Stable carbon isotopic composition of biomarker lipids of DSDP Hole 31-302

The middle Paleocene through early Eocene long-term gradual warming was superimposed by several transient warming events, such as the Paleocene-Eocene Thermal Maximum (PETM) and Eocene Thermal Maximum 2 (ETM2). Both events show evidence for extreme global warming associated with a major injection of carbon into the ocean-atmosphere system, but the mechanisms of carbon injection and many aspects of the environmental response are still poorly understood. In this study, we analyzed the concentration and stable carbon isotopic (d13C) composition of several sulfur-bound biomarkers derived from marine photoautotrophs, deposited in the Arctic Ocean at ~85°N, during ETM2. The presence of sulfur-bound biomarkers across this event points toward high primary productivity and anoxic bottom water conditions. The previously reported presence of isorenieratene derivatives indicates euxinic conditions in the photic zone, likely caused by a combination of enhanced primary productivity and salinity stratification. The negative carbon isotope excursion measured at the onset of ETM2 for several biomarkers, ranges between 3 per mil and 4.5 per mil, much larger than the ~1.4 per mil recorded in marine carbonates elsewhere, suggesting substantial enhanced isotopic fractionation by the primary producers likely due to a significant rise in pCO2. In the absence of biogenic carbonates in the ETM2 section of our core we use coeval planktonic d13C from elsewhere to estimate surface water d13C in the Arctic Ocean and then apply the relation between isotopic fractionation and pCO2, originally calibrated for haptophyte alkenones, to three selected organic biomarkers (i.e., S-bound phytane, C35 hopane, and a C25 highly branched isoprenoid). This yields pCO2 values potentially in the range of four times preindustrial levels. However, these estimates are uncertain because of a lack of knowledge on the importance of pCO2 on photosynthetic isotopic fractionation.

Proto-kerogens in Holocene sediments of ODP Hole 165-1002C

Proto-kerogens were isolated, by extraction and HF/HC1 treatment, from core samples of Holocene sediments of the Cariaco Trench, with interpolated ages of 900, 2850 and 6000 years, and examined via a combination of microscopic, spectroscopic and pyrolytic methods. It appears that these proto-kerogens were chiefly formed from phytoplanktonic components via the degradation-recondensation pathway. The natural sulfurisation pathway only afforded a minor contribution, in spite of the conditions prevailing in the water column and sediments that correspond to those generally considered as especially favourable for the formation of sulfurised organic matter. Proto-kerogen formation via sulfurisation, i.e. the endpoint of the continuum leading to insoluble high molecular weight structures cross-linked by sulfur and resistant to acid hydrolysis, is therefore a rather slow process under these conditions. However, the contribution of sulfurised moieties to the total proto-kerogen substantially increased with depth due to continuous sulfurisation in the time/depth interval, whereas formation through degradation-recondensation is almost complete for the 900 years old sample onwards. Proto-kerogen formation via carbohydrate sulfurisation is faster than lipid sulfurisation and only sulfurised carbohydrates were detected in the shallowest sample. In contrast, sulfurised lipids occur in the other two proto-kerogens. Moreover, their contribution relative to sulfurised carbohydrates increases with depth, probably due to the higher resistance of lipids to mineralisation compared to carbohydrates.

Helium-3 in different carriers from pelagic clays of DSDP Hole 91-596B and Core LR-44-GPC-3

To better understand the composition, characteristics of helium diffusion, and size distribution of interplanetary dust particles (IDPs) responsible for the long-term retention of extraterrestrial 3He, we carried out leaching, stepped heating, and sieving experiments on pelagic clays that varied in age from 0.5 Ma to ~90 Myr. The leaching experiments suggest that the host phase(s) of 3He in geologically old sediments are neither organic matter nor refractory phases, such as diamond, graphite, Al2O3, and SiC, but are consistent with extraterrestrial silicates, Fe-Ni sulfides, and possibly magnetite. Stepped heating experiments demonstrate that the 3He release profiles from the magnetic and non-magnetic components of the pelagic clays are remarkably similar. Because helium diffusion is likely to be controlled by mineral chemistry and structure, the stepped heating results suggest a single carrier that may be magnetite, or more probably a phase associated with magnetite. Furthermore, the stepped outgassing experiments indicate that about 20% of the 3He will be lost through diffusion at seafloor temperatures after 50 Myrs, while sedimentary rocks exposed on the Earth's surface for the same amount of time would lose up to 60%. The absolute magnitude of the 3He loss is, however, likely to depend upon the 3He concentration profile within the IDPs, which is not well known. Contrary to previous suggestions that micrometeorites in the size range of 50-100 µm in diameter are responsible for the extraterrestrial 3He in geologically old sediments [Stuart, F.M., Harrop, P.J., Knott, S., Turner, G., 1999. Laser extraction of helium isotopes from Antarctic micrometeorites: source of He and implications for the flux of extraterrestrial 3He flux to earth. Geochimica et Cosmochimica Acta, 63, 2653-2665, doi:10.1016/S0016-7037(99)00161-1], our sieving experiment demonstrates that at most 20% of the 3He is carried by particles greater than 50 µm in diameter. The size-distribution of the 3He-bearing particles implies that extraterrestrial 3He in sediments record the IDP flux rather than the micrometeorite flux.

