Stable carbon and oxygen isotope ratios of planktonic foraminifera from the equatorial Atlantic

Carbon isotopic records of nutrient-depleted surface water place constraints on the past fertility of the oceans and on past atmospheric pCO2 levels. The best records of nutrient-depleted delta13C are obtained from planktonic foraminifera living in the thick mixed layers of the western equatorial and tropical Atlantic Ocean. We have produced a composite, stacked Globigerinoides sacculifer delta13C record from the equatorial Atlantic, which exhibits significant spectral power at the 100,000- and 41,000-year Milankovitch periods, but no power at the 23,000-year period. Similar to the record presented by Shackleton and Pisias [1985], surface-deep ocean Delta delta13C produced with the G. sacculifer record leads the delta18O ice volume record. However, the glacial-interglacial amplitudes of Delta delta13C differ between our record and Shackleton and Pisias [1985] record. Although large changes in Delta delta13C occur in the equatorial Atlantic during early stages of the last three glacial cycles, surface-deep Delta delta13C at glacial maxima (18O stage 2, late stage 6, and late stage 8) was only about 0.2? greater than during the subsequent interglacial. Our results imply that nutrient-driven pCO2 changes account for about one third of the pCO2 decrease observed in ice cores, and consequently, Delta delta13C should not be used as a proxy pCO2 index. Enough variance in the ice core pCO2 records remains to be explained that conclusions about pCO2 and ice volume phase relationships should also be reexamined. As much as 40 ppm pCO2 change still has not been accounted for by models of past physics and chemistry of the ocean.

Shell flux and oxygen isotope data of North Atlantic foraminifera

We present an almost 3 year long time series of shell fluxes and oxygen isotopes of left-coiling Neogloboquadrina pachyderma and Turborotalita quinqueloba from sediment traps moored in the deep central Irminger Sea. We determined their response to the seasonal change from a deeply mixed water column with occasional deep convection in winter to a thermally stratified water column with a surface mixed layer (SML) of around 50 m in summer. Both species display very low fluxes during winter with a remnant summer population holding out until replaced by a vital population that seeds the subsequent blooms. This annual population overturning is marked by a 0.7 per mill increase in d18O in both species. The shell flux of N. pachyderma peaks during the spring bloom and in late summer, when stratification is close to its minimum and maximum, respectively. Both export periods contribute about equally and account for >95% of the total annual flux. Shell fluxes of T. quinqueloba show only a single broad pulse in summer, thus following the seasonal stratification cycle. The d18O of N. pachyderma reflects temperatures just below the base of the seasonal SML without offset from isotopic equilibrium. The d18O pattern of T. quinqueloba shows a nearly identical amplitude and correlates highly with the d18O of N. pachyderma. Therefore T. quinqueloba also reflects temperature near the base of the SML but with a positive offset from isotopic equilibrium. These offsets contrast with observations elsewhere and suggest a variable offset from equilibrium calcification for both species. In the Irminger Sea the species consistently show a contrast in their flux timings. Their flux-weighted delta d18O will thus dominantly be determined by seasonal temperature differences at the base of the SML rather than by differences in their depth habitat. Consequently, their sedimentary delta d18O may be used to infer the seasonal contrast in temperature at the base of the SML.

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.

Averaged sedimentation rates in the Northwest Pacific and Bering Sea during the first and the second oxygen isotope stages

