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.

Alkenone in surface sediments of the Nordic seas and the North Atlantic

Alkenone sediment data from the Nordic seas and North Atlantic are compared to those from Sikes et al. (1997) for the Southern Ocean to evaluate further UK37 and UK37' as proxies to estimate cold temperatures (<10°C) and the effect of salinity and temperature in the relative abundance of 37:4 to the total abundance of C37 alkenones (37:4%). UK37 and UK37' are found to be equally viable as proxies, but there are significant regional differences in their cold temperature dependence. The measurement of 37:4% in cores from the North Atlantic region can be used to identify situations when UK37' is not a reliable paleothermometer. Variations in salinity are probably responsible for changes in the sedimentary record of 37:4%, and a preliminary calibration has been obtained for 37:4%=f(salinity). This new relationship should be further confirmed through field or laboratory experiments, but it paves the way to derive a molecular proxy to reconstruct paleosalinity in surface waters.

Alkenone stable carbon isotopes, carbonate stable carbon and oxygen isotopes, planktic foraminifera boron isotopes and atmospheric CO2 calculations and box model results from Ras il-Pellegrin section, Malta

The development of a permanent, stable ice sheet in East Antarctica happened during the middle Miocene, about 14 million years (Myr) ago. The middle Miocene therefore represents one of the distinct phases of rapid change in the transition from the "greenhouse" of the early Eocene to the "icehouse" of the present day. Carbonate carbon isotope records of the period immediately following the main stage of ice sheet development reveal a major perturbation in the carbon system, represented by the positive d13C excursion known as carbon maximum 6 ("M6"), which has traditionally been interpreted as reflecting increased burial of organic matter and atmospheric pCO2 drawdown. More recently, it has been suggested that the d13C excursion records a negative feedback resulting from the reduction of silicate weathering and an increase in atmospheric pCO2. Here we present high-resolution multi-proxy (alkenone carbon and foraminiferal boron isotope) records of atmospheric carbon dioxide and sea surface temperature across CM6. Similar to previously published records spanning this interval, our records document a world of generally low (~300 ppm) atmospheric pCO2 at a time generally accepted to be much warmer than today. Crucially, they also reveal a pCO2 decrease with associated cooling, which demonstrates that the carbon burial hypothesis for CM6 is feasible and could have acted as a positive feedback on global cooling.

Organic temperature proxies in the subpolat region around Iceland

Subpolar regions are key areas to study natural climate variability, due to their high sensitivity to rapid environmental changes, particularly through sea surface temperature (SST) variations. Here, we have tested three independent organic temperature proxies (UK'37, TEX86 and LDI) on their potential applicability for SST reconstruction in the subpolar region around Iceland. UK'37, TEX86 and TEXL86 temperature estimates from suspended particulate matter showed a substantial discrepancy with instrumental data, while long chain alkyl diols were below detection limit in most of the stations. In the northern Iceland Basin, sedimenting particles revealed a seasonality in lipid fluxes i.e. high fluxes of alkenones and GDGTs were measured during late spring-summer, and high fluxes of long chain alkyl diols during late summer. The flux-weighted average temperature estimates had a significant negative (ca. 2.3°C for UK'37) and positive (up to 5°C for TEX86) offset with satellite-derived SSTs and temperature estimates derived from the underlying surface sediment. UK'37 temperature estimates from surface sediments around Iceland correlate well with summer mean sea surface temperatures, while TEX86 derived temperatures correspond with both annual and winter mean 0-200 m temperatures, suggesting a subsurface temperature signal. Anomalous LDI-SST values in surface sediments, and low mass flux of 1,13- and 1,15-diols compared to 1,14-diols, suggest that Proboscia diatoms are the major sources of long chain alkyl diols in this area rather than eustigmatophyte algae, and therefore the LDI cannot be applied in this region.

Comparison of TEX86 and UK'37 temperature proxies in sinking particles in the Cariaco Basin

The Cariaco Basin, a silled, permanently anoxic basin on the continental shelf of Venezuela with a dynamic chemocline (-240-350 m), has been subject of > 20 years of oceanographic observation and sediment trap studies. We evaluated UK'37 and the TEX86 temperature proxies using sinking particles collected in shallow sediment trap samples at 275 m (Trap A) and 455 m (Trap B) (within and below the chemocline). The organic geochemical temperature proxies, UK'37. (based on coccolithophorid alkenone lipids) and TEX86 (based on archaeal glycerol dialkyl glycerol tetraether (GDGT) lipids), use observed relationships between the ratio of specific lipids and measured sea surface temperature to hindcast past sea surface temperatures. In this study, both UK'37 and TEX86 temperature proxies record seasonal temperature variations, including the cooling associated with upwelling events. UK'37-based temperatures are colder than measured sea surface temperatures, and better correlated temperature at the chlorophyll maximum. In sediment trap material collected below the chemocline (Trap B), UK'37 values are higher than those in Trap A. Warmer subchemocline UK'37 based temperatures may be related to autooxidation of sinking particles, either by small amounts of available oxygen or by alternate electron acceptors concentrated in the biologically dynamic chemocline (e.g. intermediate sulfur compounds). The absolute flux weighted TEX86 temperature values measured in sinking particles from Trap A match the measured SST well. The differences in the TEX86 values between Traps A and B are small and reflect less impact of degradation. Overall, the TEX86 temperatures in sinking particles in the Cariaco Basin reflect annual SST.