Planktonic foraminifera Mg/Ca paleotemperatures and oxygen isotopes of ODP Hole 175-1075C

High resolution planktonic foraminifera Mg/Ca paleotemperatures and oxygen isotopes of seawater of Ocean Drilling Program (ODP) Site 1078 (off Angola) have been reconstructed and reveal insights into the seasonal thermal evolution of the Angola Current (AC), the Angola-Benguela Front (ABF), and the Benguela Current (BC) during the last glacial (50-23.5 ka BP). Special emphasis is put on time intervals possibly associated with the North Atlantic Heinrich Stadials (HS), which are thought to lead to an accumulation of heat in the South Atlantic due to a reduction of the Atlantic Meridional Overturning Circulation (AMOC). Within dating uncertainties, Globigerinoides ruber (pink) Mg/Ca-based sea surface temperature (SST) estimates that represent southern hemisphere summer surface conditions show several warming episodes that coincide with North Atlantic HS, thus supporting the concept of the bipolar thermal seesaw. In contrast, the Mg/Ca-based temperatures of Globigerina bulloides, representing the SST of the ABF/BC system during southern hemisphere winter, show no obvious response to the North Atlantic HS in the study area. We suggest that surface water cooling during the winter season is due to enhanced upwelling or upwelling of colder water masses which has most likely mitigated a warming of the ABF/BC system during HS. We further speculate that the seasonal asymmetry in our SST record results from seasonal differences in the dominance of atmospheric and oceanic teleconnections during periods of northern high latitude cooling.

Biomarker records of DSDP Hole 24-231 and terrestrial sediments

ntegrated terrestrial and marine records of northeast African vegetation are needed to provide long high resolution records of environmental variability with established links to specific terrestrial environments. In this study, we compare records of terrestrial vegetation preserved in marine sediments in the Gulf of Aden [Deep Sea Drilling Project (DSDP) Site 231] and an outcrop of lacustrine sediments in the Turkana Basin, Kenya, part of the East African Rift System. We analyzed higher plant biomarkers in sediments from both deposits of known equivalent age, corresponding to a ca. 50-100 ka humid interval prior to the b-Tulu Bor eruption ca. 3.40 Ma, when the Lokochot Lake occupied part of the Turkana Basin. Molecular abundance distributions indicate that long chain n-alkanoic acids in marine sediments are the most reliable proxy for terrestrial vegetation (Carbon Preference Index, CPI = 4.5), with more cautious interpretation needed for n-alkanes and lacustrine archives. Marine sediments record carbon isotopic variability in terrestrial biomarkers of 2-3 per mil, roughly equivalent to 20% variability in the C3/C4 vegetation contribution. The proportion of C4 vegetation apparently increased at times of low terrigenous dust input. Terrestrial sediments reveal much larger (2-10 per mil) shifts in n-alkanoic acid delta13C values. However, molecular abundance and isotopic composition suggest that microbial sources may also contribute fatty acids, contaminating the lacustrine sedimentary record of terrestrial vegetation.

Carbon and oxygen isotopic composition of benthic foraminifers from ODP Site 167-1014 and Hole 167-1020C

Benthic foraminiferal stable isotope data are presented for Sites 1014 (Tanner Basin, 1176 m) and 1020 (Gorda Ridge, 3040 m) to constrain past changes in Pacific deep- and intermediate-water nutrient chemistry associated with the onset of large-amplitude 100-k.y. climate cycles after ~900 ka. The Site 1014 data were based on analyses of separate species of Cibicidoides, whereas only Cibicidoides wuellerstorfi was used to generate the Site 1020 record. The present data span 380-920 and 620-950 ka at Sites 1014 and 1020, respectively.