Stable carbon isotopic composition of biomarker lipids of DSDP Hole 31-302

The middle Paleocene through early Eocene long-term gradual warming was superimposed by several transient warming events, such as the Paleocene-Eocene Thermal Maximum (PETM) and Eocene Thermal Maximum 2 (ETM2). Both events show evidence for extreme global warming associated with a major injection of carbon into the ocean-atmosphere system, but the mechanisms of carbon injection and many aspects of the environmental response are still poorly understood. In this study, we analyzed the concentration and stable carbon isotopic (d13C) composition of several sulfur-bound biomarkers derived from marine photoautotrophs, deposited in the Arctic Ocean at ~85°N, during ETM2. The presence of sulfur-bound biomarkers across this event points toward high primary productivity and anoxic bottom water conditions. The previously reported presence of isorenieratene derivatives indicates euxinic conditions in the photic zone, likely caused by a combination of enhanced primary productivity and salinity stratification. The negative carbon isotope excursion measured at the onset of ETM2 for several biomarkers, ranges between 3 per mil and 4.5 per mil, much larger than the ~1.4 per mil recorded in marine carbonates elsewhere, suggesting substantial enhanced isotopic fractionation by the primary producers likely due to a significant rise in pCO2. In the absence of biogenic carbonates in the ETM2 section of our core we use coeval planktonic d13C from elsewhere to estimate surface water d13C in the Arctic Ocean and then apply the relation between isotopic fractionation and pCO2, originally calibrated for haptophyte alkenones, to three selected organic biomarkers (i.e., S-bound phytane, C35 hopane, and a C25 highly branched isoprenoid). This yields pCO2 values potentially in the range of four times preindustrial levels. However, these estimates are uncertain because of a lack of knowledge on the importance of pCO2 on photosynthetic isotopic fractionation.

Biomarker and radiogenic isotopes from sediment core POS362-2_33

The termination of the African Humid Period in northeastern Africa during the early Holocene was marked by the southward migration of the rain belt and the disappearance of the Green Sahara. This interval of drastic environmental changes was also marked by the initiation of food production by North African huntergatherer populations and thus provides critical information on human-environment relationships. However, existing records of regional climatic and environmental changes exhibit large differences in timing and modes of the wet/dry transition at the end of the African Humid Period. Here we present independent records of changes in river runoff, vegetation and erosion in the Nile River watershed during the Holocene obtained from a unique sedimentary sequence on the Nile River fan using organic and inorganic proxy data. This high-resolution reconstruction allows to examine the phase relationship between the changes of these three parameters and provides a detailed picture of the environmental conditions during the Paleolithic/Neolithic transition. The data show that river runoff decreased gradually during the wet/arid transition at the end of the AHP whereas rapid shifts of vegetation and erosion occurred earlier between 8.7 and about 6 ka BP. These asynchronous changes are compared to other regional records and provide new insights into the threshold responses of the environment to climatic changes. Our record demonstrates that the degradation of the environment in northeastern Africa was more abrupt and occurred earlier than previously thought and may have accelerated the process of domestication in order to secure sustainable food resources for the Neolithic African populations.

Geochemistry of tetrapyrrole, tetraterpenoid, and perylene pigments in sediments from the Gulf of California

