(Table 1) Results of alkenone analyses of ODP Hole 165-1002C

We determined alkenone concentrations (µg/g dry sediment) and unsaturation indices (Uk'37) on 280 samples from Ocean Drilling Program Hole 1002C over the last full glacial cycle (marine oxygen isotope Stages [MIS] 1-6). Alkenone concentrations vary dramatically in relation to glacial-interglacial cycles, with high concentrations typical of interglacial stages, high sea level, inferred high surface productivity, and bottom-water anoxia. Our reconstruction of low productivity during the last glacial maximum is consistent with previous reports of a sharp decline in the foraminiferal species Neogloboquadrina dutertrei, an upwelling index. Alkenone paleotemperatures show little cooling at both the last glacial maximum and MIS 6. Variations of as much as 4°C occurred during the earlier part of MIS 3 and MIS 4 as well as the latter part of MIS 5. The absence of cooling during glacial maxima determined from alkenone paleothermometry is consistent with faunal reconstructions for the western Caribbean but requires that much of the oxygen isotopic record of the planktonic foraminifer Globigerinoides ruber be influenced by salinity variations rather than temperature.

Alkenone data of sediment traps off Cape Blanc, NW Africa

We analysed long-chain alkenones in sinking particles and surface sediments from the filamentous upwelling region off Cape Blanc, NW Africa, to evaluate the transfer of surface water signals into the geological record. Our study is based on time-series sediment trap records from 730 m (1990-1991) to 2195-3562 m depth (1988-1991). Alkenone fluxes showed considerable interannual variations and no consistent seasonality. The average flux of C37 and C38 alkenones to the deep traps was 1.9 µg/m**2/d from March 1988 to October 1990 and sevenfold higher in the subsequent year. Alkenone fluxes to the shallower traps were on average twice as high and showed similar temporal variations. The alkenone unsaturation indices UK'37, UK38Me and UK38Et closely mirrored the seasonal variations in sea-surface temperature (weekly Reynolds SST). Time lags of 10-48 days between the SST and unsaturation maxima suggest particle sinking rates of about 80 and 280 m/d for the periods of low and high alkenone fluxes, respectively. The average flux-weighted UK'37 temperature for the 4-year time series of the deeper traps was 22.1°C, in perfect agreement with the mean weekly SST for the same period. This and the comparison with seasonal temperature variations in the upper 100 m of the water column suggests that UK'37 records principally the yearly average of the mixed-layer temperature in this region. A comparison between the average annual alkenone fluxes to the lower traps (2400 µg/m**2/yr) and into the underlying sediments (4 µg/m**2/yr) suggests that only about 0.2% of the alkenones reaching the deep ocean became preserved in the sediments. The flux-weighted alkenone concentrations also decreased considerably, from 2466 µg/gC in the water column to 62 µg/gC in the surface sediments. Such a low degree of alkenone preservation is typical for slowly accumulating oxygenated sediments. Despite these dramatic diagenetic alkenone losses, the UK'37 ratio was not affected. The average UK'37 value of the sediments (0.796±0.010 or 22.3±0.3°C) was identical within error limits to the 4-year average of the lower traps. The unsaturation indices for C38 alkenones and the ratio between C37 and C38 alkenones also revealed a high degree of stability. Our results do not support the hypothesis that UK'37 is biased towards higher values during oxic diagenesis.

(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.

