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.

Holocene Mg/Ca, alkenones, and light stable isotope measurements on the outer North Iceland shelf, sediment core MD99-2269

We present new Holocene century to millennial-scale proxies for the well-dated piston core MD99-2269 from Húnaflóadjúp on the North Iceland Shelf. The core is located in 365 mwd and lies close to the fluctuating boundary between Atlantic and Arctic/Polar waters. The proxies are: alkenone-based SST°C, and Mg/Ca SST°C estimates and stable d13C and d18O values on planktonic and benthic foraminifera. The data were converted to 60 yr equi-spaced time-series. Significant trends in the data were extracted using Singular Spectrum Analysis and these accounted for between 50% and 70% of the variance. A comparison between these data with previously published climate proxies from MD99-2269 was carried out on a data set which consisted of 14-variable data set covering the interval 400-9200 cal yr BP at 100 yr time steps. This analysis indicated that the 1st two PC axes accounted for 57% of the variability with high loadings clustering primarily into "nutrient" and "temperature" proxies. Clustering on the 100 yr time-series indicated major changes in environment at ~6350 and ~3450 cal yr BP, which define early, mid- and late Holocene climatic intervals. We argue that a pervasive freshwater cap during the early Holocene resulted in warm SST°s, a stratified water column, and a depleted nutrient supply. The loss of the freshwater layer in the mid-Holocene resulted in high carbonate production, and the late Holocene/neoglacial interval was marked by significantly more variable sea surface conditions.

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.

Sea surface temperature estimation of sediment core 86014-12PC51

A recently developed technique for determining past sea surface temperatures (SST), based on an analysis of the unsaturation ratio of long chain C37 methyl alkenones produced by Prymnesiophyceae phytoplankton (U37 k' ), has been applied to an upper Quaternary sediment core from the equatorial Atlantic. U37 k' temperature estimates were compared to those obtained from delta18O of the planktonic foraminifer Globigerinoides sacculifer and of planktonic foraminiferal assemblages for the last glacial cycle. The alkenone method showed 1.8°C cooling at the last glacial maximum, about 1/2 to 1/3 of the decrease shown by the isotopic method (6.3°C) and foraminiferal modern analogue technique estimates for the warm season (3.8°C). Warm season foraminiferal assemblage estimates based on transfer functions are out of phase with the other estimates, showing a 1.4°C drop at the last glacial maximum with an additional 0.9°C drop in the deglaciation. Increased alkenone abundances, total organic carbon percentage and foraminiferal accumulation rates in the last glaciation indicate an increase in productivity of as much as 4 times over present day. These changes are thought to be due to increased upwelling caused by enhanced winds during the glaciation. If U37 k' estimates are correct, as much as 50-70% (up to 4.5°C) of estimated delta18O and modern analogue temperature changes in the last glaciation may have been due to changes in thermocline depth, whereas transfer functions seem more strongly influenced by seasonality changes. This indicates these estimates may be influenced as strongly by other factors as they are by SST, which in the equatorial Atlantic was only reduced slightly in the last glaciation.

Flux of biomarkers and organisms at AWI HAUSGARTEN from two moorings

Time-series sediment traps were deployed at 4 depths in the eastern Fram Strait from July 2007 to June 2008 to investigate variations in the magnitude and composition of the sinking particulate matter from upper waters to the seafloor. Sediment traps were deployed at 196 m in the Atlantic Water layer, at 1296 and 2364 m in the intermediate and deep waters, and at 2430 m on a benthic lander in the near-bottom layer. Fluxes of total particulate matter, particulate organic carbon, particulate organic nitrogen, biogenic matter, lithogenic matter, biogenic particulate silica, calcium carbonate, dominant phytoplankton cells, and zooplankton fecal pellets increased with depth, indicating the importance of lateral advection on fluxes in the deep Fram Strait. The lateral supply of particulate matter was further supported by the constant fluxes of biomarkers such as brassicasterol, alkenones, campesterol, beta-sitosterol, and IP25 at all depths sampled. However, enhanced fluxes of diatoms and appendicularian fecal pellets from the upper waters to the seafloor in the presence of ice during spring indicated the rapid export (15-35 days) of locally-produced large particles that likely contributed most of the food supply to the benthic communities. These results show that lateral supply and downward fluxes are both important processes influencing the transport of particulate matter to the seafloor in the deep eastern Fram Strait, and that particulate matter size dictates the prevailing sinking process.

