(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.

Terrigenous input and marine productivity for the Pacific sector of the Southern Ocean based on lipid biomarkers

In this study, we present a new multiproxy data set of terrigenous input, marine productivity and sea surface temperature (SST) from 52 surface sediment samples collected along E-W transects in the Pacific sector of the Southern Ocean. Allochtonous terrigenous input was characterized by the distribution of plant wax n-alkanes and soil-derived branched glycerol dialkyl glycerol tetraethers (brGDGTs). 230Th-normalized burial rates of both compound groups were highest close to the potential sources in Australia and New Zealand and are strongly related to lithogenic contents, indicating common sources and transport. Detection of both long-chain n-alkanes and brGDGTs at the most remote sites in the open ocean strongly suggests a primarily eolian transport mechanism to at least 110°W, i.e. by prevailing westerly winds. Two independent organic SST proxies were used, the UK'37 based on long-chain alkenones, and the TEX86 based on isoprenoid GDGTs. Both, UK'37 and TEX86 indices show robust relationships with temperature over a temperature range between 0.5 and 20°C, likely implying different seasonal and regional imprints on the temperature signal. While alkenone-based temperature estimates reliably reflect modern SST even at the low temperature end, large temperature residuals are observed for the polar ocean using the TEX86 index. 230Th-normalized burial rates of alkenones are highest close to the Subtropical Front and are positively related to lithogenic fluxes throughout the study area. In contrast, highest isoGDGT burial south of the Antarctic Polar Front is not related with dust flux but may be largely controlled by diatom blooms, and thus high opal fluxes during austral summer.

Biomarker distributions in sediment core PS2767-4

Here, we present a first (low-resolution) biomarker sea-ice proxy record from the High Arctic (southern Lomonosov Ridge), going back in time to about 60 ka (MIS 3 to MIS 1). Variable concentrations of the sea-ice diatom specific highly branched isoprenoid (HBI) with 25 carbon atoms ("IP25"), in combination with the phytoplankton biomarker brassicasterol, suggest variable seasonal sea-ice coverage and open-water productivity during MIS 3. During most of MIS 2, the spring to summer sea-ice margin significantly extended towards the south, resulting in a drastic decrease in phytoplankton productivity. During the Early Holocene Climate Optimum, brassicasterol reached its maximum, interpreted as signal for elevated phytoplankton productivity due to a significantly reduced sea-ice cover. During the mid-late Holocene, IP25 increased and brassicasterol decreased, indicating extended sea-ice cover and reduced phytoplankton productivity, respectively. The HBI diene/IP25 ratios probably reached maximum values during the Bølling-Allerød warm period and decreased during the Holocene, suggesting a correlation with sea-surface temperature.

(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.

Ratio of Diene/Triene of sediment core MD03-2601

Micropaleontological and biomarker data from two high-accumulation marine sites from the Coastal and Continental Shelf Zone (CCSZ) off East Antarctica (Adélie Land at w140°E and eastern Prydz Bay at w77°E) are used to reconstruct Holocene changes in sea ice and wind stress at the basin-wide scale. These data demonstrate congruent increase in sea-ice concentration/persistence and wind stress-related sea-surface turbulence in the two regions since 7 cal ka BP, with a particularly strong signal since 4.5 - 3.5 cal ka BP. Comparison of these high latitude records with sea ice and turbulence records from the southern mid-latitudes highlights distinctive climatic evolutions according to the different latitudinal bands. Sea-ice persistence and turbulence increase in East Antarctica CCSZ are opposite to sea-surface warming and sea-ice retreat recorded after 4.5 - 3.5 cal ka BP in the East Atlantic and Indian sector between 55 and 45°S. At the same period, paleodata suggest SST cooling in all major coastal upwelling systems of the southern hemisphere, caused by the northward transport of subpolar surface waters as a response to southern Westerlies reinforcement. We therefore propose, as suggested for the northern hemisphere, that Holocene changes in the latitudinal insolation gradient, primarily forced by obliquity and precession and amplified by sea-ice and glacial-ice expansions in the Antarctic realm, are responsible for the observed contrasted latitudinal patterns of southern latitudes.