Alkenone and foraminifera records from sediment samples off Namibia

Radiocarbon stratigraphy is an essential tool for high resolution paleoceanographic studies. Age models based on radiocarbon ages of foraminifera are commonly applied to a wide range of geochemical studies, including the investigation of temporal leads and lags. The critical assumption is that temporal coupling between foraminifera and other sediment constituents, including specific molecular organic compounds (biomarkers) of marine phytoplankton, e.g. alkenones, is maintained in the sediments. To test this critical assumption in the Benguela upwelling area, we have determined radiocarbon ages of total C37-C39 alkenones in 20 samples from two gravity cores and three multicorer cores. The cores were retrieved from the continental shelf and slope off Namibia, and samples were taken from Holocene, deglacial and Last Glacial Maximum core sections. The alkenone radiocarbon ages were compared to those of planktic foraminifera, total organic carbon, fatty acids and fine grained carbonates from the same samples. Interestingly, the ages of alkenones were 1000 to 4500 yr older than those of foraminifera in all samples. Such age differences may be the result of different processes: Bioturbation associated with grain size effects, lateral advection of (recycled) material and redeposition of sediment on upper continental slopes due to currents or tidal movement are examples for such processes. Based on the results of this study, the age offsets between foraminifera and alkenones in sediments from the upper continental slope off Namibia most probably do not result from particle-selective bioturbation processes. Resuspension of organic particles in response to tidal movement of bottom waters with velocities up to 25 cm/s recorded near the core sites is the more likely explanation. Our results imply that age control established using radiocarbon measurements of foraminifera may be inadequate for the interpretation of alkenone-based proxy data. Observed temporal leads and lags between foraminifera based data and data derived from alkenone measurements may therefore be secondary signals, i.e. the result of processes associated with particle settling and biological activity.

Alkenone unsaturation index and alkenones in ODP Hole 161-977A

A number of essential elements closely related to each other are involved in the Earth's climatic system. The temporal and spatial distribution of insolation determines wind patterns and the ocean's thermohaline pump. In turn, these last two are directly linked to the extension and retreat of marine and continental ice and to the chemistry of the atmosphere and the ocean. The variability of these elements may trigger, amplify, sustain or globalize rapid climatic changes. Paleoclimatic oscillations have been identified in this thesis by using fossil organic compounds synthesized by marine and terrestrial flora. High sedimentation rate deposits at the Barents and the Iberian peninsula continental margins were chosen in order to estimate the climatic changes on centennial time resolution. At the Barents margin, the sediment recovered was up to 15,000 years old (unit ''a'', from latin ''annos'') (M23258; west of the Bjørnøya island). At the Iberian margin, the sediment cores studied covered a wide range of time spans: up to 115,000 a (MD99-2343; north of the Minorca island), up to 250,000 a (ODP-977A; Alboran basin) and up to 420,000 a (MD01-2442, MD01-2443, MD01-2444, MD01-2445; close to the Tagus abyssal plain). At the northern site, inputs containing marine, continental and ancient reworked organic matter provided a detailed reconstruction of climate history at the time of the final retreat of the Barents ice sheet. At the western Barents continental slope, warm climatic conditions were observed during the early Holocene (~from 8,650 a to 5,240 a ago); in contrast, an apparent long-term cooling trend occurred in the late Holocene (~from 5,240 a to 760 a ago), in consistence with other paleoarchives from northern and southern European latitudes. The Iberian margin sites, which were never covered with large ice sheets, preserved exceptionally complete sequences of rapid events during ice ages hitherto not studied in such great detail: during the last glacial (~from 70,900 a to 11,800 a ago), the second glacial (~from 189,300 a to 127,500 a ago), the third ice age (~from 278,600 a to 244,800 a ago) and the fourth (~from 376,300 a to 337,500 a ago). In this thesis, crucial research questions were brought up concerning the severity of different glacial periods, the intensity and rates of the recorded oscillations and the long distance connections related to rapid climate change. The data obtained provide a sound basis to further research on the mechanisms involved in this rapid climate variability. An essential point of the research was the evidence that, over the past 420,000 a, at the whole Iberian margin, warm and stable long periods similar to the Holocene always ended abruptly in few centuries after a gradual deterioration of climate conditions. The detailed estimate of past climate variability provides clues to the natural end of the present warm period. Returning to an ice age in European lands would be exacerbated by a number of factors: a lack of differential solar heating between northern and southern north Atlantic latitudes, enhanced evaporation at low latitudes, and an increase in snowfall or iceberg discharges at northern regions. It must be emphasized that all climatic oscillations observed in this thesis were caused by forces of nature, i.e. the last two centuries were not taken into consideration.

