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.

(Table 1) Oxygen and carbon isotopes for planktonic foraminifers at DSDP Hole 64-480

During the cleaning of the HPC core surfaces from Hole 480 for photography, the material removed was conserved carefully in approximately 10 cm intervals (by K. Kelts); this material was made available to us in the hope that it would be possible to obtain oxygen isotope stratigraphy for the site. The samples were, of course, somewhat variable in size, but the majority were probably between 5 and 10 cm**3. Had this been a normal marine environment, such sample sizes would have contained abundant planktonic foraminifers together with a small number of benthics. However, this is clearly not the case, for many samples contained no foraminifers, whereas others contained more benthics than planktonics. Among the planktonic foraminifers the commonest species are Globigerina bulloides, Neogloboquadrina dutertrei, and N. pachyderma. A few samples contain a more normal fauna with Globigerinoides spp. and occasional Globorotalia spp. Sample 480-3-3, 20-30 cm contained Globigerina rubescens, isolated specimens of which were noted in a few other samples in Cores 3,4, and 5. This is a particularly solution-sensitive species; in the open Pacific it is only found widely distributed at horizons of exceptionally low carbonate dissolution, such as. the last glacial-to-interglacial transition.

AMS radiocarbon dates on ten monospecific samples of planktonic foraminifer Globigerinoides ruber of sediment core GeoB8509-2 (Table 1)

Aeolian and fluvial sediment transport to the Atlantic Ocean offshore Mauritania were reconstructed based on grain-size distributions of the carbonate-free silt fraction of three marine sediment records of Cap Timiris Canyon to monitor the climatic evolution of present-day arid north-western Africa. During the late Pleistocene, predominantly coarse-grained particles, which are interpreted as windborne dust, characterise glacial dry climate conditions with a low sea level and extended sand seas that reach onto the exposed continental shelf off Mauritania. Subsequent particle fining and the abrupt decrease in terrigenous supply are attributed to humid climate conditions and dune stabilisation on the adjacent African continent with the onset of the Holocene humid period. Indications for an ancient drainage system, which was discharging fluvial mud offshore via Cap Timiris Canyon, are provided by the finest end member for early to mid Holocene times. However, in comparison to the Senegal and Niger River further south, the river system connecting Cap Timiris Canyon with the Mauritanian hinterland was starved during the late Holocene and is non-discharging under present-day arid climate conditions.

(Table 1) Radiocarbon dating of a lake sediment core, southern West Greenland

The dominant processes determining biological structure in lakes at millennial timescales are complex. In this study, we used a multi-proxy approach to determine the relative importance of in-lake versus indirect processes on the Holocene development of an oligotrophic lake in SW Greenland (66.99°N, 50.97°W). A 14C and 210Pb-dated sediment core covering approximately 8500 years BP was analyzed for organic-inorganic carbon content, pigments, diatoms, chironomids, cladocerans, and stable isotopes (d13C, d18O). Relationships among the different proxies and a number of independent controlling variables (Holocene temperature, an isotope-inferred cooling period, and immigration of Betula nana into the catchment) were explored using redundancy analysis (RDA) independent of time. The main ecological trajectories in the lake biota were captured by ordination first axis sample scores (18-32% variance explained). The importance of the arrival of Betula (ca. 6500 years BP) into the catchment was indicated by a series of partial-constrained ordinations, uniquely explaining 12-17% of the variance in chironomids and up to 9% in pigments. Climate influences on lake biota were strongest during a short-lived cooling period (identified by altered stable isotopes) early in the development of the lake when all proxies changed rapidly, although only chironomids had a unique component (8% in a partial-RDA) explained by the cooling event. Holocene climate explained less variance than either catchment changes or biotic relationships. The sediment record at this site indicates the importance of catchment factors for lake development, the complexity of community trends even in relatively simple systems (invertebrates are the top predators in the lake) and the challenges of deriving palaeoclimate inferences from sediment records in low-Arctic freshwater lakes.