Sea surface temperature (TEX86), marine GDGTs and BIT index from ODP Hole 161-977A

The TEX86H temperature proxy is a relatively new proxy based on crenarchaeotal lipids and has rarely been applied together with other temperature proxies. In this study, we applied the TEX86H on a sediment core from the Alboran Sea (western Mediterranean, core ODP-977A) covering the penultimate climate cycle, that is, from 244 to 130 ka, and compared this with previously published sea surface temperatures derived from the Uk'37 of alkenones of haptophyta and Mg/Ca records of planktonic foraminifera. The TEX86H temperature record shows remarkably similar stadial-interstadial patterns and abrupt temperature changes to those observed with the Uk'37 palaeothermometer. Absolute TEX86H temperature estimates are generally higher than those of Uk'37, though this difference (<3°C in 81% of the data points) is mainly within the temperature calibration error for both proxies, suggesting that crenarchaeota and haptophyta experienced similar temperature variations. During occasional events (<5% of the analyzed time span), however, the TEX86H exhibits considerably higher absolute temperature estimates than the Uk'37. Comparison with Mg/Ca records of planktonic foraminifera as well as other Mediterranean TEX86 and Uk'37 records suggests that part of this divergence may be attributed to seasonal differences, that is, with TEX86H reflecting mainly the warm summer season while Uk'37 would show annual mean. Biases in the global calibration of both proxies or specific biases in the Mediterranean are an alternative, though less likely, explanation. Despite differences between absolute TEX86H and Uk'37 temperatures, the correlation between the two proxies (r**2 = 0.59, 95% significance) provides support for the occurrence of abrupt temperature variations in the western Mediterranean during the penultimate interglacial-to-glacial cycle.

Long chain diols and diol indices of surface sediments of the Iberian Atlantic margin

Long chain diols are lipids that have gained interest over the last years due to their high potential to serve as biomarkers and diol indices have been proposed to reconstruct upwelling conditions and sea surface temperature (SST). However, little is known about the sources of the diols and the mechanisms impacting their distribution. Here we studied the factors controlling diol distributions in the Iberian Atlantic margin, which is characterized by a dynamic continental shelf under the influence of upwelling of nutrient-rich cold deep waters, and fluvial input. We analyzed suspended particulate matter (SPM) of the Tagus river, marine SPM and marine surface sediments along five transects off the Iberian margin, as well as riverbank sediments and soil from the catchment area of the Tagus river. Relatively high fractional abundances of the C32 1,15-diol (normalized with respect to the 1,13- and 1,15-diols) were observed in surface sediments in front of major river mouths and this abundance correlates strongly with the BIT index, a tracer for continental input of organic carbon. Together with an even higher fractional abundance of the C32 1,15-diol in the Tagus river SPM, and the absence of long chain diols in the watershed riverbank sediments and soils, we suggest that this long chain diol is produced in-situ in the river. Further support for this hypothesis comes from the small but distinct stable carbon isotopic difference of 1.3? with the marine C28 1,13-diol. The 1,14-diols are relatively abundant in surface sediments directly along the northern part of the coast, close to the upwelling zone, suggesting that Diol Indices based on 1,14-diols would work well as upwelling tracers in this region. Strikingly, we observed a significant difference in stable carbon isotopic composition between the monounsaturated C30:1 1,14- and the saturated C28 1,14-diol (3.8±0.7 per mil), suggesting different sources, in accordance with their different distributions. In addition, the Long chain Diol Index (LDI), a proxy for sea surface temperature, was applied for the surface sediments. The results correlate well with satellite SSTs offshore but reveal a significant discrepancy with satellite-derived SSTs in front of the Tagus and Sado rivers. This suggests that river outflow might compromise the applicability of this proxy.