Calcareous nannofossils and C37 alkenones at ODP Site 162-982

During the late Pliocene (~3 to 2.5 Ma), oceanic records of opal and C37 alkenone accumulation from around the world show a secular shift towards lower values in the high latitudes and higher values in the low and mid latitudes. These shifts are broadly coincident with the intensification of northern hemisphere glaciation and are suggestive of changes in export productivity, with potential implications for Pliocene atmospheric carbon dioxide concentrations. The interpretation of a global latitudinal shift in productivity, however, requires testing because of the potential uncertainties associated with site to site comparisons of records that can be influenced by highly nonlinear processes associated with production, export, and preservation. Here, we assess the inferred Pliocene latitudinal productivity shift interpretation by presenting new records of C37 alkenone accumulation from Ocean Drilling Program (ODP) Site 982 in the North Atlantic and biotic assemblages (calcareous nannoplankton) from this site and ODP Site 846 in the eastern tropical Pacific. Our results corroborate the interpretation of C37 alkenone accumulation as a proxy for gross export productivity at these sites, indicating that large-scale productivity decreases at high latitudes and increases at tropical sites are recorded robustly. We conclude that the intensification of northern hemisphere glaciation during the late Pliocene was associated with a profound reorganisation of ocean biogeochemistry.

(Table 1) Alkenone concentration, UK'37 index and derived sea surface temperatures for ODP Site 167-1020

Uk'37 sea-surface temperature (SST) estimates obtained at ~2.5-k.y. resolution from Ocean Drilling Program Site 1020 show glacial-interglacial cyclicity with an amplitude of 7°-10°C over the last 780 k.y. This record shows a similar pattern of variability to another alkenone-based SST record obtained previously from the Santa Barbara Basin. Both records show that oxygen isotope Stage (OIS) 5.5 was warmer by ~3°C relative to the present and that glacial Uk'37 temperatures warm in advance of deglaciation, as inferred from benthic d18O records. The alkenone-based SST record at Site 1020 is longer than previously published work along the California margin. We show that warmer than present interglacial stages have occurred frequently during the last 800 k.y. Alkenone concentrations, a proxy for coccolithophorid productivity, indicate that sedimentary marine organic carbon content has also varied significantly over this interval, with higher contents during interglacial periods. A baseline shift to warmer SST and greater alkenone content occurs before OIS 13. We compare our results with those from previous multiproxy studies in this region and conclude that SST has increased by ~5°C since the last glacial period (21 ka). Our data show that maximum alkenone SSTs occur simultaneously with minimum ice volume at Site 1020, which is consistent with data from farther south along the margin. The presence of sea ice in the glacial northeast Pacific, the extent of which is inferred from locations of ice-rafted debris, provides further support for our notion of cold surface water within the northern California Current system, averaging 7°-8°C cooler during peak glacial conditions. The cooling of surface water during glacial stages most likely did not result from enhanced upwelling because alkenone concentrations and terrestrial redwood pollen assemblages are consistently lower during glacial periods.

Ice rafted debris, tetra-unsaturated alkenone and reconstructed sea surface temperature in sediment of ODP Hole 104-642B

Abstract of paper will be inserted here...

Geochemistry and sea-surface temperature reconstruction for sediment cores of the Iberian Margin

Biogenic records of the marine palaeoproductivity (carbonates, organic carbon, and C37 alkenones) and the molecular stratigraphy of past sea surface temperatures (SSTs; UK'37) were studied at high resolution in two cores of the Iberian Margin. The comparison of these records indicates that the oceanographic conditions switched abruptly during the past 160 kyr between three kinds of regimes. A first regime with high (17-22°C) SST and low productivity typifies the interglacial periods, marine isotopic stages (MIS) 5 and 1. Several periods during MIS 6, 2, and the terminations II and I are characterised by about 4-5°C colder SST and a higher organic matter accumulation, both of which define the second regime. This anticorrelation between SST and marine productivity suggests that these variations are related to the intensity of the coastal upwelling. By contrast with this upwelling behaviour, extremely low biological productivity and very cold SST (6-12°C) occurred during short phases of glacial MIS 6, 4, and 2, and as abrupt events (~1 kyr or less) during MIS 3. The three oceanographic regimes are consistent with micropalaeontological changes in the same cores based on foraminifera and diatoms. The general trend of these hydrologic changes follows the long-term glacial/interglacial cycle, but the millennium scale variability is clearly related to Heinrich events and Dansgaard-Oeschger cycles. Strengthening of the upwelling corresponds probably to an intensification of the subtropical atmospheric circulation over the North Atlantic which was influenced by the presence of continental ice sheets. However, extreme glacial conditions due to massive discharges of icebergs interrupted the upwelling. Interestingly, both terminations II and I coincided with strong but transient intensification of the upwelling.

