GDGT and n-alkane data of sediment core GeoB4901-8

The tight coupling between the atmospheric and oceanic circulation in the equatorial Atlantic region makes this area an important region for paleoclimatic research. Previous studies report the occurrence of large amounts of terrigenous material and soil organic carbon (SOC) within the marine sediments of the eastern Gulf of Guinea. We use the accumulation rates (AR) of branched glycerol dialkyl glycerol tetraethers (GDGTs) to identify variations in SOC delivery to the Niger Fan over the last 35 ka, and compare these records to long-chain n-alkanes as a proxy for higher plant material, to an inorganic proxy for terrigenous input (aluminum AR) and to indicators for the marine productivity (AR of carbonate and crenarchaeol). In addition, sea surface temperatures (SSTs) are calculated based on the TEX86H index and environmental factors affecting the SST-reconstructions are discussed. Our results indicate that Al AR are closely connected to the rate of mean sea level change after 15 ka BP, with an additional influence of the increased monsoonal precipitation and extended vegetation cover corresponding to the African Humid Period (14.8-5.5 ka BP). Branched GDGT AR appears to be determined by shelf erosion in addition to the interplay of monsoonal precipitation and vegetation cover controlling soil erosion. Long-chain n-alkane concentrations clearly show a different trend than the other proxies, which might be due to their predominant eolian transport. Paleo-SSTs show a clear shift from colder temperatures during the last glacial period (20-22 °C) to warmer temperatures during the Holocene (24-26 °C). However, TEX86H-based SSTs are cold-biased compared to recent SSTs and Mg/Ca-based SST reconstructions, which is probably caused by a high seasonality of the Thaumarchaeota, with a maximum productivity of these organisms during the cold summer months. However, a sub-surface production of GDGTs and/or a potential bias of SST reconstruction by terrestrial input could not be completely excluded.

Temporal variation of temperature and related proxies from the penultimate glacial towards the Eemian in the Black Sea

The last glacial-interglacial transition or Termination I (T I) is well documented in the Black Sea, whereas little is known about climate and environmental dynamics during the penultimate Termination (T II). Here we present a multi-proxy study based on a sediment core from the SE Black Sea covering the penultimate glacial and almost the entire Eemian interglacial (133.5 ±0.7-122.5 ±1.7 ka BP). Proxies comprise ice-rafted debris (IRD), O and Sr isotopes as well as Sr/Ca, Mg/Ca, and U/Ca ratios of benthic ostracods, organic and inorganic sediment geochemistry, as well as TEX86 and UK'37derived water temperatures. The ending penultimate glacial (MIS 6, 133.5 to 129.9 ±0.7 ka BP) is characterised by mean annual lake surface temperatures of about 9°C as estimated from the TEX86 palaeothermometer. This period is impacted by two Black Sea melt water pulses (BSWP-II-1 and 2) as indicated by very low Sr/Ca ostracods but high sedimentary K/Al values. Anomalously high radiogenic 87Sr/86Sr ostracod values (max. 0.70945) during BSWP-II-2 suggest a potential Himalayan source communicated via the Caspian Sea. The T II warming started at 129.9 ±0.7 ka BP, witnessed by abrupt disappearance of IRD, increasing d18O ostracod values, and a first TEX86 derived temperature rise of about 2.5°C. A second, abrupt warming step to ca. 15.5°C as the prelude of the Eemian warm period is documented at 128.3 ka BP. The Mediterranean-Black Sea reconnection most likely occurred at 128.1 ±0.7 ka BP as demonstrated by increasing Sr/Ca ostracods and U/Ca ostracods values. The disappearance of ostracods and TOC contents >2% document the onset of Eemian sapropel formation at 127.6 ka BP. During sapropel formation, TEX86 temperatures dropped and stabilised at around 9°C, while UK'37 temperatures remain on average 17°C. This difference is possibly caused by a habitat shift of Thaumarchaeota communities from surface towards nutrient-rich deeper and colder waters located above the gradually establishing halo-and redoxcline.

(Table 1) TOC content, BIT, TEX86 and UK'37 indices, and sea surface temperature reconstruction for the middle Miocene to Pliocene of ODP Hole 175-1085A