Intact and core tetraether lipids in water column profiles of suspended particulate matter and of surface sediment samples off Cape Blanc, NW Africa

In the reconstruction of sea surface temperature (SST) from sedimentary archives, secondary sources, lateral transport and selective preservation are considered to be mainly negligible in terms of influencing the primary signal. This is also true for the archaeal glycerol dialkyl glycerol tetraethers (GDGTs) that form the basis for the TEX86 SST proxy. Our samples represent four years variability on a transect off Cape Blanc (NW Africa). We studied the subsurface production, vertical and lateral transport of intact polar lipids and core GDGTs in the water column at high vertical resolution on the basis of suspended particulate matter (SPM) samples from the photic zone, the subsurface oxygen minimum zone (OMZ), nepheloid layers (NL) and the water column between these. Furthermore we compared the water column SPM GDGT composition with that in underlying surface sediments. This is the first study that reports TEX86 values from the precursor intact polar lipids (IPLs) associated with specific head groups (IPL -specific TEX86). We show a clear deviation from the sea surface GDGT composition in the OMZ between 300 and 600 m. Since neither lateral transport nor selective degradation provides a satisfactory explanation for the observed TEX-derived temperature profiles with a bias towards higher temperatures for both core- and IPL -specific TEX86 values, we suggest that subsurface in situ production of archaea with a distinct relationship between lipid biosynthesis and temperature is the responsible mechanism. However, in the NW-African upwelling system the GDGT contribution of the OMZ to the surface sediments does not seem to affect the sedimentary TEX86 as it shows no bias and still reflects the signal of the surface waters between 0 and 60 m.

Organic geochemical parameters (biomarker) in sedimentary sequences and sediment traps

For the reconstruction of sea-ice variability, a biomarker approach which is based on (1) the determination of sea-ice diatom-specific highly-branched isoprenoid (IP25) and (2) the coupling of phytoplankton biomarkers and IP25 has been used. For the first time, such a data set was obtained from an array of two sediment traps deployed at the southern Lomonosov Ridge in the central Arctic Ocean at water depth of 150 m and 1550 m and recording the seasonal variability of sea ice cover in 1995/1996. These data indicate a predominantly permanent sea ice cover at the trap location between November 1995 and June 1996, an ice-edge situation with increased phytoplankton productivity and sea-ice algae input in July/August 1996, and the start of new-ice formation in late September. The record of modern sea-ice variability is then used to better interpret data from sediment core PS2458-4 recovered at the Laptev Sea continental slope close to the interception with Lomonosov Ridge and recording the post-glacial to Holocene change in sea-ice cover. Based on IP25 and phytoplankton biomarker data from Core PS2458-4, minimum sea-ice cover was reconstructed for the Bølling/Allerød warm interval between about 14.5 and 13 calendar kyr BP, followed by a rapid and distinct increase in sea-ice cover at about 12.8 calendar kyr BP. This sea-ice event was directly preceded by a dramatic freshwater event and a collapse of phytoplankton productivity, having started about 100 years earlier. These data are the first direct evidence that enhanced freshwater flux caused enhanced sea-ice formation in the Arctic at the beginning of the Younger Dryas. In combination with a contemporaneous, abrupt and very prominent freshwater/meltwater pulse in the Yermak Plateau/Fram Strait area these data may furthermore support the hypothesis that strongly enhanced freshwater (and ice) export from the Arctic into the North Atlantic could have played an important trigger role for the onset of the Younger Dryas cold reversal. During the Early Holocene, sea-ice cover steadily increased again (ice-edge situation), reaching modern sea-ice conditions (more or less permanent sea-ice cover) probably at about 7-8 calendar kyr BP.

Diatoms and biomarkers in sediments from the Antarctic Peninsula

The Antarctic Peninsula (AP) has been identified as one of the most rapidly warming region on Earth. Satellite monitoring currently allows for a detailed understanding of the relationship between sea ice extent and duration and atmospheric and oceanic circulations in this region. However, our knowledge on ocean-ice-atmosphere interactions is still relatively poor for the period extending beyond the last 30 years. Here, we describe environmental conditions in Northwestern and Northeastern Antarctic Peninsula areas over the last century using diatom census counts and diatom specific biomarkers (HBIs) in two marine sediment multicores (MTC-38C and -18A, respectively). Diatom census counts and HBIs show abrupt changes between 1935 and 1950, marked by ocean warming and sea ice retreat in both sides of the AP. Since 1950, inferred environmental conditions do not provide evidence for any trend related to the recent warming but demonstrate a pronounced variability on pluri-annual to decadal time scale. We propose that multi-decadal sea ice variations over the last century are forced by the recent warming, while the annual-to-decadal variability is mainly governed by synoptic and regional wind fields in relation with the position and intensity of the atmospheric low-pressure trough around the AP. However, the positive shift of the SAM since the last two decades cannot explain the regional trend observed in this study, probably due to the effect of local processes on the response of our biological proxies.

