Plio-Pleistocene Mg/Ca and TEX86 sea surface temperature records of ODP Sites 184-1143 and 165-999,

The western warm pools of the Atlantic and Pacific oceans are a critical source of heat and moisture for the tropical climate system. Over the past five million years, global mean temperatures have cooled by 3-4 °C. Yet, current reconstructions of sea surface temperatures indicate that temperature in the warm pools has remained stable during this time. This stability has been used to suggest that tropical sea-surface temperatures are controlled by some sort of thermostat-like regulation. Here we reconstruct sea surface temperatures in the South China Sea, Caribbean Sea and western equatorial Pacific Ocean for the past five million years, using a combination of the Mg/Ca, TEXH86-and Uk'37 surface temperature proxies. Our data indicate that during the period of Pliocene warmth from about 5 to 2.6 million years ago, the western Pacific and western Atlantic warm pools were about 2 °C warmer than today. We suggest that the apparent lack of warming seen in the previous reconstructions was an artefact of low seawater Mg/Ca ratios in the Pliocene oceans. Taking this bias into account, our data indicate that tropical sea surface temperatures did change in conjunction with global mean temperatures. We therefore conclude that the temperature of the warm pools of the equatorial oceans during the Pliocene was not limited by a thermostat-like mechanism.

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.

Organic geochemistry of sediments at DSDP Leg 63 Holes

Selected core samples from the California Continental Borderland (Sites 467-469) were analyzed to evaluate the nature and composition of the lipids and kerogens in terms of their genetic origin and geological maturity. The lipids were of a multiple origin. On the basis of the homolog distributions of the n-alkanes and n-fatty acids, with the shape and magnitude of the unresolved branched and cyclic hydrocarbons, and the structural and stereochemical compositions of the molecular markers, these lipids were derived from primary autochthonous marine (microbial), from allochthonous terrigenous (higher plant wax), and from recycled (geologically mature organic matter) sources. The kerogens were composed of principally marine microbial detritus with a minor input of allochthonous terrestrial material. For the most part, the samples had undergone a thermal maturation according to a normal geothermal gradient, except in the proximity of intrusives. Such additional thermal stress was evident for the samples from Site 469 and to some extent for Site 467 at about a sub-bottom depth of 700 to 800 meters.

Cretaceous stable isotopic record and sea surface temperture estimation for ODP Site 207-1259

The Turonian (93.5 to 89.3 million years ago) was one of the warmest periods of the Phanerozoic eon, with tropical sea surface temperatures over 35°C. High-amplitude sea-level changes and positive d18O excursions in marine limestones suggest that glaciation events may have punctuated this episode of extreme warmth. New d18O data from the tropical Atlantic show synchronous shifts ~91.2 million years ago for both the surface and deep ocean that are consistent with an approximately 200,000-year period of glaciation, with ice sheets of about half the size of the modern Antarctic ice cap. Even the prevailing supergreenhouse climate was not a barrier to the formation of large ice sheets, calling into question the common assumption that the poles were always ice-free during past periods of intense global warming.

Comparison of TEX86 and UK'37 temperature proxies in sinking particles in the Cariaco Basin

The Cariaco Basin, a silled, permanently anoxic basin on the continental shelf of Venezuela with a dynamic chemocline (-240-350 m), has been subject of > 20 years of oceanographic observation and sediment trap studies. We evaluated UK'37 and the TEX86 temperature proxies using sinking particles collected in shallow sediment trap samples at 275 m (Trap A) and 455 m (Trap B) (within and below the chemocline). The organic geochemical temperature proxies, UK'37. (based on coccolithophorid alkenone lipids) and TEX86 (based on archaeal glycerol dialkyl glycerol tetraether (GDGT) lipids), use observed relationships between the ratio of specific lipids and measured sea surface temperature to hindcast past sea surface temperatures. In this study, both UK'37 and TEX86 temperature proxies record seasonal temperature variations, including the cooling associated with upwelling events. UK'37-based temperatures are colder than measured sea surface temperatures, and better correlated temperature at the chlorophyll maximum. In sediment trap material collected below the chemocline (Trap B), UK'37 values are higher than those in Trap A. Warmer subchemocline UK'37 based temperatures may be related to autooxidation of sinking particles, either by small amounts of available oxygen or by alternate electron acceptors concentrated in the biologically dynamic chemocline (e.g. intermediate sulfur compounds). The absolute flux weighted TEX86 temperature values measured in sinking particles from Trap A match the measured SST well. The differences in the TEX86 values between Traps A and B are small and reflect less impact of degradation. Overall, the TEX86 temperatures in sinking particles in the Cariaco Basin reflect annual SST.

