Stable Water Isotopologue data collected during HCCT-2010

Cloud samples for the isotopic analysis were collected in the framework of the Hill Cap Cloud Thuringia 2010 (HCCT-2010) campaign on Schmücke (50° 39'N/ 10° 46'E, 937 m a.s.l.; Germany) in September and October 2010 with a three-stage Caltech Active Strand Cloudwater Collector (CASCC) during 13 different cloud events with a temporal resolution of 1 to 3 hours. In a first step, we ensured that no additional fractionation occurred during sampling with the CASCC. The d values of the three sizes classes of the CASCC (4 µm to 16 µm, 16 µm to 22 µm and >22 µm) did not differ significantly, revealing that the cloud droplets of different sizes quickly equilibrate their delta value with the one of the surrounding vapor. delta values in the cloud droplets varied from -77 per mil to -15 per mil in d2H and from -12.1 per mil to -3.9 per mil in d18O and were fitted by d2H =7.8*d18O +13*10**-3. delta values decreased with temperature as well as towards the end of the campaign, representing a seasonal trend which is known from d values in precipitation. The deuterium excess of the cloud samples was generally higher than the Local Meteoric Water Line of the closest GNIP (Global Network of Isotopes in Precipitation) station. Rain decreases its deuterium excess during falling through an unsaturated air column, while the cloud droplets conserve the deuterium excess of the initial evaporation and thus have been found to be a good indicator for the airmass source region: higher deuterium excess was measured for polar air masses and lower deuterium excess for Mediterranean air masses. Changes in d values during one cloud event were up to 3.6 per mil (d2H) and 0.23 per mil (d18O), except for frontal passages, which were associated with increases of ~6 per mil per hour (d2H) and ~0.6 per mil per hour (d18O). Using a box model, we showed that the influence of condensation only was able to explain the variation in the isotope signal of two cloud passages. Consequently, we deduced that the water vapor "feeding" the cloud advected the measured changes. A trajectory analysis and moisture source diagnostic revealed that it is very likely that the variations were either related to rain out along the trajectories or to meteorological changes in the moisture source region. This was the first study using stable water isotopologues in cloud water manifesting their potential in the context of atmospheric water vapor circulation.

CPI, d13C, Corg and diploptene from ODP Hole 169-1034B varved sediments

Saanich Inlet has been a highly productive fjord since the last glaciation. During ODP Leg 169S, nearly 70 m of Holocene sediments were recovered from Hole 1034 at the center of the inlet. The younger sediments are laminated, anaerobic, and rich in organic material (1-2.5 wt.% Corg), whereas the older sediments below 70 mbsf are non-laminated, aerobic, with glacio-marine characteristics and have a significantly lower organic matter content. This difference is also reflected in the changes of interstitial fluids, and in biomarker compositions and their carbon isotope signals. The bacterially-derived hopanoid 17alpha(H),21beta(H)-hop-22(29)-ene (diploptene) occurs in Saanich Inlet sediments throughout the Holocene but is not present in Pleistocene glacio-marine sediments. Its concentration increases after ~6000 years BP up to present time to about 70 µg/g Corg, whereas terrigenous biomarkers such as the n-alkane C31 are low throughout the Holocene (<51 µg/g Corg) and even slightly decrease to 36 µg/g Corg at the most recent time. The increasing concentrations of diploptene in sediments younger than ~6000 years BP separate a recent period of higher primary productivity, stronger anoxic bottom waters, and higher bacterial activity from an older period with lesser activity, heretofore undifferentiated. Carbon isotopic compositions of diploptene in the Holocene are between ~31.5 and ~39.6 per mil PDB after ~6000 years BP. These differences in the carbon isotopic record of diploptene probably reflect changes in microbial community structure of bacteria living at the oxic-anoxic interface of the overlying water column. The heavier isotope values are consistent with the activity of nitrifying bacteria and the lighter isotope values with that of aerobic methanotrophic bacteria. Therefore, intermediate delta13C values probably represent mixtures between the populations. In contrast, carbon isotopic compositions of n-C31 are roughly constant at ~31.4 ± 1.1 per mil PDB throughout the Holocene, indicating a uniform input from cuticular waxes of higher plants. Prior to ~6000 years BP, diploptene enriched in 13C of up to -26.3 per mil PDB is indicative of cyanobacteria living in the photic zone and suggests a period of lower primary productivity, more oxygenated bottom waters, and hence lower bacterial activity during the earliest Holocene.