A four-year record of UK'37- and TEX86-derived sea surface temperature estimates from sinking particles in the filamentous upwelling region off Cape Blanc, Mauritania

Lipid biomarker records from sinking particles collected by sediment traps are excellent tools to study the seasonality of biomarker production as well as processes of particle formation and settling, ultimately leading to the preservation of the biomarkers in sediments. Here we present records of the biomarker indices UK'37 based on alkenones and TEX86 based on isoprenoid glycerol dialkyl glycerol tetraethers (GDGTs), both used for the reconstruction of sea surface temperatures (SST). These records were obtained from sinking particles collected using a sediment trap moored in the filamentous upwelling zone off Cape Blanc, Mauritania, at approximately 1300 water depth during a four-year time interval between 2003 and 2007. Mass and lipid fluxes are highest during peak upwelling periods between October and June. The alkenone and GDGT records both display pronounced seasonal variability. Sinking velocities calculated from the time lag between measured SST maxima and minima and corresponding index maxima and minima in the trap samples are higher for particles containing alkenones (14-59 m/d) than for GDGTs (9-17 m/d). It is suggested that GDGTs are predominantly exported from shallow waters by incorporation in opal-rich particles. SST estimates based on the UK'37 index faithfully record observed fluctuations in SST during the study period. Temperature estimates based on TEX86 show smaller seasonal amplitudes, which can be explained with either predominant production of GDGTs during the warm season, or a contribution of GDGTs exported from deep waters carrying GDGTs in a distribution that translates to a high TEX86 signal.

Geological investigations on sediment core MD07-3128

Glacial millennial-scale paleoceanographic changes in the Southeast Pacific and the adjacent Southern Ocean are poorly known due to the scarcity of well-dated and high resolution sediment records. Here we present new surface water records from sediment core MD07-3128 recovered at 53°S off the Pacific entrance of the Strait of Magellan. The alkenone-derived sea surface temperature (SST) record reveals a very strong warming of ca. 8°C over the last Termination and substantial millennial-scale variability in the glacial section largely consistent with our planktonic foraminifera oxygen isotope (d18O) record of Neogloboquadrina pachyderma (sin.). The timing and structure of the Termination and some of the millennial-scale SST fluctuations are very similar to those observed in the well-dated SST record from ODP Site 1233 (41°S) and the temperature record from Drowning Maud Land Antarctic ice core supporting the hemispheric-wide Antarctic timing of SST changes. However, differences in our new SST record are also found including a long-term warming trend over Marine Isotope Stage (MIS) 3 followed by a cooling toward the Last Glacial Maximum (LGM). We suggest that these differences reflect regional cooling related to the proximal location of the southern Patagonian Ice Sheet and related meltwater supply at least during the LGM consistent with the fact that no longer SST cooling trend is observed in ODP Site 1233 or any SST Chilean record. This proximal ice sheet location is documented by generally higher contents of ice rafted debris (IRD) and tetra-unsaturated alkenones, and a slight trend toward lighter planktonic d18O during late MIS 3 and MIS 2.

Uk'37, derived sea surface temperatures and coccolith abundances in North Atlantic sediment cores