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.

Seawater carbonate chemistry and biological processes duirng experiments with bryozoan Myriapora truncata, 2010

There are serious concerns that ocean acidification will combine with the effects of global warming to cause major shifts in marine ecosystems, but there is a lack of field data on the combined ecological effects of these changes due to the difficulty of creating large-scale, long-term exposures to elevated CO2 and temperature. Here we report the first coastal transplant experiment designed to investigate the effects of naturally acidified seawater on the rates of net calcification and dissolution of the branched calcitic bryozoan Myriapora truncata (Pallas, 1766). Colonies were transplanted to normal (pH 8.1), high (mean pH 7.66, minimum value 7.33) and extremely high CO2 conditions (mean pH 7.43, minimum value 6.83) at gas vents off Ischia Island (Tyrrhenian Sea, Italy). The net calcification rates of live colonies and the dissolution rates of dead colonies were estimated by weighing after 45 days (May-June 2008) and after 128 days (July-October) to examine the hypothesis that high CO2 levels affect bryozoan growth and survival differently during moderate and warm water conditions. In the first observation period, seawater temperatures ranged from 19 to 24 °C; dead M. truncata colonies dissolved at high CO2 levels (pH 7.66), whereas live specimens maintained the same net calcification rate as those growing at normal pH. In extremely high CO2 conditions (mean pH 7.43), the live bryozoans calcified significantly less than those at normal pH. Therefore, established colonies of M. truncata seem well able to withstand the levels of ocean acidification predicted in the next 200 years, possibly because the soft tissues protect the skeleton from an external decrease in pH. However, during the second period of observation a prolonged period of high seawater temperatures (25-28 °C) halted calcification both in controls and at high CO2, and all transplants died when high temperatures were combined with extremely high CO2 levels. Clearly, attempts to predict the future response of organisms to ocean acidification need to consider the effects of concurrent changes such as the Mediterranean trend for increased summer temperatures in surface waters. Although M. truncata was resilient to short-term exposure to high levels of ocean acidification at normal temperatures, our field transplants showed that its ability to calcify at higher temperatures was compromised, adding it to the growing list of species now potentially threatened by global warming.

Sedimentary n-alkanes, their hydrogen isotopes, GDGTs and d15N as well as d13Corg of lake Nam Co, Tibet

The transition from the last Glacial to the current Interglacial, the Holocene, represents an important period with climatic and environmental changes impacting ecosystems. In this study, we examined the interplay between the Indian Ocean Summer Monsoon (IOSM) and the Westerlies at lake Nam Co, southern Tibet to understand the climatic effects on the ecosystem. Different organic geochemical proxies (n-alkanes, glycerol dialkyl glycerol tetraethers, dD, d13Corg, d15N) are applied to reconstruct the environmental and hydrological changes on one of the longest available paleorecords at the Tibetan Plateau. Based on our paleohydrological dD proxies, the aquatic signal lags the terrestrial one due to specific ecological thresholds, which, in addition to climatic changes, can influence aquatic organisms. The aquatic organisms' response strongly depends on temperature and associated lake size, as well as pH and nutrient availability. Because the terrestrial vegetation reacts faster and more sensitively to changes in the monsoonal and climatic system, the dD of n-C29 and the reconstructed inflow water signal represent an appropriate IOSM proxy. In general, the interplay of the different air masses seems to be primarily controlled by solar insolation. In the Holocene, the high insolation generates a large land-ocean pressure gradient associated with strong monsoonal winds and the strongest IOSM. In the last glacial period, however, the weak insolation promoted the Westerlies, thereby increasing their influence at the Tibetan Plateau. Our results help to elucidate the variable IOSM, and they illustrate a remarkable shift in the lake system regarding pH, d13Corg and d15N from the last glacial to the Holocene interglacial period.