The initiation of the Benguela upwelling has been dated to the late Miocene, but estimates of its sea surface temperature evolution are not available. This study presents data from Ocean Drilling Program (ODP) Site 1085 recovered from the southern Cape Basin. Samples of the middle Miocene to Pliocene were analyzed for alkenone-based (UK'37, SSTUK) and glycerol dialkyl glycerol tetraether (GDGT) based (TEX86, TempTEX) water temperature proxies. In concordance with global cooling during the Miocene, SSTUK and TempTEX exhibit a decline of about 8°C and 16°C, respectively. The temperature trends suggest an inflow of cold Antarctic waters triggered by Antarctic ice sheet expansion and intensification of Southern Hemisphere southeasterly winds. A temperature offset between both proxies developed with the onset of upwelling, which can be explained by differences in habitat: alkenone-producing phytoplankton live in the euphotic zone and record sea surface temperatures, while GDGT-producing Thaumarchaeota are displaced to colder subsurface waters in upwelling-influenced areas and record subsurface water temperatures. We suggest that variations in subsurface water temperatures were driven by advection of cold Antarctic waters and thermocline adjustments that were due to changes in North Atlantic deep water formation. A decline in surface temperatures, an increased offset between temperature proxies, and an increase in primary productivity suggest the establishment of the Benguela upwelling at 10 Ma. During the Messinian Salinity Crisis, between 7 and 5 Ma, surface and subsurface temperature estimates became similar, likely because of a strong reduction in Atlantic overturning circulation, while high total organic carbon contents suggest a "biogenic bloom." In the Pliocene the offset between the temperature estimates and the cooling trend was reestablished.

Radiocarbon dating and alkenone-based proxies of sediment core GeoB7702-3

In this study we utilize two organic geochemical proxies, the Uk'37 index and TEX86, to examine past sea surface temperatures (SST) from a site located near the Nile River Delta in the eastern Mediterranean (EM) Sea. The Uk'37 and TEX86 records generally are in agreement and indicate SST ranges of 14°C-26°C and 14°C-28°C, respectively, during the last 27 cal ka. During the Holocene, TEX86-based SST estimates are usually higher than Uk'37-based SST estimates, which is likely due to seasonal differences between the timing of the haptophyte and crenarchaeota blooms in the EM and is related to the onset of the modern flow regime of the Nile River. Both records show that SST varied on centennial to millennial timescales in response to global climate events, i.e., cooling during the Last Glacial Maximum (LGM), Heinrich event 1 (H1), and the Younger Dryas (YD) and warming during the Bølling-Allerød and in the early Holocene during deposition of sapropel S1. The H1 cooling was particularly severe and is marked by a drop in SST of ~4.5°C in comparison to pre-H1 SST, with temperatures >1°C cooler than during the LGM. In contrast to high-latitude and western Mediterranean records, which indicate both an abrupt onset and termination of the YD event, the transition from the YD to the Holocene was much more gradual in the EM.

14C specific radiocarbon ages and bulk ages accompanied by geochemical proxys from surface sediment samples in the Black Sea

Transfer of organic carbon (OC) from the terrestrial to the oceanic carbon pool is largely driven by riverine and aeolian transport. Before transport, however, terrigenous organic matter can be retained in intermediate terrestrial reservoirs such as soils. Using compound-specific radiocarbon analysis of terrigenous biomarkers their average terrestrial residence time can be evaluated. Here we show compound-specific radiocarbon (14C) ages of terrigenous biomarkers and bulk 14C ages accompanied by geochemical proxy data from core top samples collected along transects in front of several river mouths in the Black Sea. 14C ages of long chain n-alkanes, long chain n-fatty acids and total organic carbon (TOC) are highest in front of the river mouths, correlating well with BIT (branched and isoprenoid tetraether) indices, which indicates contribution of pre-aged, soil-derived terrigenous organic matter. The radiocarbon ages decrease further offshore towards locations where organic matter is dominated by marine production and aeolian input potentially contributes terrigenous organic matter. Average terrestrial residence times of vascular plant biomarkers deduced from n-C29+31 alkanes and n-C28+30 fatty acids ages from stations directly in front of the river mouths range from 900 ± 70 years to 4400 ± 170 years. These average residence times correlate with size and topography in climatically similar catchments, whereas the climatic regime appears to control continental carbon turnover times in morphologically similar drainage areas of the Black Sea catchment. Along-transect data imply petrogenic contribution of n-C29+31 alkanes and input via different terrigenous biomarker transport modes, i.e., riverine and aeolian, resulting in aged biomarkers at offshore core locations. Because n-C29+31 alkanes show contributions from petrogenic sources, n-C28+30 fatty acids likely provide better estimates of average terrestrial residence times of vascular plant biomarkers. Moreover, sedimentary n-C28 and n-C30 fatty acids appear clearly much less influenced by autochthonous sources than n-C24 and n-C26 fatty acids as indicated by increasing radiocarbon ages with increasing chain-length and are, thus, more representative as vascular plant biomarkers.

