Compilation of 220 sediment core d13C data from the glacial Atlantic Ocean

We compare a compilation of 220 sediment core d13C data from the glacial Atlantic Ocean with three-dimensional ocean circulation simulations including a marine carbon cycle model. The carbon cycle model employs circulation fields which were derived from previous climate simulations. All sediment data have been thoroughly quality controlled, focusing on epibenthic foraminiferal species (such as Cibicidoides wuellerstorfi or Planulina ariminensis) to improve the comparability of model and sediment core carbon isotopes. The model captures the general d13C pattern indicated by present-day water column data and Late Holocene sediment cores but underestimates intermediate and deep water values in the South Atlantic. The best agreement with glacial reconstructions is obtained for a model scenario with an altered freshwater balance in the Southern Ocean that mimics enhanced northward sea ice export and melting away from the zone of sea ice production. This results in a shoaled and weakened North Atlantic Deep Water flow and intensified Antarctic Bottom Water export, hence confirming previous reconstructions from paleoproxy records. Moreover, the modeled abyssal ocean is very cold and very saline, which is in line with other proxy data evidence.

Stable isotope ratios on planktonic foraminifer N. pachyderma of surface sediments from the Arctic Ocean (Table 1)

Planktic foraminifers Neogloboquadrina pachyderma (sin.) from 87 eastern and central Arctic Ocean surface sediment samples were analyzed for stable oxygen and carbon isotope composition. Additional results from 52 stations were taken from the literature. The lateral distribution of delta18O (18O/16O) values in the Arctic Ocean reveals a pattern of roughly parallel, W-E stretching zones in the Eurasian Basin, each ~0.5 per mil wide on the delta18O scale. The low horizontal and vertical temperature variability in the Arctic halocline waters (0-100 m) suggests only little influence of temperature on the oxygen isotope distribution of N. pachyderma (sin.). The zone of maximum delta18O values of up to 3.8 per mil is situated in the southern Nansen Basin and relates to the tongue of saline (> 33%.) Atlantic waters entering the Arctic Ocean through the Fram Strait. delta18O values decrease both to the Barents Shelf and to the North Pole, in accordance with the decreasing salinities of the halocline waters. In the Nansen Basin, a strong N-S delta18O gradient is in contrast with a relatively low salinity change and suggests contributions from different freshwater sources, i.e. salinity reduction from sea ice meltwater in the south and from light isotope waters (meteoric precipitation and river-runoff) in the northern part of the basin. North of the Gakkel Ridge, delta18O and salinity gradients are in good accordance and suggest less influence of sea ice melting processes. The delta13C (13C/12C) values of N. pachyderma (sin.) from Arctic Ocean surface sediment samples are generally high (0.75-0.95 per mil). Lower values in the southern Eurasian Basin appear to be related to the intrusion of Atlantic waters. The high delta13C values are evidence for well ventilated surface waters. Because the perennial Arctic sea ice cover largely prevents atmosphere-ocean gas exchange, ventilation on the seasonally open shelves must be of major importance. Lack of delta13C gradients along the main routes of the ice drift from the Siberian shelves to the Fram Strait suggests that primary production (i.e. CO2 consumption) does probably not change the CO2 budget of the Arctic Ocean significantly.

(Table 1) Bulk geochemistry of sediment cores KH-79-3_L3 and KH-79-3_C3

The organic and isotopic geochemical study of two sediment cores (KH-79-3, L-3, and KH-79-3, C-3) from the Oki Ridge in the Japan Sea has revealed that total organic carbon (TOC) mass accumulation rates are extremely high in the 12-11 ka (calendar age) interval and TOC in the sections in the 24-17 ka interval is depleted in 13C by 3.5? relative to Holocene sediments. Alkenone sea surface temperature (SST) shows a decrease from 18° to 14°C from 17.5 to 11.6 ka and a sharp increase from 14° to 19°C from 11.6 to 11.1 ka. The SST changes are associated with the inflow of cold seawater with the vertical water mixing and the inflowof warm Tsushima Current into the Japan Sea. The d13C values for both 24-methylcholesta-5,22-dien-3?-ol (diatom marker) and dinosterol (dinoflagellate marker), are at their minimum from 24 to 17 ka, while those for long-chain alkenones are not. The theoretical considerations on d13C for biomarkers suggest low photosynthetic carbon demand of diatoms and dinoflagellates from 24 to 17 ka.

