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.

Planktic foraminifers, oxygen- and carbon isotopic compositions, and radiocarbon age in bottom sediments from Core AMK4-316GC

In a sediment core AMK4-316 (460 cm long) on the basis of radiocarbon, oxygen isotope, and lithological data climatostratigraphy is established for time interval about 145 ka. The method of factor analysis and spline interpolation applied to data on distribution of planktic foraminifera species has allowed to reconstruct average annual and seasonal temperatures and salinity at the surface and at depth 100 m. The optimum of the Last Interglaciation (5e) is characterized by maximal temperatures, low amplitudes of seasonal fluctuations, and by increased thickness of the upper homogeneous layer. The glacial hydrological mode has arisen here 115 ka ago. Coolings outstripped appropriate events of the global continental glaciation. Minimal average annual temperatures (4-4.5°C) are reconstructed for 47-45, 42, 36, 29-30, and 10 ka. For 50-30 ka interval numerous strong temperature fluctuations that reflect migrations of the polar front are established. Maximal differences of salinity at the surface and depth 100 m showing influence of melting waters were in the beginning of deglaciations (135 and 20 ka) and repeatedly arose in 50-30 ka interval. The Last Glacial Maximum (18 ka) is characterized by the lowest salinity but not by a peak of low temperatures at the surface. Surface temperature was lowered up to 10 ka. Average annual surface temperature of the Holocene optimum was 2°C above the modern one and 2°C below temperature in the Interglaciation optimum (5e), thickness of the upper homogeneous layer exceeded 100 m.

Grain size and mineral compositions of Pacific red clays

Hypotheses of origin of ocean deep red clays are under discussion. On an example of the Pacific Ocean grain size, mineralogy and chemical composition of clays are considered. It is shown that they formed from atmospheric dust and andesite pyroclastics. Accumulation of the clays occurred through deposition particle-by-particle and by pellet transport.

Table 2. Lead and Ba concentrations and Pb isotopic compositions measured in Law Dome ice cores

Lead isotopic compositions and Pb and Ba concentrations have been measured in ice cores from Law Dome, East Antarctica, covering the past 6500 years. 'Natural' background concentrations of Pb (ab. 0.4 pg/g) and Ba (ab. 1.3 pg/g) are observed until 1884 AD, after which increased Pb concentrations and lowered 206Pb/207Pb ratios indicate the influence of anthropogenic Pb. The isotopic composition of 'natural' Pb varies within the range 206Pb/207Pb=1.20-1.25 and 208Pb/207Pb=2.46-2.50, with an average rock and soil dust Pb contribution of 8-12%. A major pollution event is observed at Law Dome between 1884 and 1908 AD, elevating the Pb concentration four-fold and changing 206Pb/207Pb ratios in the ice to ab. 1.12. Based on Pb isotopic systematics and Pb emission statistics, this is attributed to Pb mined at Broken Hill and smelted at Broken Hill and Port Pirie, Australia. Anthropogenic Pb inputs are at their greatest from 1900 to 1910 and from ab. 1960 to ab. 1980. During the 20th century, Ba concentrations are consistently higher than 'natural' levels and are attributed to increased dust production, suggesting the influence of climate change and/or changes in land coverage with vegetation.

Table 2: Isotopic and elemental compositions of Mesoproterozoic carbonates from Yanshan, North China

In Yanshan, located in the northern part of North China, Mesoproterozoic carbonate sequences (1.6-1.4 Ga) form a 10, 000m thick succession in an aulacogen basin. Carbon and oxygen isotope (d13O and d18O, resp.) data were obtained from 110 carbonate samples across three sections of these Mesoproterozoic deposits. From the early to late Mesoproterozoic, low negative values of d13O appear, followed by low positive variation and then a stable increase. An abrupt decrease in d13O values, with subsequent rapid increase, is found at the end of the Mesoproterozoic. During the whole Mesoproterozoic, d18O shows a mainly negative trend and occasional highly negative isotopic shifts (from lower to upper deposits). Whole-rock carbon and oxygen isotopic compositions and profilesmust be studied to provide a paleogeochemical record that can be associated with paleocean sedimentary environments, temperature, biological productivity, and sea-level fluctuations. Results of the present study correlate well with other international carbon and oxygen isotope profiles, suggesting that a global marine geochemical system existed during the interval of 1.6-1.4 Ga under a globally united tectonic, sedimentary, and geochemical background.