Elemental contents, non-carbonate, fatty acids and alcohols analysis from different Holes of IODP Expedition 310

During IODP Expedition 310 (Tahiti Sea Level), drowned Pleistocene-Holocene barrier-reef terraces were drilled on the slope of the volcanic island. The deglacial reef succession typically consists of a coral framework encrusted by coralline algae and later by microbialites; the latter make up < 80% of the rock volume. Lipid biomarkers were analyzed in order to identify organisms involved in reef-microbialite formation at Tahiti, as the genesis of deglacial microbialites and the conditions favoring their formation are not fully understood. Sterols plus saturated and monounsaturated short-chain fatty acids predominantly derived from both marine primary producers (algae) and bacteria comprise 44 wt% of all lipids on average, whereas long-chain fatty acids and long-chain alcohols derived from higher land plants represent an average of only 24 wt%. Bacterially derived mono-O-alkyl glycerol ethers (MAGEs) and branched fatty acids (10-Me-C16:0; iso- and anteiso-C15:0 and -C17:0) are exceptionally abundant in the microbial carbonates (average, 19 wt%) and represent biomarkers of intermediate-to-high specificity for sulfate-reducing bacteria. Both are relatively enriched in 13C compared to eukaryotic lipids. No lipid biomarkers indicative of cyanobacteria were preserved in the microbialites. The abundances of Al, Si, Fe, Mn, Ba, pyroxene, plagioclase, and magnetite reflect strong terrigenous influx with Tahitian basalt as the major source. Chemical weathering of the basalt most likely elevated nutrient levels in the reefs and this fertilization led to an increase in primary production and organic matter formation, boosting heterotrophic sulfate reduction. Based on the observed biomarker patterns, sulfate-reducing bacteria were apparently involved in the formation of microbialites in the coral reefs off Tahiti during the last deglaciation.

Animation of micro-computed tomography of bioerosion trace Entobia megastoma made by East Australian bioeroding sponge Cliona celata

Endolithic bioerosion is difficult to analyse and to describe, and it usually requires damaging of the sample material. Sponge erosion (Entobia) may be one of the most difficult to evaluate as it is simultaneously macroscopically inhomogeneous and microstructurally intricate. We studied the bioerosion traces of the two Australian sponges Cliona celata Grant, 1826 (sensu Schönberg 2000) and Cliona orientalis Thiele, 1900 with a newly available radiographic technology: high resolution X-ray micro-computed tomography (MCT). MCT allows non-destructive visualisation of live and dead structures in three dimensions and was compared to traditional microscopic methods. MCT and microscopy showed that C. celata bioerosion was more intense in the centre and branched out in the periphery. In contrast, C. orientalis produced a dense, even trace meshwork and caused an overall more intense erosion pattern than C. celata. Extended pioneering filaments were not usually found at the margins of the studied sponge erosion, but branches ended abruptly or tapered to points. Results obtained with MCT were similar in quality to observations from transparent optical spar under the dissecting microscope. Microstructures could not be resolved as well as with e.g. scanning electron microscopy (SEM). Even though sponge scars and sponge chips were easily recognisable on maximum magnification MCT images, they lacked the detail that is available from SEM. Other drawbacks of MCT involve high costs and presently limited access. Even though MCT cannot presently replace traditional techniques such as corrosion casts viewed by SEM, we obtained valuable information. Especially for the possibility to measure endolithic pore volumes, we regard MCT as a very promising tool that will continue to be optimised. A combination of different methods will produce the best results in the study of Entobia.

Carbon, hydrocarbon and alkenone composition and indices of ODP Hole 167-1016C sediments

Total organic carbon (TOC) and calcium carbonate (CaCO3) concentrations were determined for 304 samples, and biomarkers were analyzed for 101 samples from Core 167-1016C-1H. TOC varies between 1% and 2%, and CaCO3 is typically 1%-4%, with peaks reaching 14%. Paleotemperature estimated from Uk'37 varies from 8.5° to 17.5°C. The Uk'37 variation implies that Core 167-1016C-1H covers oxygen isotope Stages 1-6. Peaks of diatom-derived C25:1 HBI alkene concentrations occur during warming intervals, suggesting intensified upwelling during deglaciation. The concentrations of haptophyte-derived alkenones and diatom-derived C25:1 HBI alkene vary out of phase, which presumably resulted from the changes in the mode of nutrient supply to surface mixed layer. Maximal CaCO3 contents (>10%) were observed in both warming and cooling intervals. The peak in cooling interval relates to an alkenone maximum, whereas the peaks in warming intervals do not. This implies that carbonate production is not the only factor controlling carbonate compensation depth at this site, and it suggests considering the changes in North Pacific deep-water chemistry. Petroleum-type compounds are present in Site 1016 sediments. Their concentrations are maximized in the warming intervals that correspond to the timing of destruction of a huge tar mound off Point Conception. The tarry material was presumably transported by the Arguello Fan system to Site 1016.