Results and discussion cover pigment analyses of 36 sediment samples recovered by Deep Sea Drilling Project Leg 64, and six samples from the Leg 64 site-survey cruise in the Guaymas Basin (Scripps Institution of Oceanography, Leg 3). Pigments investigated were tetrapyrroles, tetraterpenoids, and the PAH compound perylene. Traces of mixed nickel and copper ETIO-porphyrins were ubiquitous in all sediment samples, except for the very surface (i.e., <2 m sub-bottom), and their presence is taken as an indication of minor influxes of previously oxidized allochthonous (terrestrial) organic matter. Phorbides and chlorins isolated from Site 479 sediment samples (i.e., the oxygen-minimum locale, northeast of the Guaymas Basin) well represent the reductive diagenesis ("Treibs Scheme"; see Baker and Palmer, 1978; Treibs, 1936) of chlorophyll derivatives. Three forms of pheophytin-a, plus a variety of phorbides, were found to give rise to freebase porphyrins, nickel phylloerythrin, and nickel porphyrins, with increasing depth of burial (increasing temperature). Sediments from Sites 481, 10G, and 18G yielded chlorophyll derivatives characteristic of early oxidative alterations. Included among these pigments are allomerized pheophytin-a, purpurin-18, and chlorin-p6. The high thermal gradient imposed upon the late Quaternary sediments of Site 477 greatly accelerated chlorophyll diagenesis in the adjacent overlying sediments, that is, the production of large quantities of free-base desoxophylloerythroetioporphyrin (DPEP) occurred in a section (477-7-5) presently only 49.8 meters sub-bottom. Present depth and age of these sediments are such that only chlorins and phorbides would be expected. Carotenoid (i.e., tetraterpenoids) concentrations were found to decrease rapidly with increasing sub-bottom depth. Less deeply buried sediments (e.g., 0-30 m) yielded mixtures of carotenes and oxygen-substituted carotenoids. Oxygencontaining (oxy-, oxo-, epoxy-) carotenoids were found to be lost preferentially with increased depth of burial. Early carotenoid diagenesis is suggested as involving interacting reductions and dehydrations whereby dehydro-, didehydro-, and retro-carotenes are generated. Destruction of carotenoids as pigments may involve oxidative cleavage of the isoprenoid chain through epoxy intermediates, akin to changes in the senescent cells of plants. Perylene was found to be a common component of the extractable organic matter from all sediments investigated. The generation of alkyl perylenes was found to parallel increases in the existing thermal regime at all sites. Igneous sills and sill complexes within the sediment profile of Site 481 altered (i.e., scrambled) the otherwise straightforward thermally induced alkylation of perylene. The degree of perylene alkylation is proposed as an indicator of geothermal stress for non-contemporaneous marine sediments.

Biomarker distributions and calculated sea surface temperatures from the North Pacific Ocean

In order to study the modern sea surface characteristics of the sub-polar North Pacific and the Bering Sea, i.e. sea surface temperature (SST) and sea ice cover, surface sediments recovered during the RV Sonne Expedition 202 in 2009 were analysed. To distinguish between marine and terrestrial organic carbon, hydrogen index values, long chain n-alkanes and specific sterols have been determined. The results show that in the Bering Sea, especially on the sea slope, the organic carbon source is mainly caused by high primary production. In the North Pacific, on the other hand, the organic material originates predominantly from terrestrial higher plants, probably related to dust input from Asia. SST has been reconstructed using the modified alkenone unsaturation index. Calibration from Müller et al. (1998, doi:10.1016/S0016-7037(98)00097-0) offers the most reliable estimate of mean annual temperature in the central North Pacific but does not correlate with mean annual temperature throughout the study area. In the eastern North Pacific and the Bering Sea, the Sikes et al. (1997, doi:10.1016/S0016-7037(97)00017-3) calibration seems to be more accurate and matches summer SST. The distribution of the novel sea ice proxy IP25 (highly branched C25 isoprenoid alkene) in surface sediments is in accord with the modern spring sea ice edge and shows the potential of this proxy to track past variation in sea ice cover in the study area.

Sea surface temperture reconstruction for ODP Site 189-1172

Relative to the present day, meridional temperature gradients in the Early Eocene age (~56-53 Myr ago) were unusually low, with slightly warmer equatorial regions (Pearson et al., 2007, doi:10.1130/G23175A.1 ) but with much warmer subtropical Arctic (Sluijs et al., 2008, doi:10.1029/2007PA001495) and mid-latitude (Sluijs et al., 2007, doi:10.1038/nature06400) climates. By the end of the Eocene epoch (~34 Myr ago), the first major Antarctic ice sheets had appeared (Zachos et al., 1992, doi:10.1130/0091-7613(1992)020<0569:EOISEO>2.3.CO;2; Barker et al., 2007, doi:10.1016/j.dsr2.2007.07.027), suggesting that major cooling had taken place. Yet the global transition into this icehouse climate remains poorly constrained, as only a few temperature records are available portraying the Cenozoic climatic evolution of the high southern latitudes. Here we present a uniquely continuous and chronostratigraphically well-calibrated TEX86 record of sea surface temperature (SST) from an ocean sediment core in the East Tasman Plateau (palaeolatitude ~65° S). We show that southwest Pacific SSTs rose above present-day tropical values (to ~34° C) during the Early Eocene age (~53 Myr ago) and had gradually decreased to about 21° C by the early Late Eocene age (~36 Myr ago). Our results imply that there was almost no latitudinal SST gradient between subequatorial and subpolar regions during the Early Eocene age (55-50 Myr ago). Thereafter, the latitudinal gradient markedly increased. In theory, if Eocene cooling was largely driven by a decrease in atmospheric greenhouse gas concentration Zachos et al. (2008, doi:10.1038/nature06588), additional processes are required to explain the relative stability of tropical SSTs given that there was more significant cooling at higher latitudes.

