nutrients from the east were eventually used for biologic carbon export, thereby effectively negating the impact of changes in upwelling on atmospheric CO2 levels. Our findings indicate that the equatorial Atlantic exerted a minimal role in contributing to lower glacial-age atmospheric CO2.

Water temperature reconstructions based on paired Uk'37 and Tex86 records, and paired surface and subsurface Mg/Ca records

This dataset contains the collection of available published paired Uk'37 and Tex86 records spanning multi-millennial to multi-million year time scales, as well as a collection of Mg/Ca-derived temperatures measured in parallel on surface and subsurface dwelling foraminifera, both used in the analyses of Ho and Laepple, Nature Geoscience 2016. As the signal-to-noise ratios of proxy-derived Holocene temperatures are relatively low, we selected records that contain at least the last deglaciation (oldest sample >18kyr BP).

Expanded GHOST database

In this study we review a global set of alkenone- and foraminiferal Mg/Ca-derived sea surface temperatures (SST) records from the Holocene and compare them with a suite of published Eemian SST records based on the same approach. For the Holocene, the alkenone SST records belong to the actualized GHOST database (Kim, J.-H., Schneider R.R., 2004). The actualized GHOST database not only confirms the SST changes previously described but also documents the Holocene temperature evolution in new oceanic regions such as the Northwestern Atlantic, the eastern equatorial Pacific, and the Southern Ocean. A comparison of Holocene SST records stemming from the two commonly applied paleothermometry methods reveals contrasting - sometimes divergent - SST evolution, particularly at low latitudes where SST records are abundant enough to infer systematic discrepancies at a regional scale. Opposite SST trends at particular locations could be explained by out-of-phase trends in seasonal insolation during the Holocene. This hypothesis assumes that a strong contrast in the ecological responses of coccolithophores and planktonic foraminifera to winter and summer oceanographic conditions is the ultimate reason for seasonal differences in the origin of the temperature signal provided by these organisms. As a simple test for this hypothesis, Eemian SST records are considered because the Holocene and Eemian time periods experienced comparable changes in orbital configurations, but had a higher magnitude in insolation variance during the Eemian. For several regions, SST changes during both interglacials were of a similar sign, but with higher magnitudes during the Eemian as compared to the Holocene. This observation suggests that the ecological mechanism shaping SST trends during the Holocene was comparable during the penultimate interglacial period. Although this "ecology hypothesis" fails to explain all of the available results, we argue that any other mechanism would fail to satisfactorily explain the observed SST discrepancies among proxies.