Isotope chronostratigraphy of Upper Quaternary sediments from the Northwest Pacific and the Bering Sea was established by oxygen isotope records in planktonic and benthic foraminifera. The main regularities of temporal variations of calcium carbonate, organic carbon and opal contents, as well as of magnetic susceptibility in sediments of the study region with regard to climatic variations and productivity were established by means of isotopic-geochemical and lithophysical analyses of bottom sediments. Correlation of volcanogenic interbeds in the sediments was carried out, and their stratigraphy and age were preliminarily ascertained. Correlation was accomplished of A.P. Jouse diatom horizons determined by an analysis of the main ecological variations in diatom assemblages in Upper Quaternary sediments of the Northwest Pacific, Bering and Okhotsk Seas, and their comparison with similar variations in sediment cores with standard oxygen isotope stages. Also variations in lithology and contents of biogenic components in sediments of the region and in the cores were taken into account. A ratio of abundance of "neritic" species to the sum of "neritic" and oceanic species abundance (coefficient Id) can be a criterion of ecological changes of diatom assemblages in the studied region. It is determined by climate variability and mostly by sea ice influence. Schemes of average sedimentation rates in the Northwest Pacific and Bering Sea for periods of the first and the second oxygen isotope stages (12.5-1 and 24-12.5 ka, respectively) were plotted on the basis of obtained results and correlation of diatom horizons and lithological units in early studied cores with the oxygen isotope stages. Closure of the Bering Strait and aeration of the north-eastern shelf of the Bering Sea during the second stage induced increase of sedimentation rates in the Bering Sea, as compared with the first stage, and suspended material transport from the Bering Sea through the Kamchatka Strait into the Northwest Pacific and its accumulation in the southeast direction.

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.

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.

Carbon and oxygen isotope ratios, and geochemistry of the Precambrian-Cambrian Sukharikha River section, northwestern Siberian platform

A high-resolution carbon isotope profile through the uppermost Neoproterozoic-Lower Cambrian part of the Sukharikha section at the northwestern margin of the Siberian platform shows prominent secular oscillations of d13C with peak-to-peak range of 6-10 ?. There are six minima, 1n-6n, and seven maxima 1p-7p, in the Sukharikha Formation and a rising trend of d13C from the minimum 1n of -8.6 ? to maximum 6p of +6.4 ?. The trough 1n probably coincides with the isotopic minimum at the Precambrian-Cambrian boundary worldwide. Highly positive d13C values of peaks 5p and 6p are typical of the upper portion of the Precambrian-Cambrian transitional beds just beneath the Tommotian Stage in Siberia. A second rising trend of d13C is observed through the Krasnoporog and lower Shumny formations. It consists of four excursions with four major maxima that can be cor related with Tommotian-Botomian peaks II, IV, V, and VII of the reference profile from the southeastern Siberian platform. According to the chemostratigraphic cor relation, the first appearances of the index forms of archaeocyaths are earlier in the Sukharikha section than in the Lena-Aldan region.

Stable oxygen and carbon isotopes ratios of sediment core GeoB9528-3

The carbon isotopic composition of individual plant leaf waxes (a proxy for C3 vs. C4 vegetation) in a marine sediment core collected from beneath the plume of Sahara-derived dust in northwest Africa reveals three periods during the past 192,000 years when the central Sahara/Sahel contained C3 plants (likely trees), indicating substantially wetter conditions than at present. Our data suggest that variability in the strength of Atlantic meridional overturning circulation (AMOC) is a main control on vegetation distribution in central North Africa, and we note expansions of C3 vegetation during the African Humid Period (early Holocene) and within Marine Isotope Stage (MIS) 3 (approx. 50-45 ka) and MIS 5 (approx. 120-110 ka). The wet periods within MIS 3 and 5 coincide with major human migration events out of sub-Saharan Africa. Our results thus suggest that changes in AMOC influenced North African climate and, at times, contributed to amenable conditions in the central Sahara/Sahel, allowing humans to cross this otherwise inhospitable region.

Stable carbon and oxygen isotope ratios of Planulina wuellerstorfi from sediments of the Vema Channel