Decadal-to-centennial scale variations during the Holocene reconstructed from sediment core D13902

Sea surface temperature (SST), marine productivity, and fluvial input have been reconstructed for the last 11.5 calendar (cal) ka B.P. using a high-resolution study of C37 alkenones, coccolithophores, iron content, and higher plant n-alkanes and n-alkan-1-ols in sedimentary sequences from the inner shelf off the Tagus River Estuary in the Portuguese Margin. The SST record is marked by a continuous decrease from 19C, at 10.5 and 7 ka, to 15C at present. This trend is interrupted by a fall from 18C during the Roman and Medieval Warm Periods to 16C in the Little Ice Age. River input was very low in the early Holocene but increased in the last 3 cal ka B.P. in association with an intensification of agriculture and deforestation and possibly the onset of the North Atlantic Oscillation/Atlantic Multidecadal Oscillation modes of variability. River influence must have reinforced the marine cooling trend relative to the lower amplitude in similar latitude sites of the eastern Atlantic. The total concentration of alkenones reflects river-induced productivity, being low in the early Holocene but increasing as river input became more important. Rapid cooling, of 1-2C occurring in 250 years, is observed at 11.1, 10.6, 8.2, 6.9, and 5.4 cal ka B.P. The estimated age of these events matches the ages of equivalent episodes common in the NE Atlantic- Mediterranean region. This synchronicity reveals a common widespread climate feature, which considering the twentieth century analog between colder SSTs and negative North Atlantic Oscillation (NAO), is likely to reflect periods of strong negative NAO.

(Table 1) Lipid biomarkers in surface sediments from the Gulf of Genoa

A series of molecular organic markers were determined in surface sediments from the Gulf of Genoa (Ligurian Sea) in order to evaluate their potential for palaeo-environmental reconstructions. Allochthonous input can be characterized by the distributions of n-C29 and n-C31 alkanes, n-C26 and n-C28 alkanols and branched glycerol dialkyl glycerol tetraethers (GDGTs), whose concentrations are generally highest near the river mouths. In the open basin however, terrestrial n-alkanes and n-alkanols may have an additional, aeolian source. Autochthonous input is represented by crenarchaeol and isoprenoid GDGTs. Their concentrations are highest in the open basin showing the preference of Thaumarchaeota for oligotrophic waters. Indications of a significant degradation of sterols and C37 alkenones exclude these lipids as reliable productivity proxies. Using terrestrial and aquatic lipids as end-members allows estimating the percentage of terrestrial organic matter between 20% and 58% in the coastal area decreasing to 1 to 30% in the deep basin. The spatial distribution of sea surface temperature (SST) estimates using the alkenone-based UK'37 index is very similar to the autumnal (November) mean satellite-based SST distribution. Conversely, TEXH86-derived SST estimates are close to winter SSTs in the coastal area and summer SSTs in the open basin. This pattern reflects presumably a shift in the main production of Thaumarchaeota from the coastal area in winter to the open basin in summer. This study represents a major prerequisite for the future application of lipid biomarkers on sediment cores from the Gulf of Genoa.

(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.

Alkenone stable carbon isotopes, carbonate stable carbon and oxygen isotopes, planktic foraminifera boron isotopes and atmospheric CO2 calculations and box model results from Ras il-Pellegrin section, Malta

The development of a permanent, stable ice sheet in East Antarctica happened during the middle Miocene, about 14 million years (Myr) ago. The middle Miocene therefore represents one of the distinct phases of rapid change in the transition from the "greenhouse" of the early Eocene to the "icehouse" of the present day. Carbonate carbon isotope records of the period immediately following the main stage of ice sheet development reveal a major perturbation in the carbon system, represented by the positive d13C excursion known as carbon maximum 6 ("M6"), which has traditionally been interpreted as reflecting increased burial of organic matter and atmospheric pCO2 drawdown. More recently, it has been suggested that the d13C excursion records a negative feedback resulting from the reduction of silicate weathering and an increase in atmospheric pCO2. Here we present high-resolution multi-proxy (alkenone carbon and foraminiferal boron isotope) records of atmospheric carbon dioxide and sea surface temperature across CM6. Similar to previously published records spanning this interval, our records document a world of generally low (~300 ppm) atmospheric pCO2 at a time generally accepted to be much warmer than today. Crucially, they also reveal a pCO2 decrease with associated cooling, which demonstrates that the carbon burial hypothesis for CM6 is feasible and could have acted as a positive feedback on global cooling.