Calcium carbonate, biogenic opal, and organic carbon content and d15N ratios of sediments from the Bering Sea

Millennial-scale paleoceanographic changes in the Bering Sea during the last 71 kyrs were reconstructed using geochemical and isotope proxies (biogenic opal, CaCO3, and total organic carbon (TOC), nitrogen and carbon isotopes of sedimentary organic matters) and microfossil (radiolaria and foraminifera) data from two cores (PC23A and PC24A) which were collected from the northern continental slope area at intermediate water depths. Biogenic opal and TOC contents were generally high with high sedimentation rates during the last deglaciation. Laminated sediment depositions during the Early-Holocene (EH) and Bølling-Allerød (BA) were closely related with the increased primary productivity recorded by high biogenic opal and TOC contents and high d15N values. Enhanced surface-water productivity was attributed to increased nutrient supply from strengthened Bering Slope Current (BSC) and from increased amount of glacial melt-water, resulting in high C/N ratios and low d13C values, and high proportion of Rhizoplegma boreale during the last deglaciation. In contrast, low surface-water productivity during the last glacial period was due to depleted nutrient supply caused by strong stratification and to restricted phytoplankton bloom by extensive sea ice distribution under cold climates. Extensive formation of sea ice produces more oxygen-rich intermediate-water, leading to oxic bottom-water conditions due to active ventilation, which favored good preservation of oxic benthic foraminifera species. Remarkable CaCO3 peaks coeval with high biogenic opal and TOC contents in both cores during MIS 3 to MIS 4 are most likely correlated with Dansgaard-Oeschger (D-O) events. High d15N and d13Corg values during D-O interstadials support increased surface-water productivity resulting from nutrients supplied mainly by intensified BSC. During the EH, BA and D-O interstadials, dominant benthic foraminifera species indicate dysoxic bottom-water conditions as a result of increased surface-water productivity and weak ventilation of intermediate-water with mitigated sea ice development caused by strengthening of the Alaskan Stream. It is of note that the bottom-water conditions and formation of intermediate-water in the Bering Sea during the last glacial period are related to the variation of dissolved oxygen concentration of the bottom-water in the northeastern Pacific and to strong ventilation of intermediate-water in the northwestern Pacific. Thus, the millennial-scale paleoceanographic events in the Bering Sea during the D-O interstadials are closely associated with the intermediate-water ventilation, ultimately leading to weakening of North Pacific Intermediate Water.

Chronology and stable carbon isotopic ratios of sediments from the Western Pacific Warm Pool region

Instrumental data suggest that major shifts in tropical Pacific atmospheric dynamics and hydrology have occurred within the past century, potentially in response to anthropogenic warming. To better understand these trends, we use the hydrogen isotopic ratios of terrestrial higher plant leaf waxes (DDwax) in marine sediments from southwest Sulawesi, Indonesia, to compile a detailed reconstruction of central Indo-Pacific Warm Pool (IPWP) hydrologic variability spanning most of the last two millennia. Our paleodata are highly correlated with a monsoon reconstruction from Southeast Asia, indicating that intervals of strong East Asian summer monsoon (EASM) activity are associated with a weaker Indonesian monsoon (IM). Furthermore, the centennial-scale oscillations in our data follow known changes in Northern Hemisphere climate (e.g., the Little Ice Age and Medieval Warm Period) implying a dynamic link between Northern Hemisphere temperatures and IPWP hydrology. The inverse relationship between the EASM and IM suggests that migrations of the Intertropical Convergence Zone and associated changes in monsoon strength caused synoptic hydrologic shifts in the IPWP throughout most of the past two millennia.