Oxygen- and carbon-isotopic analyses have been performed on the benthic foraminifer Planulina wuellerstorfi in seven Late Quaternary cores from the Vema Channel-Rio Grande Rise region. The cores are distributed over the water-depth interval of 2340 to 3939 m, which includes the present transition from North Atlantic Deep Water (NADW) to Antarctic Bottom Water (AABW). The carbon-isotopic records in the cores vary as a function of water depth. The shallowest and deepest cores show no significant glacial-interglacial difference in delta13C. Four of the five cores presently located in the NADW have benthic foraminiferal delta13C that is lower during glacial isotopic stages. Based on bathymetric gradients in delta13C, we conclude that, like today, there were two water masses present in the Vema Channel during glacial intervals: a water mass enriched in 13C overlying another water mass depleted in 13C. The largest gradient of change of delta13C with depth, however, occurred at 2.7 km, ~1 km shallower than the present position of this gradient. On the basis of paleontologic and sedimentologic evidence, we consider it unlikely that the NADW:AABW transition shallowed to this level. Reduced carbon-isotopic gradients between the deep basins of the North Atlantic and Pacific Oceans during the last glaciation suggest that production of NADW was reduced. Lower production of NADW may have modified the local abyssal circulation pattern in the Vema Channel region.

Stable oxygen isotope data of Thoracosphaera heimii in surface sediment samples of the equatorial Atlantic and South Atlantic

To investigate the potential use of the stable isotope composition of the vegetative cysts of the photosynthetic dinoflagellate Thoracosphaera heimii for quantitative palaeotemperature reconstructions a method has been developed to purify T. heimii cysts from sediment samples. Stable oxygen and carbon isotopes have been measured on T. heimii cysts from 21 surface sediment samples from the equatorial Atlantic and South Atlantic Oceans. Calculated temperatures based on the palaeotemperature equation for inorganic calcite precipitation generally reflect mean annual temperatures of the upper water column, notably of thermocline depths. Although the present results suggest that the isotopic composition of T. heimii shells might be formed in equilibrium with the seawater in which the shells are being formed, future investigations are required to determine possible effects of metabolic and kinetic processes on the fractionation process. This pilot study therefore forms the basis for future investigations on the development of this tool and the determination of a species-specific palaeotemperature equation. The wide geographic and stratigraphic distribution of T. heimii cysts in sediments, the stable position of T. heimii within the water column and the high resistance of its cysts against calcite dissolution underline its potential for a wide usability in palaeotemperature reconstructions.

Chemical and isotopic composition of carbonate veins from ODP Leg 209

Carbonate veins hosted in ultramafic basement drilled at two sites in the Mid Atlantic Ridge 15°N area record two different stages of fluid-basement interaction. A first generation of carbonate veins consists of calcite and dolomite that formed syn- to postkinematically in tremolite-chlorite schists and serpentine schists that represent gently dipping large-offset faults. These veins formed at temperatures between 90 and 170 °C (oxygen isotope thermometry) and from fluids that show intense exchange of Sr and Li with the basement (87Sr/86Sr = 0.70387 to 0.70641, d7Li L-SVEC = + 3.3 to + 8.6 per mil). Carbon isotopic compositions range to high d13C PDB values (+ 8.7 per mil), indicating that methanogenesis took place at depth. The Sr-Li-C isotopic composition suggests temperatures of fluid-rock interaction that are much higher (T > 350-400 °C) than the temperatures of vein mineral precipitation inferred from oxygen isotopes. A possible explanation for this discrepancy is that fluids cooled conductively during upflow within the presumed detachment fault. Aragonite veins were formed during the last 130 kyrs at low-temperatures within the uplifted serpentinized peridotites. Chemical and isotopic data suggest that the aragonites precipitated from cold seawater, which underwent overall little exchange with the basement. Oxygen isotope compositions indicate an increase in formation temperature of the veins by 8-12 °C within the uppermost ~ 80 m of the subseafloor. This increase corresponds to a high regional geothermal gradient of 100-150 °C/km, characteristic of young lithosphere undergoing rapid uplift.