Strontium and neodymium concentrations and isotopic compositions of Arctic marine sediments

Sr and Nd isotopic compositions of Arctic marine sediments characterize changes of sediment source regions and trace shelf-ocean particle pathways during glacial-interglacial transitions in the eastern Arctic Ocean. In the 140-ka sedimentary record of a marine core from Yermak Plateau, north of Svalbard, 87Sr/86Sr ratios and epsion-Nd values vary between 0.717 and 0.740 and 39.3 and 314.9, respectively. Sr and Nd isotopic composition both change characteristically during glacial-interglacial cycles and are correlated with the extension of the Svalbard/Barents Sea ice sheet (SBIS). The downcore variation in Sr and Nd isotopic composition indicates climatically induced changes in sediment provenance from two isotopically distinct end-members: (1) Eurasian shelf sediments as a distal source; and (2) Svalbard bedrock as a proximal source that coincide with a change in transport mechanism from sea ice to glacial ice. During glacier advance from Svalbard and intensified glacial bedrock erosion, epsion-Nd values decrease gradually to a minimum value of 314.9 due to increased input of crystalline Svalbard bedrock material. During glacial maxima, the SBIS covered the entire Barents Sea shelf and supplied increasing amounts of Eurasian shelf material to the Arctic Ocean as ice rafted detritus (IRD). Epsion-Nd values in glacial sediments reach maximum values that are comparable to the average value of modern Eurasian shelf and sea ice sediments (epsion-Nd = 310.3). This confirms ice rafting as a major sediment transport mechanism for Eurasian shelf sediments into the Arctic Ocean and trace a sediment origin from the Kara Sea/Laptev Sea shelf area. After the decay of the shelf-based SBIS, the glacial shelf sediment spikes during glacial terminations I (epsion-Nd = 310.6) and II (epsion-Nd = 310.1) epsion-Nd values rapidly decrease to values of 312.5 typical for interglacial averages. The downcore Sr isotopic composition is anticorrelated to the Nd isotopic composition, but may be also influenced by grain-size effects. In contrast, the Nd isotopic composition in clay- to silt-size fractions of one bulk sediment sample is similar to within 0.3-0.8 epsion-Nd units and seems to be a grain-size independent provenance tracer.

Radiocarbon, stable isotopic compositions and seawater chemical properties of Black Sea core-top sediments and CTD stations

Chloropigments and their derivative pheopigments preserved in sediments can directly be linked to photosynthesis. Their carbon and nitrogen stable isotopic compositions have been shown to be a good recorder of recent and past surface ocean environmental conditions tracing the carbon and nitrogen sources and dominant assimilation processes of the phytoplanktonic community. In this study we report results from combined compound-specific radiocarbon and stable carbon and nitrogen isotope analysis to examine the time-scales of synthesis and fate of chlorophyll-a and its degradation products pheophytin-a, pyropheophytin-a, and 132,173-cyclopheophorbide-a-enol until burial in Black Sea core-top sediments. The pigments are mainly of marine phytoplanktonic origin as implied by their stable isotopic compositions. Pigment ?15N values indicate nitrate as the major uptake substrate but 15N-depletion towards the open marine setting indicates either contribution from N2-fixation or direct uptake of ammonium from deeper waters. Radiocarbon concentrations translate into minimum and maximum pigment ages of approximately 40 to 1200 years. This implies that protective mechanisms against decomposition such as association with minerals, storage in deltaic anoxic environments, or eutrophication-induced hypoxia and light limitation are much more efficient than previously thought. Moreover, seasonal variations of nutrient source, growth period, and habitat and their associated isotopic variability are likely at least as strong as long-term trends. Combined triple isotope analysis of sedimentary chlorophyll and its primary derivatives is a powerful tool to delineate biogeochemical and diagenetic processes in the surface water and sediments, and to assess their precise time-scales.

Oxygen and carbon isotopic compositions of foraminifers at DSDP Hole 72-517

Oxygen and carbon isotope analyses were performed on monospecific or mixed-species samples of benthic foraminifers, as well as on the planktonic species Globigerinoides ruber from a 24-m hydraulic piston core raised on the western flank of the Rio Grande Rise, at DSDP Site 517 (30°56.81'S and 38°02.47'W, water depth 2963 m) in the southwestern Atlantic. This site is presently located in the core of North Atlantic Deep Water (NADW). This is the first long isotopic record of Quaternary benthic foraminifers; it displays at least 30 isotopic stages, 25 of them readily correlated with the standard sequence of Pacific Core V28-239. The depths of both the Bruhnes/Matuyama boundary and the Jaramillo Event based on oxygen isotope stratigraphy agree well with paleomagnetic results. Quaternary faunal data from this part of the Atlantic are dated through isotopic stratigraphy and partially contradict data previously published by Williams and Ledbetter (1979). There was a substantial increase in the size of the earth's major ice sheets culminating at Stage 22 and corresponding to a l per mil progressive increase of d18O maximal values. Further, ice volume-induced isotopic changes were not identical for different glacial cycles. Oxygen and carbon isotope analyses of benthic foraminifers show that during Pleistocene glacial episodes, NADW was cooler than today and that Mediterranean outflow might still have contributed to the NADW sources. The comparison of coiling ratio changes of Globorotalia truncatulinoides with planktonic and benthic oxygen isotope records shows that there might have been southward excursions of the Brazil Current during the Pleistocene, perhaps related to Antarctic surface water surges. The question of the location of NADW sources during glacial maxima remains open.