Geochemical and palynological measurements from the ODP Leg 189 at Site 1172 on the East Tasman Plateau

A brief (~150 kyr) period of widespread global average surface warming marks the transition between the Paleocene and Eocene epochs, ~56 million years ago. This so-called "Paleocene-Eocene thermal maximum" (PETM) is associated with the massive injection of 13C-depleted carbon, reflected in a negative carbon isotope excursion (CIE). Biotic responses include a global abundance peak (acme) of the subtropical dinoflagellate Apectodinium. Here we identify the PETM in a marine sedimentary sequence deposited on the East Tasman Plateau at Ocean Drilling Program (ODP) Site 1172 and show, based on the organic paleothermometer TEX86, that southwest Pacific sea surface temperatures increased from ~26 °C to ~33°C during the PETM. Such temperatures before, during and after the PETM are >10 °C warmer than predicted by paleoclimate model simulations for this latitude. In part, this discrepancy may be explained by potential seasonal biases in the TEX86 proxy in polar oceans. Additionally, the data suggest that not only Arctic, but also Antarctic temperatures may be underestimated in simulations of ancient greenhouse climates by current generation fully coupled climate models. An early influx of abundant Apectodinium confirms that environmental change preceded the CIE on a global scale. Organic dinoflagellate cyst assemblages suggest a local decrease in the amount of river run off reaching the core site during the PETM, possibly in concert with eustatic rise. Moreover, the assemblages suggest changes in seasonality of the regional hydrological system and storm activity. Finally, significant variation in dinoflagellate cyst assemblages during the PETM indicates that southwest Pacific climates varied significantly over time scales of 103 - 104 years during this event, a finding comparable to similar studies of PETM successions from the New Jersey Shelf.

Alkenones and TEX86 temperature proxies for core-top sediments from the southern Adriatic Sea

The Mediterranean Sea is at the transition between temperate and tropical air masses and as such of importance for studying climate change. The Gulf of Taranto and adjacent SW Adriatic Sea are at the heart of this region. Their sediments are excellently suited for generating high quality environmental records for the last millennia with a sub-decadal resolution. The quality of these records is dependent on a careful calibration of the transfer functions used to translate the sedimentary lipid signals to the local environment. Here, we examine and calibrate the UK'37 and TEX86 lipid-based temperature proxies in 48 surface sediments and relate these to ambient sea surface temperatures and other environmental data. The UK'37-based temperatures in surface sediments reflect winter/spring sea surface temperatures in agreement with other studies demonstrating maximum haptophyte production during the colder season. The TEX86-based temperatures for the nearshore sites also reflect winter sea surface temperatures. However, at the most offshore sites, they correspond to summer sea surface temperatures. Additional lipid and environmental data including the distribution of the BIT index and remote-sensed chlorophyll-a suggest a shoreward increase of the impact of seasonal and spatial variability in nutrients and control of planktonic archaeal abundance by primary productivity, particle loading in surface waters and/or overprint by a cold-biased terrestrial TEX86 signal. As such the offshore TEX86 values seem to reflect a true summer signal to the effect that offshore UK'37 and TEX86 reconstruct winter and summer temperature, respectively, and hence provide information on the annual temperature amplitude.

Age model, lipids, and iron/calcium-ratios of sediment core GeoB9307-3

Hide Intense debate persists about the climatic mechanisms governing hydrologic changes in tropical and subtropical southeast Africa since the Last Glacial Maximum, about 20,000 years ago. In particular, the relative importance of atmospheric and oceanic processes is not firmly established. Southward shifts of the intertropical convergence zone (ITCZ) driven by high-latitude climate changes have been suggested as a primary forcing, whereas other studies infer a predominant influence of Indian Ocean sea surface temperatures on regional rainfall changes. To address this question, a continuous record representing an integrated signal of regional climate variability is required, but has until now been missing. Here we show that remote atmospheric forcing by cold events in the northern high latitudes appears to have been the main driver of hydro-climatology in southeast Africa during rapid climate changes over the past 17,000 years. Our results are based on a reconstruction of precipitation and river discharge changes, as recorded in a marine sediment core off the mouth of the Zambezi River, near the southern boundary of the modern seasonal ITCZ migration. Indian Ocean sea surface temperatures did not exert a primary control over southeast African hydrologic variability. Instead, phases of high precipitation and terrestrial discharge occurred when the ITCZ was forced southwards during Northern Hemisphere cold events, such as Heinrich stadial 1 (around 16,000 years ago) and the Younger Dryas (around 12,000 years ago), or when local summer insolation was high in the late Holocene, i.e., during the last 4,000 years.

