Lipid biomarkers in urface sediments of the Southeast Atlantic

Surface sediments from the eastern South Atlantic were investigated for their lipid biomarker contents and bulk organic geochemical characteristics to identify sources, transport pathways and preservation processes of organic components. The sediments cover a wide range of depositional settings with large differences in mass accumulation rates. The highest marine organic carbon (OC) contributions are detected along the coast, especially underlying the Benguela upwelling system. Terrigenous OC contributions are highest in the Congo deep-sea fan. Lipid biomarker fluxes are significantly correlated to the extent of oxygen exposure in the sediment. Normalization to total organic carbon (TOC) contents enabled the characterization of regional lipid biomarker production and transport mechanisms. Principal component analyses revealed five distinct groups of characteristic molecular and bulk organic geochemical parameters. Combined with information on lipid sources, the main controlling mechanisms of the spatial lipid distributions in the surface sediments are defined, indicating marine productivity related to river-induced mixing and oceanic upwelling, wind-driven deep upwelling, river-supply of terrigenous organic material, shallow coastal upwelling and eolian supply of plant-waxes.

Sea surface temperature variations in the western Mediterranean Sea

A high-resolution sea surface temperature (SST) reconstruction of the western Mediterranean was accomplished using two independent, algae-based molecular organic proxies, i.e. the UK'37 index based on long-chain unsaturated ketones and the novel long-chain diol index (LDI) based on the relative abundances of C28 and C30 1,13- and 1,15-diols. Two marine records, from the western and eastern Alboran Sea basin, spanning the last 14 and 20 kyr, respectively, were studied. Results from the surface sediments suggest that the two proxies presently reflect seasons with similar SST, or simply annual mean SST. Both proxy records reveal the transition from the Last Glacial Maximum to the Holocene in the eastern Alboran Sea with an SST increase of ca. 7 °C for UK'37 and 9 °C for LDI. Minimum SSTs (10-12 °C) are reached at the end of the Last Glacial Maximum and during the last Heinrich event with a subsequent rapid SST increase in LDI-SST towards the beginning of the Bölling period (20 °C), while UK'37-SST remains constantly low (~12 °C). The Bölling-Alleröd is characterized by a rapid increase and subsequent decrease in UK'37-SST, while the LDI-SST decrease continuously. Short-term fluctuations in UK'37-SST are probably related to availability of nutrients and seasonal changes. The Younger Dryas is recorded as a short cold interval followed by progressively warmer temperatures. During the Holocene, the general lower UK'37-derived temperature values in the eastern Alboran (by ca. 1.5-2 °C) suggest a southeastward cold water migration by the western Alboran gyre and divergence in the haptophyte blooming season between both basins.

Age determination and paleotemperatures of sediment cores TTR17-1_384B and TTR17-1_436B in the Alboran Sea

Climate conditions in the westernmost Mediterranean (Alboran Sea basin) over the last two millennia have been reconstructed through integration of molecular proxies applied for the first time in this region at such high resolution. Two temperature proxies, one based on isoprenoid membrane lipids of marine Thaumarchaeota (TEXH86-tetraether index of compounds consisting of 86 carbons) and the other on alkenones produced by haptophytes (UK'37 ratio) were applied to reconstruct sea surface temperature (SST). Both records reveal a progressive long term decline in SST over the last two millennia and an increased rate of warming during the second half of the twentieth century. This is in accord with previous temperature reconstructions for the Northern Hemisphere. TEXH86 temperature values are higher than those inferred from UK'37, probably due to differences in the bloom season of haptophytes and Thaumarchaeota, and reflect summer SST. The branched vs. isoprenoid tetraether index (BIT index) suggests a low contribution of soil organic matter (OM) to the sedimentary OM. The stable carbon isotopic composition of long chain n-alkanes indicates a predominant C3 plant contribution, with no major change in vegetation over the last 2000 yr. The distribution of long chain 1,14-diols (most likely sourced by Proboscia species in this setting) provided insight into variation in upwelling conditions during the last 2000 yr and depicts a correlation with the North Atlantic Oscillation (NAO) index, providing evidence of enhanced wind induced upwelling during periods of a persistent positive mode of the NAO.

Long chain diol index and paleotemperature reconstruction for IODP Hole 306-U1313C

Recently, a new organic geochemical paleothermometer based on the relative abundance of long chain alkyl 1,13- and 1,15-diols, the so-called long chain diol index (LDI), was proposed. Because of its novelty, the proxy has not been reported for sediments older than 43 ka. We therefore determined the LDI for 14 sediment samples from the early Pleistocene between 2.49 and 2.41 Ma, comprising Marine Isotope Stage (MIS) 98 to 95, and converted the values to sea surface temperature (SST) estimates to test whether the LDI could be applied or not to the early Quaternary. We show that the long chain diols can be preserved in marine sediments from the early Pleistocene, although at our study site this is limited to periods of increased biomarker accumulation (glacials). Although the results are based on a limited time interval and number of samples, the similarity between LDI-based SST and alkenone-based SST from the same samples suggests that the LDI proxy may have potential for studies covering the entire Quaternary.

Long chain alkyl diol distribution in Arabian Sea surface sediments

Oxygen exposure has a large impact on lipid biomarker preservation in surface sediments and may affect the application of organic proxies used for reconstructing past environmental conditions. To determine its effect on long chain alkyl diol and keto-ol based proxies, the distributions of these lipids was studied in nine surface sediments from the Murray Ridge in the Arabian Sea obtained from varying water depths (900 to 3000 m) but in close lateral proximity and, therefore, likely receiving a similar particle flux. Due to substantial differences in bottom water oxygen concentration (<3 to 77 µmol/L) and sedimentation rate, substantial differences exist in the time the biomarker lipids are exposed to oxygen in the sediment. Long chain alkyl diol and keto-ol concentrations in the surface sediments (0-0.5 cm) decreased progressively with increasing oxygen exposure time, suggesting increased oxic degradation. The 1,15-keto-ol/diol ratio (DOXI) increased slightly with oxygen exposure time as diols had apparently slightly higher degradation rates than keto-ols. The ratio of 1,14- vs. 1,13- or 1,15-diols, used as upwelling proxies, did not show substantial changes. However, the C30 1,15-diol exhibited a slightly higher degradation rate than C28 and C30 1,13-diols, and thus the Long chain Diol Index (LDI), used as sea surface temperature proxy, showed a negative correlation with the maximum residence time in the oxic zone of the sediment, resulting in ca. 2-3.5 °C change, when translated to temperature. The UK'37 index did not show significant changes with increasing oxygen exposure. This suggests that oxic degradation may affect temperature reconstructions using the LDI in oxic settings and where oxygen concentrations have varied substantially over time.