(Table 1) Radiocarbon dates of core JM05-085-GC, South-Barents Sea

The Late Weichselian-Early Holocene variability of the North Atlantic Current has been studied with focus on the zonal component of this meridional transport during the transition from glacial to interglacial conditions. The investigated sediment core is from 409 m water depth in the SW Barents Sea. Eight Accelerator mass spectrometry (AMS) 14C dates show that the core covers the last 20,000 cal yr B.P. with a centennial scale resolution during Late Weichselian-Early Holocene. Planktic foraminiferal assemblages were analyzed using the >100 ?m size fraction and foraminiferal planktic and benthic d13C and d18O isotopes were measured. Furthermore, a range of physical and chemical analyses has been carried out on the bulk sediment samples. Four time periods have been identified which represent the varying oceanographic conditions in Ingøydjupet, a glacial trough located off the north coast of Norway in the SW Barents Sea. 1) The late glacial (before ca 15,000 cal yr B.P.) influenced by the nearby ice sheets with high amounts of sea ice- or iceberg-transported detritus. 2) The late Oldest Dryas stadial and the Bølling-Allerød interstadial (ca 15,000-12,700 cal yr B.P.) with cold surface water conditions influenced by the collapse of the nearby ice sheets, high amounts of sea ice- or iceberg-transported detritus and melt water and weak subsurface inflow of Atlantic Water. 3) The Younger Dryas cold stadial (12,700-11,650 cal yr B.P.) with low primary productivity and extensive sea ice cover and 4) The Preboreal and Early Holocene (11,650-6800 cal yr B.P. cal yr B.P.) with strong influx of Atlantic Water into the area, near absence of ice rafted debris and generally ameliorated conditions in both surface and bottom water masses as seen from a high flux of foraminifera and increased marine primary production.

Epibenthic foraminiferal d13C in the Recent deep Arctic Ocean

Low planktic and benthic d18O and d13C values in sediments from the Nordic seas of cold stadials of the last glaciation have been attributed to brines, formed similar to modern ones in the Arctic Ocean. To expand on the carbon isotopes of this hypothesis I investigated benthic d13C from the modern Arctic Ocean. I show that mean d13C values of live epibenthic foraminifera from the deep Arctic basins are higher than mean d13C values of upper slope epibenthic foraminifera. This agrees with mean high d13C values of dissolved inorganic carbon (DIC) in Arctic Bottom Water (ABW), which are higher than mean d13CDIC values from shallower water masses of mainly Atlantic origin. However, adjustments for oceanic 13C-Suess depletion raise subsurface and intermediate water d13CDIC values over ABW d13CDIC ones. Accordingly, during preindustrial Holocene times, the d13CDIC of ABW was as high or higher than today, but lower than the d13CDIC of younger subsurface and intermediate water. If brine-enriched water significantly ventilated ABW, brines should have had high d13CDIC values. Analogously, high-d13CDIC brines may have been formed in the Nordic seas during warm interstadials. During cold stadials, when most of the Arctic Ocean was perennially sea-ice covered, a cessation of high-d13CDIC brine rejection may have lowered d13CDIC values of ABW, and ultimately the d13CDIC in Nordic seas intermediate and deep water. So, in contrast to the idea of enhanced brine formation during cold stadials, the results of this investigation imply that a cessation of brine rejection would be more likely.

Chemical and isotopic compositions of water, particulates, plankton, gases, sediments, and minerals from the Kara Sea and lower Ob and Yenisei Rivers

The Kara Sea is an area uniquely suitable for studying processes in the river-sea system. This is a shallow sea, into which two great Siberian rivers, Yenisei and Ob, flow. From 1995 to 2003, the sea was studied by six international expeditions onboard the R/V Akademik Boris Petrov. This publication summarizes the results obtained, within the framework of this project, at the Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences. Various hydrogeochemical parameters, concentrations and isotopic composition of organic and carbonate carbon of the sediments, plankton, particulate organic matter, hydrocarbons, and dissolved CO2 were examined throughout the whole sea area at more than 200 sites. The d13C varies from -22 and -24 per mil where Atlantic waters enter the Kara Sea and in the north-eastern part of the water area to -27 per mil in the Yenisei and Ob estuaries. The value of d13C of the plankton is only weakly correlated with the d13C of the organic matter from the sediments and is lower by as much as 3-4 per mil. The paper presents the results obtained from a number of meridional river-sea profiles. It was determined from the relations between the isotopic compositions of plankton and particulate matter that the river waters carry material consisting of 70% detrital-humus matter and 30% planktonogenic material in the river part, and the material contained in the offshore waters consists of 30% terrigenous components, with the contribution of bioproducers amounting to 70%. The carbon isotopic composition of the plankton ranges from -29 to -35 per mil in the riverine part, from -28 to -27 per mil in the estuaries, and from -27.0 to -25 per mil in the marine part. The relative lightness of the carbon isotopic composition of plankton in Arctic waters is explained by the temperature effect, elevated CO2 concentrations, and long-distance CO2 supply to the sea with river waters. The data obtained on the isotopic composition of CO2 in the surface waters of the Kara Sea were used to map the distribution of d13C. The complex of hydrocarbon gases extracted from the waters included methane, C2-C5, and unsaturated C2=-C4= hydrocarbons, for which variations in the concentrations in the waters were studied along river-estuary-sea profiles. The geochemistry of hydrocarbon gases in surface fresh waters is characterized by comparable concentrations of methane (0.3-5 µl/l) and heavier hydrocarbons, including unsaturated ones. Microbiological methane with d13C from -105 to -90 per mil first occurs in the sediments at depths of 40-200 cm. The sediments practically everywhere display traces of methane oxidation in the form of a shift of the d13C of methane toward higher values and the occurrence of autogenic carbonate material, including ikaite, enriched in the light isotope. Ikaite (d13C from -25 to -60 per mil) was found and examined in several profiles. The redox conditions in the sediments varied from normal in the southern part of the sea to highly oxidized along the Novaya Zemlya Trough. Vertical sections through the sediments of the latter exemplify the complete suppression of the biochemical activity of microorganisms. Our data provide insight into the biogeochemistry of the Kara Sea and make it possible to specify the background values needed for ecological control during the future exploration operations and extraction of hydrocarbons in the Kara Sea.