Salinity estimation from Gulf of Guinea, sediment core MD03-2707

The isotopic composition of surface seawater is widely used to infer past changes in sea surface salinity using paired foraminiferal Mg/Ca and d18O from marine sediments. At low latitudes, paleosalinity reconstructions using this method have largely been used to document changes in the hydrological cycle. This method usually assumes that the modern seawater d18O (d18Osw)/salinity relationship remained constant through time. Modelling studies have shown that such assumptions may not be valid because large-scale atmospheric circulation patterns linked to global climate changes can alter the seawater d18Osw/salinity relationship locally. Such processes have not been evidenced by paleo-data so far because there is presently no way to reconstruct past changes in the seawater d18Osw/salinity relationship. We have addressed this issue by applying a multi-proxy salinity reconstruction from a marine sediment core collected in the Gulf of Guinea. We measured hydrogen isotopes in C37:2 alkenones (dDa) to estimate changes in seawater dD. We find a smooth, long-term increase of ~10 per mil in dDa between 10 and 3 kyr BP, followed by a rapid decrease of ~10 per mil in dDa between 3 kyr BP and core top to values slightly lighter than during the early Holocene. Those features are inconsistent with published salinity estimations based on d18Osw and foraminiferal Ba/Ca, as well as nearby continental rainfall history derived from pollen analysis. We combined dDa and d18Osw values to reconstruct a Holocene record of salinity and compared it to a Ba/Ca-derived salinity record from the same sedimentary sequence. This combined method provides salinity trends that are in better agreement with both the Ba/Ca-derived salinity and the regional precipitation changes as inferred from pollen records. Our results illustrate that changes in atmospheric circulation can trigger changes in precipitation isotopes in a counter-intuitive manner that ultimately impacts surface salinity estimates based on seawater isotopic values. Our data suggest that the trends in Holocene rainfall isotopic values at low latitudes may not uniquely result from changes in local precipitation associated with the amount effect.

Isotopic composition and lithic grains concentration of sediment core SI90-09

Theories explaining the origin of the abrupt, massive discharges of ice-rafted detritus (IRD) into the glacial North Atlantic (the Heinrich layers (HLs)) generally point to the Laurentide ice sheet as the sole source of these events, until it was found that the IRDs also originated from Icelandic and European ice sheets (Bond and Lotti, 1995, doi:10.1126/science.267.5200.1005; Snoeckx et al., 1999, doi:10.1016/S0025-3227(98)00168-6; Grousset et al., 2000, doi:10.1130/0091-7613(2000)28<123:WTNAHE>2.0.CO;2). This apparent contradiction must be reconciled as it raises fundamental questions about the mechanism(s) of HL origin. We have analyzed two ~12 cm thick HLs in an ultrahigh-resolution mode (1-2 century intervals) in a mid-Atlantic ridge piston core. The d18O record (N. pachyderma left coiling) reveals strong excursions induced by the melting of the icebergs; these excursions are associated with a strong decrease in the amount of planktic foraminafersand with a 3°C cooling of the surface waters. Counts of coarse detrital grains reveal that IRD are deposited according to a typical sequence (1) volcanic glass, (2) quartz and feldspars, (3) detrital carbonate, that implies a chronology in the melting of the differentpan-Atlantic ice sheets. Sr and Nd isotopic composition confirm that in both Heinrich layers H1 and H2, "precursor" IRD came from first Europe/Iceland, followed then by Laurentide-derived IRD. An internal cyclicity can be identified: during H1 and H2, about four to six major, abrupt discharges occurred roughly on a century timescale. The d13C and d15N records reveal that dominant inputs of continent-derived organic matter are associated with IRD within the HLs, hiding the plankton productivity signal.

Isotopic signatures and mercury content of arctic char and their prey, and water chemistry of 18 arctic Canadian lakes

Concentrations of mercury (Hg) have increased slowly in landlocked Arctic char over a 10- to 15-year period in the Arctic. Fluxes of Hg to sediments also show increases in most Arctic lakes. Correlation of Hg with trophic level (TL) was used to investigate and compare biomagnification of Hg in food webs from lakes in the Canadian Arctic sampled from 2002 to 2007. Concentrations of Hg (total Hg and methylmercury [MeHg]) in food webs were compared across longitudinal and latitudinal gradients in relation to d13C and d15N in periphyton, zooplankton, benthic invertebrates, and Arctic char of varying size-classes. Trophic magnification factors (TMFs) were calculated for the food web in each lake and related to available physical and chemical characteristics of the lakes. The relative content of MeHg increased with trophic level from 4.3 to 12.2% in periphyton, 41 to 79% in zooplankton, 59 to 72% in insects, and 74 to 100% in juvenile and adult char. The d13C signatures of adult char indicated coupling with benthic invertebrates. Cannibalism among char lengthened the food chain. Biomagnification was confirmed in all 18 lakes, with TMFs ranging from 3.5 ± 1.1 to 64.3 ± 0.8. Results indicate that TMFs and food chain length (FCL) are key factors in explaining interlake variability in biomagnification of [Hg] among different lakes.