Stable carbon and oxygen isotope rates of Maastrichtian ODP samples from Shatsky Rise

We present new isotopic and micropaleontological data from a depth transect on Shatsky Rise that record the response of the tropical Pacific to global biotic and oceanographic shifts during the mid-Maastrichtian. Results reveal a coupling between the upper ocean, characterized by a weak thermocline and low to intermediate productivity, and intermediate waters. During the earliest Maastrichtian, oxygen and neodymium isotope data suggest a significant contribution of relatively warm intermediate water from the North Pacific. Isotopic shifts through the early Maastrichtian suggest that this warmer water mass was gradually replaced by cooler waters originating in the Southern Ocean. Although the cooler water mass remained dominant through the remainder of the Maastrichtian, it was displaced intermittently at shallow intermediate depths by North Pacific intermediate water. The globally recognized "mid-Maastrichtian event" ~69 Ma, manifested by the brief appearance of abundant inoceramid bivalves over shallow portions of Shatsky Rise, is characterized by an abrupt increase (~2°-3°C) in sea surface temperatures, a greater flux of organic matter out of the surface ocean, and warmer (~4°C) intermediate waters. Results implicate simultaneous changes in surface waters and the sources/distribution patterns of intermediate water masses as an underlying cause for widespread biotic and oceanographic changes during mid-Maastrichtian time.

(Table 1) Oxygen and carbon isotope ratios of benthic foraminifera of DSDP Holes 82-563

Previous studies of benthic foraminiferal isotopic composition have demonstrated that a latest Eocene-earliest Oligocene benthic foraminiferal d18O increase occurred in the Pacific, Southern and Atlantic Oceans (Douglas and Savin, 1973, doi:10.2973/dsdp.proc.17.120.1973; Savin et al., 1977, doi:10.1130/0016-7606(1975)86<1499:TMP>2.0.CO;2; Shackleton and Kennett, 1975, doi:10.2973/dsdp.proc.29.117.1975; Kennett and Shackleton, 1976, doi:10.1038/260513a0; Savin, 1977, doi:10.1146/annurev.ea.05.050177.001535; Keigwin, 1980, doi:10.1038/287722a0; Boersma and Shackleton, 1979, doi:10.2973/dsdp.proc.39.139.1977; Miller and Curry, 1982, doi:10.1038/296347a0; Miller et al., 1985, doi:10.2973/dsdp.proc.80.113.1985). A Middle Miocene d18O increase has been noted in the Pacific, Southern and South Atlantic Oceans (Douglas and Savin, 1973, doi:10.2973/dsdp.proc.17.120.1973; Savin et al., 1975, doi:10.1130/0016-7606(1975)86<1499:TMP>2.0.CO;2; Shackleton and Kennett, 1975, doi:10.2973/dsdp.proc.29.117.1975; Boersma and Shackleton, 1979, doi:10.2973/dsdp.proc.39.139.1977; Woodruff et al., 1981, doi:10.1126/science.212.4495.665; Savin et al., 1981, doi:10.1016/0377-8398(81)90031-1; and tentatively identified in the North Atlantic (Blanc et al., 1980, doi:10.1038/283553a0; Blanc and Duplessy, 1982, doi:10.1016/0198-0149(82)90033-4). Due to the incomplete nature of the North Atlantic stratigraphical record, however, the Oligocene to Middle Miocene isotopic record (Moore et al., 1978, Miller and Tucholke, 1983) of this ocean is poorly understood. In the modern ocean, the North Atlantic and its marginal seas has a critical role in abyssal circulation, influencing deep- and bottom-water hydrography as far away as the North Pacific (Reid and Lynn, 1971, doi:10.1016/0011-7471(71)90094-5; Worthington, 1976; Reid, 1971, doi:10.1016/0198-0149(79)90064-5). We now report oxygen isotope measurements on Oligocene to Middle Miocene (12-36 Myr BP) benthic foraminifera in the western North Atlantic which show two periods of enriched 18O values: early Oligocene and early Middle Miocene. These enriched intervals are interpreted as resulting, in part, from the build-up of continental ice sheets. The Oligocene to Middle Miocene d13C record shows three cycles of enrichment and depletion of large enough magnitude to be useful for time-Stratigraphical correlations. Within the biostratigraphical age resolution, d18O and d13C records correlate with records from other oceans, helping to establish a useful Tertiary isotopic stratigraphy. An Atlantic-Pacific d13C contrast of 0.3-0.9 per mil during the latest Oligocene to Middle Miocene (12-26 Myr BP) indicates North Atlantic deep and bottom-water production analogous to modern North Atlantic deep water (NADW).