Sediment and pore water chemistry of cores 214 and 755 recovered during Meteor M72/1 and POSEIDON cruise POS317/2, northwestern Black Sea

High-resolution sedimentary records of major and minor elements (Al, Ba, Ca, Sr, Ti), total organic carbon (TOC), and profiles of pore water constituents (SO42-, CH4, Ca2+, Ba2+, Mg2+, alkalinity) were obtained for two gravity cores (core 755, 501 m water depth and core 214, 1686 m water depth) from the northwestern Black Sea. The records were examined in order to gain insight into the cycling of Ba in anoxic marine sediments characterized by a shallow sulfate-methane transition (SMT) as well as the applicability of barite as a primary productivity proxy in such a setting. The Ba records are strongly overprinted by diagenetic barite (BaSO4) precipitation and remobilization; authigenic Ba enrichments were found at both sites at and slightly above the current SMT. Transport reaction modeling was applied to simulate the migration of the SMT during the changing geochemical conditions after the Holocene seawater intrusion into the Black Sea. Based on this, sediment intervals affected by diagenetic Ba redistribution were identified. Results reveal that the intense overprint of Ba and Baxs (Ba excess above detrital average) strongly limits its correlation to primary productivity. These findings have implications for other modern and ancient anoxic basins, such as sections covering the Oceanic Anoxic Events for which Ba is frequently used as a primary productivity indicator. Our study also demonstrates the limitations concerning the use of Baxs as a tracer for downward migrations of the SMT: due to high sedimentation rates at the investigated sites, diagenetic barite fronts are buried below the SMT within a relatively short period. Thus, 'relict' barite fronts would only be preserved for a few thousands of years, if at all.

Pollen profile and age determination for sediment core M72/5_619-1 (22-GC3)

Sediments from the Black Sea, a region historically dominated by forests and steppe landscapes, are a valuable source of detailed information on the changes in regional terrestrial and aquatic environments at decadal to millennial scales. Here we present multi-proxy environmental records (pollen, dinoflagellate cysts, Ca, Ti and oxygen isotope data) from the uppermost 305 cm of the core 22-GC3 (42°13.53' N, 36°29.55' E) collected from a water depth of 838 m in the southern part of the Black Sea in 2007. The records span the last ~ 18 kyr (all ages are given in cal kyr BP). The pollen data reveal the dominance of the Artemisia-steppe in the region, suggesting rather dry/cold environments ~ 18-14.5 kyr BP. Warming/humidity increase during melt-water pulses (~ 16.1-14.5 kyr BP), indicated by d18O records from the 22-GC3 core sediment and from the Sofular Cave stalagmite, is expressed in more negative d13C values from the Sofular Cave, usually interpreted as the spreading of C3 plants. The records representing the interstadial complex (~ 14.5-12.9 kyr BP) show an increase in temperature and moisture, indicated by forest development, increased primary productivity and reduced surface run-off, whereas the switch from primary terrigenous to primary authigenic Ca origin occurs ~ 500 yr later. The Younger Dryas cooling is clearly demonstrated by more negative d13C values from the Sofular Cave and a reduction of pines. The early Holocene (11.7-8.5 kyr BP) interval reveals relatively dry conditions compared to the mostly moist and warm middle Holocene (8.5-5 kyr BP), which is characterized by the establishment of the species-rich warm mixed and temperate deciduous forests in the low elevation belt, temperate deciduous beech-hornbeam forests in the middle and cool conifer forest in upper mountain belt. The border between the early and middle Holocene in the vegetation records coincides with the opening of the Mediterranean corridor at ~ 8.3 kyr BP, as indicated by a marked change in the dinocyst assemblages and in the sediment lithology. Changes in the pollen assemblages indicate a reduction in forest cover after ~ 5 kyr BP, which was likely caused by increased anthropogenic pressure on the regional vegetation.