(Table S1) TEX86 and BIT record from sediment core PBBC-1

A molecular organic geochemical proxy (TEX86) for sea surface temperature (SST) is compared with a foraminifera-based SST proxy (Mg/Ca) in a decadal-resolution marine sedimentary record spanning the last 1000 years from the Gulf of Mexico. We assess the relative strengths of the organic and inorganic paleoceanographic techniques for reconstructing high-resolution SST variability during recent climate events, including the Little Ice Age (LIA) and the Medieval Warm Period (MWP). SST estimates based on the molecular organic proxy TEX86 show a similar magnitude and pattern of SST variability to foraminiferal Mg/Ca-SST estimates but with some important differences. For instance, both proxies show a cooling (1°C-2°C) of Gulf of Mexico SSTs during the LIA. During the MWP, however, Mg/Ca-SSTs are similar to near-modern SSTs, while TEX86 indicates SSTs that were cooler than modern. Using the respective SST calibrations for each proxy results in TEX86-SST estimates that are 2°C-4°C warmer than Mg/Ca-SST throughout the 1000 year record. We interpret the TEX86-SST as a summer-weighted SST signal from the upper mixed layer, whereas the Mg/Ca-SST better reflects the mean annual SST. Downcore differences in the SST estimates between the two proxies (DeltaT = TEX86 - Mg/Ca) are interpreted in the context of varying seasonality and/or changing water column temperature gradients.

Bulk and molecular proxies of sediment core GeoB6518-1

A 20 kyr long sediment sequence from the Congo deep sea fan (core GeoB 6518-1), one of the world's largest deep sea river fans, has been analysed for bulk and molecular proxies in order to reconstruct the marine, soil and plant organic carbon (OC) contributions to these sediments since the last glacial maximum. The bulk proxies applied, C/N ratio and d13Corg, ranged from 10 to 12.5 and from -24.5 to -21 per mill VPDB, respectively. As molecular proxies, concentrations of marine derived alkenones and terrestrial derived odd-numbered n-alkanes were used, which varied between 0.2 and 4 µg/g dry weight sediment. In addition, the branched vs. isoprenoid tetraether (BIT) index, a proxy for soil organic matter input, was used, which varied from 0.3 to 0.5 in this core. Application of binary mixing models, based on the different individual proxies, showed estimates for terrestrial OC input varying by up to 50% due to the heterogeneous nature of the OC. Application of a three end-member mixing model using the d13Corg content, the C/N ratio and the BIT index, enabled the distinction of soil and plant organic matter as separate contributors to the sedimentary OC pool. The results show that marine OC accounts for 20% to 40% of the total OC present in the deep sea fan sediments over the last 20 kyr and that soil OC accounts for about half (45% on average) of the OC present. This suggests that soil OC represents the majority of the terrestrial OC delivered to the fan sediments. Accumulation rates of the plant and soil OC fractions over the last 20 kyr varied by a factor of up to 5, and are strongly related to sediment accumulation rates. They showed an increase starting at ca. 17 kyr BP, a decline during the Younger Dryas, peak values during the early Holocene and lower values in the late Holocene. This pattern matches with reconstructions of past central African humidity and Congo River discharge from the same core and revealed that central African precipitation patterns exert a dominant control on terrestrial OC deposition in the Congo deep sea fan. Marine OC accumulation rates are only weakly related to sediment accumulation rates and vary only little over time compared to the terrigenous fractions. These variations are likely a result of enhanced preservation during times of higher sedimentation rates and of relative small fluctuations in primary production due to wind-driven upwelling.

Concentrations and abundance ratios of long-chain alkenones and glycerol dialkyl glycerol tetraethers in sinking particles south of Java

In this study, we obtained concentrations and abundance ratios of long-chain alkenones and glycerol dialkyl glycerol tetraethers (GDGTs) in a one-year time-series of sinking particles collected with a sediment trap moored from December 2001 to November 2002 at 2200 m water depth south of Java in the eastern Indian Ocean. We investigate the seasonality of alkenone and GDGT fluxes as well as the potential habitat depth of the Thaumarchaeota producing the GDGTs entrained in sinking particles. The alkenone flux shows a pronounced seasonality and ranges from 1 µg m-**2 d**-1 to 35 µg m**-2 d**-1. The highest alkenone flux is observed in late September during the Southeast monsoon, coincident with high total organic carbon fluxes as well as high net primary productivity. Flux-weighted mean temperature for the high flux period using the alkenone-based sea-surface temperature (SST) index UK'37 is 26.7°C, which is similar to satellite-derived Southeast (SE) monsoon SST (26.4°C). The GDGT flux displays a weaker seasonality than that of the alkenones. It is elevated during the SE monsoon period compared to the Northwest (NW) monsoon and intermonsoon periods (approximately 2.5 times), which is probably related to seasonal variation of the abundance of Thaumarchaeota, or to enhanced export of GDGTs by aggregation with sinking phytoplankton detritus. Flux-weighted mean temperature inferred from the GDGT-based TEXH86 index is 26.2°C, which is 1.8 °C lower than mean annual (ma) SST but similar to SE monsoon SST. As the time series of TEXH86 temperature estimates, however, does not record a strong seasonal amplitude, we infer that TEXH86 reflects ma upper thermocline temperature at approximately 50 m water depth.

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.

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.

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.