Organic geochemistry records from two Palaeocene-Eocene Thermal Maximum sections in Denmark

Analysis of sediments deposited at different latitudes around the world during the Palaeocene-Eocene Thermal Maximum (PETM; ~56 Ma) have revealed a globally profound warming phase, regionally varying from 5-8 °C. Such records from Europe have not yet been obtained. We studied the variations in sea surface and continental mean annual air temperatures (SST and MAT, respectively) and the distribution patterns and stable carbon isotopes of higher plant derived n-alkanes in two proximal PETM sections (Fur and Store Bælt, Denmark) from the epicontinental North Sea Basin. A negative carbon isotope excursion (CIE) of 4-7 per mil was recorded in land plant derived n-alkanes, similar to what has been observed for other PETM sections. However, differences observed between the two proximal sites suggest that local factors, such as regional vegetation and precipitation patterns, also influenced the CIE. The presence of S-bound isorenieratene derivatives at the onset of the PETM and increased organic carbon contents points to a rapid shift in depositional environment; from well oxygenated to anoxic and sulfidic. These euxinic conditions are comparable with those during the PETM in the Arctic Ocean. SSTs inferred from TEX86 show relatively low temperatures followed by an increase of ~7 °C across the PETM. At the Fur section, a remarkably similar temperature record was obtained for MAT using the MBT'/CBT proxy. However, the MAT record of the Store Bælt section did not reveal this warming.

Fractional abundance and indices for brGDGTs and crenarchaeol in dust samples, surface water samples and surface sediment samples

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are membrane lipids produced by soil bacteria and occur in near coastal marine sediments as a result of soil organic matter input. Their abundance relative to marine-derived crenarchaeol, quantified in the BIT index, generally decreases offshore. However, in distal marine sediments, low relative amounts of brGDGTs can often still be observed. Sedimentary in situ production as well as dust input have been suggested as potential, though as yet not well constrained, sources. In this study brGDGT distributions in dust were examined and compared with those in distal marine sediments. Dust was sampled along the equatorial West African coast and brGDGTs were detected in most of the samples, albeit in low abundance. Their degree of methylation and cyclisation, expressed in the MBT' (methylation index of branched tetraethers) and DC (degree of cyclisation) indices, respectively, were comparable with those for African soils, their presumed source. Comparison of DC index values for brGDGTS in global soils, Congo deep-sea river fan sediments and dust with those of distal marine sediments clearly showed, however, that distal marine sediments had significantly higher values. This distinctive distribution is suggestive of sedimentary in situ production as a source of brGDGTs in marine sediments, rather than dust input. The presence of in situ produced brGDGTs in marine sediments means that caution should be exercised when applying the MBT'-CBT palaeothermometer to sediments with low BIT index values, i.e. < 0.1, based on our dataset.

Sources and proxy potential of long chain alkyl diols in lacustrine environments

Long chain 1,13- and 1,15-alkyl diols form the base of a number of recently proposed proxies used for climate reconstruction. However, the sources of these lipids and environmental controls on their distribution are still poorly constrained. We have analyzed the long chain alkyl diol (LCD) composition of cultures of ten eustigmatophyte species, with three species from different families grown at various temperatures, to identify the effect of species composition and growth temperature on the LCD distribution. The results were compared with the LCD distribution of sixty-two lake surface sediments, and with previously reported LCD distributions from marine environments. The different families within the Eustigmatophyceae show distinct LCD patterns, with the freshwater family Eustigmataceae most closely resembling LCD distributions in both marine and lake environments. Unlike the other two eustigmatophyte families analyzed (Monodopsidaceae and Goniochloridaceae), C28 and C30 1,13-alkyl diols and C30 and C32 1,15-alkyl diols are all relatively abundant in the family Eustigmataceae, while the mono-unsaturated C32 1,15-alkyl diol was below detection limit. In contrast to the marine environment, LCD distributions in lakes did not show a clear relationship with temperature. The Long chain Diol Index (LDI), a proxy previously proposed for sea surface temperature reconstruction, showed a relatively weak correlation (R2 = 0.33) with mean annual air temperature used as an approximation for annual mean surface temperature of the lakes. A much-improved correlation (R2 = 0.74, p-value<0.001) was observed applying a multiple linear regression analysis between LCD distributions and lake temperatures reconstructed using branched tetraether lipid distributions. The obtained regression model provides good estimates of temperatures for cultures of the family Eustigmataceae, suggesting that algae belonging to this family have an important role as a source for LCDs in lacustrine environments, or, alternatively, that the main sources of LCDs are similarly affected by temperature as the Eustigmataceae. The results suggest that LCDs may have the potential to be applicable as a palaeotemperature proxy for lacustrine environments, although further calibration work is still required.