Mesocosm bloom experiment results with the coccolithophore Emiliania huxleyi

We investigated the effect of CO2 and primary production on the carbon isotopic fractionation of alkenones and particulate organic matter (POC) during a natural phytoplankton bloom dominated by the coccolithophore Emiliania huxleyi. In nine semi-closed mesocosms (~11 m**3 each), three different CO2 partial pressures (pCO2) in triplicate represented glacial (~180 ppmv CO2), present (380 ppmv CO2), and year 2100 (~710 ppmv CO2) CO2 conditions. The largest shift in alkenone isotopic composition (4-5 per mil) occurred during the exponential growth phase, regardless of the CO2 concentration in the respective treatment. Despite the difference of ~500 ppmv, the influence of pCO2 on isotopic fractionation was marginal (1-2 per mil). During the stationary phase, E. huxleyi continued to produce alkenones, accumulating cellular concentrations almost four times higher than those of exponentially dividing cells. Our isotope data indicate that, while alkenone production was maintained, the interaction of carbon source and cellular uptake dynamics by E. huxleyi reached a steady state. During stationary phase, we further observed a remarkable increase in the difference between d13C of bulk organic matter and of alkenones spanning 7-12 per mil. We suggest that this phenomenon is caused mainly by a combination of extracellular release of 13C-enriched polysaccharides and subsequent particle aggregation induced by the production of transparent exopolymer particles (TEP).

Proxy calibration on two sedimentary sequences off Lisbon

High-resolution proxy data analyzed on two high-sedimentation shallow water sedimentary sequences (PO287-26B and PO287-28B) recovered off Lisbon (Portugal) provide the means for comparison to long-term instrumental time series of marine and atmospheric parameters (sea surface temperature (SST), precipitation, total river flow, and upwelling intensity computed from sea level pressure) and the possibility to do the necessary calibration for the quantification of past climate conditions. XRF Fe is used as proxy for river flow, and the upwelling-related diatom genus Chaetoceros is our upwelling proxy. SST is estimated from the coccolithophore-synthesized alkenones and Uk'37 index. Comparison of the Fe record to the instrumental data reveals its similarity to a mean average run of the instrumentally measured winter (JFMA) river flow on both sites. The upwelling diatom record concurs with the upwelling indices at both sites; however, high opal dissolution, below 20-25 cm, prevents its use for quantitative reconstructions. Alkenone-derived SST at site 28B does not show interannual variation; it has a mean value around 16°C and compares quite well with the instrumental winter/spring temperature. At site 26B the mean SST is the same, but a high degree of interannual variability (up to 4°C) appears to be determined by summer upwelling conditions. Stepwise regression analyses of the instrumental and proxy data sets provided regressions that explain from 65 to 94% of the variability contained in the original data, and reflect spring and summer river flow, as well as summer and winter upwelling indices, substantiating the relevance of seasons to the interpretation of the different proxy signals. The lack of analogs and the small data set available do not allow quantitative reconstructions at this time, but this might be a powerful tool for reconstructing past North Atlantic Oscillation conditions, should we be able to find continuous high-resolution records and overcome the analog problem.

(Table 2) Radiocarbon contents of TOC and alkenone samples

Radiocarbon age relationships between co-occurring planktic foraminifera, alkenones, and total organic carbon in sediments from the continental margins of southern Chile, northwest Africa, and the South China Sea were compared with published results from the Namibian margin. Age relationships between the sediment components are site-specific and relatively constant over time. Similar to the Namibian slope, where alkenones have been reported to be 1000-4500 years older than co-occurring foraminifera, alkenones were significantly (~1000 years) older than co-occurring foraminifera in the Chilean margin sediments. In contrast, alkenones and foraminifera were of similar age (within 2 sigma error or better) in the NW African and South China Sea sediments. Total organic matter and alkenone ages were similar off Namibia (age difference TOC alkenones: 200-700 years), Chile (100-450 years), and NW Africa (360-770 years), suggesting minor contributions of preaged terrigenous material. In the South China Sea, total organic carbon is significantly (2000-3000 years) older owing to greater inputs of preaged terrigenous material. Age offsets between alkenones and planktic foraminifera are attributed to lateral advection of organic matter. Physical characteristics of the depositional setting, such as seafloor morphology, shelf width, and sediment composition, may control the age of co-occurring sediment components. In particular, offsets between alkenones and foraminifera appear to be greatest in deposition centers in morphologic depressions. Aging of organic matter is promoted by transport. Age offsets are correlated with organic richness, suggesting that formation of organic aggregates is a key process.

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.

Sea surface temperatures and UK37 of three sediment cores from the Arctic Ocean

Sediment proxy data from the Norwegian, Greenland, and Iceland seas (Nordic seas) are presented to evaluate surface water temperature (SST) differences between Holocene and Eemian times and to deduce from these data the particular mode of surface water circulation. Records from planktic foraminiferal assemblages, CaCO3 content, oxygen isotopes of foraminifera, and iceberg-rafted debris form the main basis of interpretation. All results indicate for the Eemian comparatively cooler northern Nordic seas than for the Holocene due to a reduction in the northwardly flow of Atlantic surface water towards Fram Strait and the Arctic Ocean. Therefore, the cold polar water flow from the Arctic Ocean was less influencial in the southwestern Nordic seas during this time. As can be further deduced from the Eemian data, slightly higher Eemian SSTs are interpreted for the western Iceland Sea compared to the Norwegian Sea (ca. south of 70°N). This Eemian situation is in contrast to the Holocene when the main mass of warmest Atlantic surface water flows along the Norwegian continental margin northwards and into the Arctic Ocean. Thus, a moderate northwardly decrease in SST is observed in the eastern Nordic seas for this time, causing a meridional transfer in ocean heat. Due to this distribution in SSTs the Holocene is dominated by a meridional circulation pattern. The interpretation of the Eemian data imply a dominantly zonal surface water circulation with a steep meridional gradient in SSTs.