The UK37' index has proven to be a robust proxy to estimate past sea surface temperatures (SSTs) over a range of time scales, but like any other proxy, it has uncertainties. For instance, in reconstructions of the Last Glacial Maximum (LGM) in the northern North Atlantic, UK37' indicates higher temperatures than those derived from foraminiferal proxies. Here we evaluate whether such warm glacial estimates are caused by the advection of reworked alkenones in ice-rafted debris (IRD) to deep-sea sediments. We have quantified both coccolith assemblages and alkenones in sediments from glaciogenic debris flows in the continental margins of the northern North Atlantic, and from a deep-sea core from the Reykjanes Ridge. Certain debris flow deposits in the North Atlantic were generated by the presence of massive ice-sheets in the past, and their associated ice streams. Such deposits are composed of the same materials that were present in the IRD at the time they were generated. We conclude that ice rafting from some locations was a transport pathway to the deep sea floor of reworked alkenones and pre-Quaternary coccolith species during glacial stages, but that not all of the IRD contained alkenones, even when reworked coccoliths were present. We speculate that the ratio of reworked coccoliths to alkenone concentration might be useful to infer whether significant reworked alkenone inputs from IRD did occur at a particular site in the glacial North Atlantic. We also observe that alkenones in some of the debris flows contain a colder signal than estimated for LGM sediments in the northern North Atlantic. This is also clear in the deep-sea core studied where the warmest intervals do not correspond to the intervals with large inputs of reworked coccoliths or IRD. We conclude that any possible bias to UK37' estimates associated with reworked alkenones is not necessarily towards higher values, and that the high SST anomalies for the LGM are unlikely to be the result of a bias caused by IRD inputs.

Organic geochemistry of sediment cores from the Arbian Sea

Two deep-sea sediment cores from the northeastern and the southeastern Arabian Sea were studied in order to reconstruct the palaeoenvironments of the past glacial cycles. Core 136KL was recovered from the high-productivity area off Pakistan within the modern oxygen-minimum zone (OMZ). By contrast, modern primary productivity at the site of MD900963 close to Maldives is moderate and bottom waters are today well oxygenated. For both cores, we reconstructed the changes in palaeoproductivity using a set of biomarkers (alkenones, dinosterol and brassicasterol); the main result is that primary productivity is enhanced during glacial stages and lowered during interstadials. The proxies associated with productivity show a 23 kyr cyclicity corresponding to the precession-related insolation cycle. Palaeoredox conditions were studied in both cores using a new organic geochemical parameter (C35/C31-n-alkane ratio) developed by analysing surface sediments from a transect across the OMZ off Pakistan. The value of this ratio in core 136KL shows many variations during the last 65 kyr, indicating that the OMZ was not stable during this time: it disappeared completely during Heinrich- and the Younger Dryas events, pointing to a connection between global oceanic circulation and the stability of the OMZ. The C35/C31 ratio determined in sediments of core MD900963 shows that bottom waters remained rather well oxygenated over the last 330 kyr, which is confirmed by comparison with authigenic metal concentrations in the same sediments. A zonally averaged, circulation-biogeochemical ocean model was used to explore how the intermediate Indian Ocean responds to a freshwater flux anomaly at the surface of the North Atlantic. As suggested by the geochemical time series, both the abundance of Southern Ocean Water and the oxygen concentration are significantly increased in response to this freshwater perturbation.

Marine and terrigenous lipids in ODP Leg 175 holes

Lipid compositions of sediments recovered during Ocean Drilling Program Leg 175 in the eastern South Atlantic reflect a variety of oceanographic and climatological environments. Most of the identified lipids can be ascribed to marine sources, notably haptophytes, eustigmatophytes, dinoflagellates, archaea, and diatoms. Elevated concentrations of cholesterol suggest zooplankton herbivory, characteristic for sites influenced by upwelling. At these sites, sulfurized highly branched isoprenoids from diatoms are also present in high amounts. Sterols, sterol ethers, hopanoids, and midchain hydroxy fatty acids could also be detected. Terrigenous lipids are n-alkanes, fatty acids, n-alcohols, and triterpenoid compounds like taraxerol and -amyrine. n-Alkanes, fatty acids, and n-alcohols are derived from leaf waxes of higher land plants and transported to the sea by airborne dust or fresh water. Triterpenoid compounds are most probably derived from mangroves and transported solely by rivers. Lipid compositions below the Congo low-salinity plume are strongly influenced by terrigenous material from the Congo River. Elevated organic carbon contents and predominantly marine lipid distributions at the Angola margin may indicate a highly productive plankton population, probably sustained by the Angola Dome. Sedimentary lipids in the Walvis Basin contain an upwelling signal, likely transported by the Benguela Current. Sedimentary lipids off Lüderitz Bay and in the southern Cape Basin are dominated by plankton lipids in high to intermediate amounts, reflecting persistent and seasonal upwelling, respectively.