Alkenones in surface waters of the Nordic seas

Samples of filtered particulate organic matter (POM) were obtained during the summers of 1999 and 2000 from the surface waters of the Nordic seas to monitor the spatial distribution of long-chain alkenones. The aim of the study was to appraise existing alkenone-based climatic proxies in northern high latitudes. Unusually high percentages of the tetraunsaturated alkenone were measured in the polar waters of the East Greenland Current, with C37:4 of up to 77% in 80% of sea-ice cover. Values of percent C37:4 across the Nordic seas showed a strong association with water mass type. Analysis of coccoliths in filters indicated that calcified Emiliania huxleyi could not be discounted as the biological precursor of alkenones in all the water masses. A combined data set of 69 samples of POM revealed a stronger correlation of percent C37:4 to sea surface salinity (SSS; R2 = 0.72) than to sea surface temperature (SST; R2 = 0.50). Values of percent C37:4 in sea surface POM were much higher than those in surficial sediments of the northern North Atlantic. To explain the discrepancy in sedimentary and surface water column percent C37:4, we propose that the alkenone contents in surface sediments underlying arctic and polar waters are a combination of autochthonous and allochthonous inputs of alkenones. Our results show that percent C37:4 can be used to reconstruct the relative extension of arctic/polar water masses in the North Atlantic. However, the results prevent confirmation of percent C37:4 as a paleo-SSS proxy in the Nordic seas, given its multivariate nature in our data set and the decoupling between its range of values in surface waters and sediments.

Specific microbial biomarker signatures from Congo fan sediments of ODP site 175-1075, Congo soils, wetland and estuary sediments

Methane (CH4) is a strong greenhouse gas known to have perturbed global climate in the past, especially when released in large quantities over short time periods from continental or marine sources. It is therefore crucial to understand and, if possible, quantify the individual and combined response of these variable methane sources to natural climate variability. However, past changes in the stability of greenhouse gas reservoirs remain uncertain and poorly constrained by geological evidence. Here, we present a record from the Congo fan of a highly specific bacteriohopanepolyol (BHP) biomarker for aerobic methane oxidation (AMO), 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol), that identifies discrete periods of increased AMO as far back as 1.2 Ma. Fluctuations in the concentration of aminopentol, and other 35-aminoBHPs, follow a pattern that correlates with late Quaternary glacial-interglacial climate cycles, with highest concentrations during warm periods. We discuss possible sources of aminopentol, and the methane consumed by the precursor methanotrophs, within the context of the Congo River setting, including supply of methane oxidation markers from terrestrial watersheds and/or marine sources (gas hydrate and/or deep subsurface gas reservoir). Compound-specific carbon isotope values of -30 per mil to -40 per mil for BHPs in ODP 1075 and strong similarities between the BHP signature of the core and surface sediments from the Congo estuary and floodplain wetlands from the interior of the Congo River Basin, support a methanotrophic and likely terrigenous origin of the 35-aminoBHPs found in the fan sediments. This new evidence supports a causal connection between marine sediment BHP records of tropical deep sea fans and wetland settings in the feeding river catchments, and thus tropical continental hydrology. Further research is needed to better constrain the different sources and pathways of methane emission. However, this study identifies the large potential of aminoBHPs, in particular aminopentol, to trace and, once better calibrated and understood, quantify past methane sources and fluxes from terrestrial and potentially also marine sources.

Alkenone and boron based Oligocene pCO2 records

The Pliocene period is the most recent time when the Earth was globally significantly (~3°C) warmer than today. However, the existing pCO2 data for the Pliocene are sparse and there is little agreement between the various techniques used to reconstruct palaeo-pCO2. Moreover, the temporal resolution of the published records does not allow a robust assessment of the role of declining pCO2 in the intensification of the Northern Hemisphere Glaciation (INHG) and a direct comparison to other proxy records are lacking. For the first time, we use a combination of foraminiferal (delta11B) and organic biomarker (alkenone-derived carbon isotopes) proxies to determine the concentration of atmospheric CO2 over the past 5 Ma. Both proxy records show that during the warm Pliocene pCO2 was between 330 and 400 ppm, i.e. similar to today. The decrease to values similar to pre-industrial times (275-285 ppm) occurred between 3.2 Ma and 2.8 Ma - coincident with the INHG and affirming the link between global climate, the cryosphere and pCO2.