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.

Cholesterol and C30 of sediment profile MD90-963

In a deep-sea sediment core recovered from a site lying well above the local lysocline, several organic geochemical proxies, and two different calcite dissolution indicators, are compared in order to evaluate the relationship between calcite dissolution and paleoproductivity over the past three glacial-interglacial cycles. The degree of foraminiferal break-up, and the CaCO3 particle size distribution, both point to significant periods of dissolution every 22 kyr during glacial stages and substages. These dissolution events are concomitant with periods of enhanced primary productivity, as indicated by the abundance of several biomarkers (alkenones, cholesterol, brassicasterol, keto-ol), used here to indicate changes in paleoproductivity. Dissolution fluctuations are highly coherent and in phase with the estimated paleoproductivity variations providing strong evidence that the observed dissolution is due to organic matter remineralization within the sediments rather, than to changes in CO32? concentration in the overlying water column.

TOC, CaCO3, n-alkane and alkenone concentrations of ODP Sites 202-1237 and 202-1239

We generated preliminary downcore records of total organic carbon content, calcium carbonate, long-chain n-alkane concentration, total alkenone concentration, and alkenone-based sea-surface temperature for samples from the easternmost flank of Nazca Ridge (Site 1237) and the eastern crest of Carnegie Ridge (Site 1239). Total organic carbon and long-chain n-alkane concentrations will be used to evaluate terrestrial sediment sources. Downcore records of alkenone sea-surface temperature will benefit studies of paleoceanography of the southeastern Pacific. Since these sites are located under the influence of major tectonic events, such as the uplift of the Andes Mountains and the closure of the Isthmus of Panama, the records will help us to examine the effects of the tectonic events on the oceanic environment.

(Table 1) Age determination of sediment core SO136-003GC

We compile and compare data for the last 150,000 years from four deep-sea cores in the midlatitude zone of the Southern Hemisphere. We recalculate sea surface temperature estimates derived from foraminifera and compare these with estimates derived from alkenones and magnesium/calcium ratios in foraminiferal carbonate and with accompanying sedimentological and pollen records on a common absolute timescale. Using a stack of the highest-resolution records, we find that first-order climate change occurs in concert with changes in insolation in the Northern Hemisphere. Glacier extent and inferred vegetation changes in Australia and New Zealand vary in tandem with sea surface temperatures, signifying close links between oceanic and terrestrial temperature. In the Southern Ocean, rapid temperature change of the order of 6°C occurs within a few centuries and appears to have played an important role in midlatitude climate change. Sea surface temperature changes over longer periods closely match proxy temperature records from Antarctic ice cores. Warm events correlate with Antarctic events A1-A4 and appear to occur just before Dansgaard-Oeschger events 8, 12, 14, and 17 in Greenland.

(Table 1) Sea surface temperature reconstruction for eastern equatorial Pacific surface sediment samples

Significant uncertainties persist in the reconstruction of past sea surface temperatures in the eastern equatorial Pacific, especially regarding the amplitude of the glacial cooling and the details of the post-glacial warming. Here we present the first regional calibration of alkenone unsaturation in surface sediments versus mean annual sea surface temperatures (maSST). Based on 81 new and 48 previously published data points, it is shown that open ocean samples conform to established global regressions of Uk'37 versus maSST and that there is no systematic bias from seasonality in the production or export of alkenones, or from surface ocean nutrient concentrations or salinity. The flattening of the regression at the highest maSSTs is found to be statistically insignificant. For the near-coastal Peru upwelling zone between 11-15°S and 76-79°W, however, we corroborate earlier observations that Uk'37 SST estimates significantly over-estimate maSSTs at many sites. We posit that this is caused either by uncertainties in the determination of maSSTs in this highly dynamic environment, or by biasing of the alkenone paleothermometer toward El Niño events as postulated by Rein et al. (2005).

(Table 1) Age determination of sediment core SO139-74KL

A multiproxy record has been acquired from a piston core (SO139-74KL) taken offshore southern Sumatra, an area which is situated in the southwestern sector of the tropical Indo-Pacific Warm Pool. The high-resolution data sets (X-ray fluorescence, total organic carbon, and C37 alkenones) were used to track changes in paleoproductivity, freshwater budget, and sea surface temperature (SST) of the tropical climate system at orbital time scales over the past 300 ka. Our paleoclimatic data show that enhanced marine paleoproductivity was directly related to strengthening of coastal upwelling during periods of increased boreal summer insolation and associated SE monsoon strength with a precessional cyclicity. Changes in freshwater supply were primarily forced by precession-controlled changes in boreal NW winter monsoon rainfall enclosing an additional sea level component. SST variations of 2°-5°C occurred at eccentricity and precessional cyclicity. We suggest that the sea surface temperature variability off southern Sumatra is predominantly related to three major causes: (1) variations in upwelling intensity; (2) an elevated freshwater input into the southern Makassar Strait leading to reduced supply of warmer surface waters from the western Pacific and increased subsurface water transport via the Indonesian Throughflow into the Indian Ocean; and (3) long-term changes in the intensity or frequency of low-latitude climate phenomena, such as El Niño-Southern Oscillation.