(Table 1) Isotopic composition of organic compinents of DSDP Hole 24-231

Plant leaf wax hydrogen isotope (dDwax) reconstructions are increasingly being used to reconstruct hydrological change. This approach is based upon the assumption that variations in hydroclimatic variables, and in particular, the isotopic composition of precipitation (dDP), dominate dDwax. However modern calibration studies suggest that offsets between plant types may bias the dDwax hydrological proxy at times of vegetation change. In this study, I pair leaf wax analyses with published pollen data to quantify this effect and construct the first vegetation-corrected hydrogen isotopic evidence for precipitation (dDcorrP). In marine sediments from Deep Sea Drilling Program Site 231 in the Gulf of Aden spanning 11.4-3.8 Ma (late Miocene and earliest Pliocene), I find 77 per mil swings in dDwax that correspond to pollen evidence for substantial vegetation change. Similarities between dDP and dDcorrP imply that the hydrological tracer is qualitatively robust to vegetation change. However, computed vegetation corrections can be as large as 31 per mil indicating substantial quantitative uncertainty in the raw hydrological proxy. The resulting dDcorrP values quantify hydrological change and allow us to identify times considerably wetter than modern at 11.09, 7.26, 5.71 and 3.89 Ma. More generally, this novel interpretative framework builds the foundations of improved quantitative paleohydrological reconstructions with the dDwax proxy, in contexts where vegetation change may bias the plant-based proxy. The vegetation corrected paleoprecipitation reconstruction dDcorrP, represents the best available estimate as proof-of-concept, for an approach that I hope will be refined and more broadly applied.

(Table 1) Age determination of sediment cores EW9302-JPC1 and EW9302-JPC2

Results from two deep sea cores from northeast of Newfoundland at 1251 and 2527 m water depth, respectively, indicate that during the time period from 160,000 to 10,000 years BP, ice rafting events in the Labrador Sea were accompanied by rapid variations in deep and surface water circulation. Twelve ice-rafting events occurred, each coinciding with high concentrations of detrital carbonate and oxygen isotopic depletion of both surface and bottom waters. Eleven of these can be correlated with the North Atlantic Heinrich events H1-H11. The remaining very conspicuous ice-rafting event took place early in MIS substage 5e, at a time when the planktic faunal assemblage suggests marked warming of the sea surface. In the shallower core, benthic d13C values rise from a minimum during the deglaciation to peak substage 5e values following the last ice-rafting event, indicating that the ventilation of intermediate depths was renewed after the deglaciation was complete and continued throughout substage 5e. The benthic foraminifera suggest that this well-ventilated water mass was comparable to the modern Labrador Sea Water (LSW). The benthic faunas suggest that a relatively warm intermediate water mass entered the SE Labrador Sea during Heinrich events. Generally low benthic d13C values indicate that this water mass was poorly ventilated and rich in inorganic nutrients. Isotope data and benthic faunal distributions indicate that North Atlantic Deep Water (NADW) formed in the Norwegian-Greenland Sea reached the SE Labrador Sea between the Heinrich events.

Accumulation rates of plant-wax-derived long-chain C25 to C35 odd-numbered n-alkanes and d13C values of the n-C31 alkane of ODP Hole 175-1077B

The dominant forcing factors for past large-scale changes in vegetation are widely debated. Changes in the distribution of C4 plants-adapted to warm, dry conditions and low atmospheric CO2 concentrations (Collatz et al., 1998, doi:10.1007/s004420050468) -have been attributed to marked changes in environmental conditions, but the relative impacts of changes in aridity, temperature (Pagani et al., 1999, doi:10.1126/science.285.5429.876; Huang et al., 2001, doi:10.1126/science.1060143) and CO2 concentration (Cerling et al., 1993, doi:10.1038/361344a0; Kuypers et al., 1999, doi:10.1038/20659) are not well understood. Here, we present a record of African C4 plant abundance between 1.2 and 0.45 million years ago, derived from compound-specific carbon isotope analyses of wind-transported terrigenous plant waxes. We find that large-scale changes in African vegetation are linked closely to sea surface temperatures in the tropical Atlantic Ocean. We conclude that, in the mid-Pleistocene, changes in atmospheric moisture content - driven by tropical sea surface temperature changes and the strength of the African monsoon - controlled aridity on the African continent, and hence large-scale vegetation changes.