Sea surface temperature reconstruction for the middle Pleistocene from sediment core MD03-2699

Past sea surface water conditions of the western Iberian Margin were reconstructed based on biomarker analyses of a marine deep sea core MD03-2699 from the Estremadura Spur north off Lisbon, providing new insights into orbital and suborbital-scale climate variability between marine isotope stage (MIS) 15 to MIS 9 (580 to 300 ka). We use biomarker-based proxy records such as the alkenone unsaturated index to estimate sea surface temperature (SST), the total alkenone concentration to reconstruct phytoplankton productivity, and terrestrial biomarkers to evaluate the continental input. The results extend the existing biomarker record, namely the SST for the Iberian Margin, back to the sixth climatic cycle (580 ka). A general trend of stable interglacials contrasts with glacial periods and glacial inceptions which are marked by high-frequency variability. Thus, several short-lived climatic coolings were identified by large SST decreases, the occurrence of ice-rafted detritus and high percentages of the tetraunsaturated alkenone C 37:4. Some of these events were extremely cold and similar in their general trends to the well-known Heinrich events of the last glaciation. We identified eight Heinrich-type events between 580 and 300 ka. The general deglaciation pattern detected between MIS 15 and MIS 9 is similar in their general trends to that characterizing the more recent climatic cycles, i.e., marked by two coolings separated by a short warming episode which may reflect the southward, northward, and southward migration of the Polar Front.

Delta 13C measured on alkenones of surface sediment samples GeoB1008-6 to GeoB3603-1 from the South Atlantic

We have analyzed the stable carbon isotopic composition of the diunsaturated C37 alkenone in 29 surface sediments from the equatorial and South Atlantic Ocean. Our study area covers different oceanographic settings, including sediments from the major upwelling regions off South Africa, the equatorial upwelling, and the oligotrophic western South Atlantic. In order to examine the environmental influences on the sedimentary record the alkenone-based carbon isotopic fractionation (Ep) values were correlated with the overlying surface water concentrations of aqueous CO2 ([CO2(aq)]), phosphate, and nitrate. We found Ep positively correlated with 1/[CO2(aq)] and negatively correlated with [PO43-] and [NO3-]. However, the relationship between Ep and 1/[CO2(aq)] is opposite of what is expected from a [CO2(aq)] controlled, diffusive uptake model. Instead, our findings support the theory of Bidigare et al. (1997, doi:10.1029/96GB03939) that the isotopic fractionation in haptophytes is related to nutrient-limited growth rates. The relatively high variability of the Ep-[PO4] relationship in regions with low surface water nutrient concentrations indicates that here other environmental factors also affect the isotopic signal. These factors might be variations in other growth-limiting resources such as light intensity or micronutrient concentrations.

Age model and chemistry of sediment core STK7 from Steisslinger See

Stable isotope records for carbon and oxygen in bulk carbonates, carbon in bulk organic matter, and for total and chromium-reducible sulfur in a lacustrine sediment core from Lake Steisslingen (Southwest Germany) show several distinct and abrupt shifts during the last 15,000 years. Variations in the isotopic composition of authigenic carbonates indicate two major phases in the lake history. In the pre-Holocene, the hydrological budget of the lake was apparently stable. Variations of delta18O values of authigenic carbonates were, therefore, dominantly controlled by temperature changes. A decrease in the delta18Ocarb values of about 2 per mil at the Allerød/Younger Dryas transition is interpreted as a drop in mean annual air temperatures of approximately 5°C. An abrupt temperature increase of a similar magnitude is inferred at the Younger Dryas/Preboreal boundary. Throughout most of the Holocene, the isotopic composition of authigenic carbonates was influenced by marked changes in the hydrological budget of the lake. A major positive excursion in the delta13Ccarb and delta18Ocarb values at the beginning of the Atlantic and a smaller one in the Preboreal were related to evaporation effects, which indicate that dry climatic conditions must have prevailed at that time. A simultaneous increase in delta13C values of bulk organic matter at the beginning of the Atlantic suggests a high level of productivity in the lake. As a consequence, aqueous sulfate became limited as indicated by variations in the delta34S values of total and chromium-reducible sedimentary sulfur. Therefore, we conclude that the beginning of the Atlantic was characterized not only by dry but also by warm climatic conditions, which triggered a higher productivity in the lake. In the Subatlantic sediments, large variations in carbon, oxygen, and sulfur isotope ratios were observed as a result of human activities, causing considerable perturbations in the biogeochemical element cycling of Lake Steisslingen. Results obtained by the study of the continuous 15 ka record of Lake Steisslingen document clearly that isotopic proxy data from lacustrine sediments can provide useful information on environmental and climatic changes of local, regional, and in the case of the Younger Dryas event, of even hemispherical significance.