Palynology and sea surface temperature reconstruction for the mid-Cretaceous Oceanic Anoxic Event 2 at ODP Hole 210-1276A

The mid-Cretaceous is thought to be a greenhouse world with significantly higher atmospheric pCO2 and sea-surface temperatures as well as a much flatter latitudinal thermal gradient compared to the present. This time interval was punctuated by the Cenomanian/Turonian Oceanic Anoxic Event (OAE-2, ~ 93.5 Myr ago), an episode of global, massive organic carbon burial that likely resulted in a large and abrupt pCO2 decline. However, the climatic consequences of this pCO2 drop are yet poorly constrained. We determined the first, high-resolution sea-surface temperature (SST) record across OAE-2 from a deep-marine sedimentary sequence at Ocean Drilling Program (ODP) Site 1276 in the mid-latitudinal Newfoundland Basin, NW Atlantic. By employing the organic palaeothermometer TEX86, we found that SSTs across the OAE-2 interval were extremely high, but were punctuated by a remarkably large cooling (5-11 °C), which is synchronous with the 2.5-5.5 °C cooling in SST records from equatorial Atlantic sites, and the "Plenus Cold Event". Because this global cooling event is concurrent with increased organic carbon burial, it likely acted in response to the associated pCO2 drop. Our findings imply a substantial increase in the latitudinal SST gradient in the proto-North Atlantic during this period of global cooling and reduced atmospheric pCO2, suggesting a strong coupling between pCO2 and latitudinal thermal gradients under greenhouse climate conditions.

Abrupt vegetation change after the Late Quaternary megafaunal extinction in southeastern Australia

A substantial extinction of megafauna occurred in Australia between 50 and 45 kyr ago, a period that coincides with human colonization of Australia. Large shifts in vegetation also occurred around this time, but it is unclear whether the vegetation changes were driven by the human use of fire-and thus contributed to the extinction event-or were a consequence of the loss of megafaunal grazers. Here we reconstruct past vegetation changes in southeastern Australia using the stable carbon isotopic composition of higher plant wax n-alkanes and levels of biomass burning from the accumulation rates of the biomarker levoglucosan from a well-dated sediment core offshore from the Murray-Darling Basin. We find that from 58 to 44 kyr ago, the abundance of plants with the C-4 carbon fixation pathway was generally high-between 60 and 70%. By 43 kyr ago, the abundance of C-4 plants dropped to 30% and biomass burning increased. This transient shift lasted for about 3,000 years and came after the period of human arrival and directly followed megafauna extinction at 48.9-43.6 kyr ago. We conclude that the vegetation shift was not the cause of the megafaunal extinction in this region. Instead, our data are consistent with the hypothesis that vegetation change was the consequence of the extinction of large browsers and led to the build-up of fire-prone vegetation in the Australian landscape.

Paleoclimate record combinatio of speleothems and of sediment core GeoB3910-2

A substantial strengthening of the South American monsoon system (SAMS) during Heinrich Stadials (HS) points toward decreased cross-equatorial heat transport as the main driver of monsoonal hydroclimate variability at millennial time-scales. In order to better constrain the exact timing and internal structure of HS1 over tropical South America we assessed two precisely dated speleothem records from central-eastern and northeastern Brazil in combination with two marine records of terrestrial organic and inorganic matter input into the western equatorial Atlantic. During HS1 we recognize at least two events of widespread intensification of the SAMS across the entire region influenced by the South Atlantic Convergence Zone (SACZ) at 16.11-14.69 kyr BP and 18.1-16.66 kyr BP (labeled as HS1a and HS1c, respectively), separated by a dry excursion from 16.66-16.11 kyr BP (HS1b). In view of the spatial structure of precipitation anomalies, the widespread increase of monsoon precipitation over the SACZ domain was termed 'Mega-SACZ'.