Temperature proxies of sediment cores from the Sea of Marmara

Reconstructing ocean temperature values is a major target in paleoceanography and climate research. However, most temperature proxies are organism-based and thus suffer from an "ecological bias". Multiproxy approaches can potentially overcome this bias but typically require more investment in time and resources, while being susceptible to errors induced by sample preparation steps necessary before analysis. Three lipid-based temperature proxies are widely used: UK'37 (based on long chain alkenones from phytoplanktonic haptophytes), TEX86 [based on glycerol dialkyl glycerol tetraethers (GDGTs) from pelagic archaea] and LDI (based on long chain diols from phytoplanktonic eustigmatophytes). So far, separate analytical methods, including gas chromatography (GC) and liquid chromatography (LC), have been used to determine these proxies. Here we present a sensitive method for determining all three in a single normal phase high performance LC-atmospheric pressure chemical ionization mass spectrometry (NP-HPLC-APCI-MS) analysis. Each of the long chain alkenones and long chain diols was separated and unambiguously identified from the accurate masses and characteristic fragmentation during multiple stage MS analysis (MS2). Comparison of conventional GC and HPLC-MS methods showed similar results for UK'37 and LDI, respectively, using diverse environmental samples and an Emiliania huxleyi culture. Including the three sea surface temperature (SST) proxies; the NP-HPLC-APCI-MS method in fact allows simultaneous determination of nine paleoenvironmental proxies. The extent to which the ecology of the source organisms (ecological bias) influences lipid composition and thereby the reconstructed temperature values was demonstrated by applying the new method to a sediment core from the Sea of Marmara, covering the last 21 kyr BP. Reconstructed SST values differed considerably between the proxies for the Last Glacial Maximum (LGM) and the period of Sapropel S1 formation at ca. 10 kyr BP, whereas the trends during the late Holocene were similar. Changes in the composition of alkenone-producing species at the transition from the LGM to the Bølling/Allerød (B/A) were inferred from unreasonably high UK'37-derived SST values (ca. 20 °C) during the LGM. We ascribe discrepancies between the reconstructed temperature records during S1 deposition to habitat change, e.g. a different depth due to changes in nutrient availability.

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.

Organic matter preservation in turbidites on the Madeira Abyssal Plain

Oxidized intervals of five organic-rich Madeira Abyssal Plain (MAP) turbidites deposited during the Miocene, Pliocene, and Pleistocene all displayed comparable major loss of total organic carbon (TOC) (84 ± 3.1%) accompanied by a negative isotopic (d13C) shift ranging from -0.3 to -2.9 per mil. Major but significantly lower loss of total nitrogen (Ntot, 61 ± 7.1%) also occurred, leading to a decrease in TOC relative to Ntot (C/Ntot) and a +1.3 to 2.7 per mil Ntot isotopic (d15N) shift. Compound specific isotopic measurements on plant wax n-alkanes indicate the terrestrial organic component in the unoxidized deposits is 13C-enriched owing to significant C4 contribution. Selective preservation of terrestrial relative to marine organic carbon could account for the d13C behavior of TOC upon oxidation but only if a 13C-depleted component of the bulk terrestrial signal is selectively preserved in the process. Although the C/Ntot decrease and positive d15N shift seems inconsistent with selective terrestrial organic preservation, results from analysis of a Modern eolian dust sample collected in the vicinity indicate these observations are compatible. Regardless of the specific explanation for these isotopic observations, however, our findings provide evidence that paleoreconstruction of properties such as pCO2 using the d13C of TOC is a goal fraught with uncertainty whether or not the marine sedimentary record considered is 'contaminated' with significant terrestrial input. Nonetheless, despite major and selective loss of both marine and terrestrial components as a consequence of postdepositional oxidation, intensive organic geochemical proxies such as the alkenone unsaturation index, UK'37, appear resistant to change and thereby retain their paleoceanographic promise.

Salinity estimation from Gulf of Guinea, sediment core MD03-2707

The isotopic composition of surface seawater is widely used to infer past changes in sea surface salinity using paired foraminiferal Mg/Ca and d18O from marine sediments. At low latitudes, paleosalinity reconstructions using this method have largely been used to document changes in the hydrological cycle. This method usually assumes that the modern seawater d18O (d18Osw)/salinity relationship remained constant through time. Modelling studies have shown that such assumptions may not be valid because large-scale atmospheric circulation patterns linked to global climate changes can alter the seawater d18Osw/salinity relationship locally. Such processes have not been evidenced by paleo-data so far because there is presently no way to reconstruct past changes in the seawater d18Osw/salinity relationship. We have addressed this issue by applying a multi-proxy salinity reconstruction from a marine sediment core collected in the Gulf of Guinea. We measured hydrogen isotopes in C37:2 alkenones (dDa) to estimate changes in seawater dD. We find a smooth, long-term increase of ~10 per mil in dDa between 10 and 3 kyr BP, followed by a rapid decrease of ~10 per mil in dDa between 3 kyr BP and core top to values slightly lighter than during the early Holocene. Those features are inconsistent with published salinity estimations based on d18Osw and foraminiferal Ba/Ca, as well as nearby continental rainfall history derived from pollen analysis. We combined dDa and d18Osw values to reconstruct a Holocene record of salinity and compared it to a Ba/Ca-derived salinity record from the same sedimentary sequence. This combined method provides salinity trends that are in better agreement with both the Ba/Ca-derived salinity and the regional precipitation changes as inferred from pollen records. Our results illustrate that changes in atmospheric circulation can trigger changes in precipitation isotopes in a counter-intuitive manner that ultimately impacts surface salinity estimates based on seawater isotopic values. Our data suggest that the trends in Holocene rainfall isotopic values at low latitudes may not uniquely result from changes in local precipitation associated with the amount effect.