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.

Organic carbon and biomarker record from the Laptev Sea continental margin

In order to understand the processes controlling organic carbon deposition (i.e., primary productivity vs. terrigenous supply) and their paleoceanographic significance, three sediment cores (PS2471, PS2474. and PS2476) from the Laptev Sea continental margin were investigated for their content and composition of organic carbon. The characterization of organic matter indudes the determination of buk parameters (hydrogen index values and C/N ratios) and the analysis of specific biomarkers (n-alaknes, fatty acids, alkenones, and pigments). Total organic carbon (TOC) values vary between 0.3 and 2%. In general, the organic matter from the Laptev Sea continental margin is dominated by terrigenous matter throughout. However. significant amounts of marine organic carbon occur. The turbidites, according to a still preliminary stratigraphy probably deposited during glacial Oxygen Isotope Stages 2 and 4, are characterized by maximum amounts of organic carbon of terrigenous origin. Marine organic carbon appears to show enhanced relative abundances in the Termination I (?) and early Holocene time intervals, as indicated by maximum amounts of short chain n-alkanes, short-chain fatty acids, and alkenones. The increased amounts of faity acids, however, may also have a freshwater origin due to increased river discharge at that time. The occurrence of alkenones is suggested to indicate an intensification of Atlantic water inflow along the Eurasian continental margin starting at that time. Oxygen Isotope Stage l accumutation rates of total organic carhon are 0.3, 0.17, and 0.02 C/cm**2/ky in cores PS2476, PS2474, and PS2471, respectively.

Alkenon concentrations of Creatcesous sediments of DSDP Hole 76-534A (Table 1)

We here report the discovery of unusual distributions of long-chain alkenones (C37-C42) in two Cretaceous black shales from the Blake-Bahama Basin, western North Atlantic. These sediments are Cenomanian (c. 95 Ma) and mid-Albian (c. 105 Ma) in age, thus significantly extending the geological range of these compounds. The precise source of these lipids is, as yet, unknown, although they may derive from an ancient ancestor of Emiliania huxleyi.

Alkenones and sea surface reconstruction of sediments from, the Arabian Sea

Deep-sea sediments of two cores from the western (TY93-929/P) and the southeastern (MD900963) Arabian Sea were used to study the variations of the Indian monsoon during previous climatic cycles. Core TY93-929/P was located between the SW monsoon driven upwelling centres off Somalia and Oman, which are characterized by large seasonal sea surface temperature (SST) and particle flux changes. By contrast, core MD900963, was situated near the Maldives platform, an equatorial ocean site with a rather small SST seasonality (less than 2°C). For both cores we have reconstructed SST variations by means of the unsaturation ratio of C37 alkenones, which is compared with the delta18O records established on planktonic foraminifera. In general, the SST records follow the delta18O variations, with an SST maximum during oxygen isotope stage 5.5 (the Last Interglacial at about 120-130 kyr) and a broad SST minimum during isotope stage 4 and 3.3 (approximately 40-50 kyr). The SST difference between the Holocene and the Last Glacial Maximum (LGM) is of the order of 2°C. In both cores the SSTs during isotope stage 6 are distinctly higher by 1-2°C than the cold SST minima during the last glacial cycle (LGM and stage 3). To reconstruct qualitatively the past productivity variations for the two cores, we used the concentrations and fluxes of alkenones and organic carbon, together with a productivity index based on coccolith species (Florisphaera profunda relative abundance). Within each core, there is a general agreement between the different palaeoproductivity proxies. In the southeastern Arabian Sea (core MD900963), glacial stages correspond to relatively high productivity, whereas warm interstadials coincide with low productivity. All time series of productivity proxies are dominated by a cyclicity of about 21-23 kyr, which corresponds to the insolation precessional cycle. A hypothesis could be that the NE monsoon winds were stronger during the glacial stages, which induced deepening of the surface mixed layer and injection of nutrients to the euphotic zone. By contrast, the records are more complicated in the upwelling region of the western Arabian Sea (core TY93-929/P). This is partly due to large changes in the sedimentation rates, which were higher during specific periods (isotope stages 6, 5.4, 5.2, 3 and 2). Unlike core MD900963, no simple relationship emerges from the comparison between the delta18O stratigraphy and productivity records. The greater complexity observed for core TY93-929/P could be the result of the superimposition of different patterns of productivity fluctuations for the two monsoon seasons, the SW monsoon being enhanced during interglacial periods, whereas the NE monsoon was increased during glacial intervals. A similar line of reasoning also could help explain the SST records by the superimposition of variations of three components: global atmospheric temperature, and SW and NE monsoon dynamics.

(Table 1) TOC, d13C, concentrations of C37 alkenones, crenarchaeol and GDGTs of turbidites

One of the primary prerequisites for the application of organic proxies is that they should not be substantially affected by diagenesis. However, studies have shown that oxic degradation of biomarker lipids can affect their relative distribution. We tested the diagenetic stability of the UK'37 and TEX86 palaeothermometers upon long term oxygen exposure. For this purpose, we studied the distributions of alkenones and glycerol dialkyl glycerol tetraethers (GDGTs) in different sections of turbidites at the Madeira Abyssal Plain (MAP) that experienced different degrees of oxygen exposure. Sediments were deposited anoxically on the shelf and then transported by turbidity currents to the MAP, which has oxic bottom water. This resulted in partial degradation of the turbidite organic matter as a result of long term exposure to oxic bottom water. Concentrations of GDGTs and alkenones were reduced by one to two orders of magnitude in the oxidized parts of the turbidites compared to the unoxidized parts, indicating substantial degradation. High-resolution analysis of the Pleistocene F-turbidite showed that the UK'37 index of long chain alkenones increased only slightly (0.01, corresponding to <0.5 °C) in the oxidized part of the turbidite, suggesting minor preferential degradation of the C37:3 alkenone, in agreement with previous studies. TEX86 values showed a small increase (0.02, corresponding to ~2 °C) in the F-turbidite, like UK'37 , while for other Pliocene/Miocene turbidites it either remained unchanged or decreased substantially (up to 0.06, corresponding to ~6 °C). Previous observations showed that the BIT index, a proxy for the contribution of soil organic matter to total organic carbon, was always substantially higher in the oxidized part in all the turbidites, as a result of preferential degradation of marine-derived GDGTs. This relative increase in soil-derived GDGTs affects TEX86, as the isoprenoid GDGT distribution on the continent can be quite different from that in the marine environment. Our results indicate that the organic proxies are affected by long term oxic degradation to different extents; this should be taken into account when applying these proxies in palaeoceanographic studies of sediments which have been exposed to prolonged oxic degradation.