Radiogenic Hf isotopic composition of continental eolian dust in Pacific Ocean sediments

The inorganic silicate fraction extracted from bulk pelagic sediments from the North Pacific Ocean is eolian dust. It monitors the composition of continental crust exposed to erosion in Asia. 176Lu/177Hf ratios of modern dust are subchondritic between 0.011 and 0.016 but slightly elevated with respect to immature sediments. Modern dust samples display a large range in Hf isotopic composition (IC), -4.70 < epsilon-Hf < +16.45, which encompasses that observed for the time series of DSDP cores 885/886 and piston core LL44-GPC3 extending back to the late Cretaceous. Hafnium and neodymium isotopic results are consistent with a dominantly binary mixture of dust contributed from island arc volcanic material and dust from central Asia. The Hf-Nd isotopic correlation for all modern dust samples, epsilon-Hf= =0.78 epsilon-Nd = +5.66 (n =22, R**2 =0.79), is flatter than those reported so far for terrestrial reservoirs. Moreover, the variability in epsilon-Hf of Asian dust exceeds that predicted on the basis of corresponding epsilon-Nd values (34.76 epsilon-Hf < +2.5; -10.96< epsilon-Nd <-10.1). This is attributed to: (1) the fixing of an important unradiogenic fraction of Hf in zircons, balanced by radiogenic Hf that is mobile in the erosional cycle, (2) the elevated Lu/Hf ratio in chemical sediments which, given time, results in a Hf signature that is radiogenic compared with Hf expected from its corresponding Nd isotopic components, and (3) the possibility that diagenetic resetting of marine sediments may incorporate a significant radiogenic Hf component into diagenetically grown minerals such as illite. Together, these processes may explain the variability and more radiogenic character of Hf isotopes when compared to the Nd isotopic signatures of Asian dust. The Hf-Nd isotope time series of eolian dust are consistent with the results of modern dust except two samples that have extremely radiogenic Hf for their Nd (epsilon-Hf =+8.6 and +10.3, epsilon-Nd =39.5 and 39.8). These data may point to a source contribution of dust unresolved by Nd and Pb isotopes. The Hf IC of eolian dust input to the oceans may be more variable and more radiogenic than previously anticipated. The Hf signature of Pacific seawater, however, has varied little over the past 20 Myr, especially across the drastic increase of eolian dust flux from Asia around 3.5 Ma. Therefore, continental contributions to seawater Hf appear to be riverine rather than eolian. Current predictions regarding the relative proportions of source components to seawater Hf must account for the presence of a variable and radiogenic continental component. Data on the IC and flux of river-dissolved Hf to the oceans are urgently required to better estimate contributions to seawater Hf. This then would permit the use of Hf isotopes as a monitor of past changes in erosion.

(Table 3) Isotopic composition of pyrite sulfur and carbonate carbon in carbonate nodules and host sediments from Core DM9-666, Gulf of California

Isotopic-geochemical study revealed presence of mantle He (3He/4He up to 223x10**-8) in gases from mud volcanoes of Eastern Georgia. This fact confirms that the Middle Kura basin fill encloses an intrusive body previously distinguished from geophysical data. Wide variations of carbon isotopic composition d13C in CH4 and CO2 and chemical composition of gas and water at temporally constant 3He/4He ratio indicate their relation with crustal processes. Unusual direct correlations of 3He/4He ratio with concentrations of He and CH4 and 40Ar/36Ar ratio can be explained by generation of gas in the Cenozoic sequence of the Middle Kura basin.

(Table 1, 2) Foraminifera biometric data, and boron isotopic composition of Globigerinoides sacculifer of sediments from the Ontong-Java Plateau

Sediment samples from the Ontong-Java Plateau in the Pacific and the 90° east ridge in the Indian Ocean were used to investigate whether shell size and early diagenesis affect d11B of the symbiont-bearing planktonic foraminifer Globigerinoides sacculifer. In pristine shells from both study locations we found a systematic increase of d11B and Mg/Ca with shell size. Shells in the sieve size class 515-865 µm revealed d11B values +2.1 to +2.3 per mil higher than shells in the 250-380 µm class. This pattern is most likely due to differences in symbiont photosynthetic activity and its integrated effect on the pH of the foraminiferal microenvironment. We therefore suggest smaller individuals must live at approximately 50-100 m water depth where ambient light levels are lower. Using the empirical calibration curve for d11B in G. sacculifer, only shells larger than 425 µm reflect surface seawater pH. Partial dissolution of shells derived from deeper sediment cores was determined by shell weight analyses and investigation of the shell surface microstructure by scanning electron microscopy. The d11B in partially dissolved shells is up to 2 per mil lower relative to pristine shells of the same size class. In agreement with a relatively higher weight loss in smaller shells, samples from the Ontong-Java Plateau show a more pronounced dissolution effect than larger shells. On the basis of the primary size effect and potential postdepositional dissolution effects, we recommend the use of shells that are visually pristine and, in the case of G. sacculifer, larger than 500 ?m for paleoreconstructions.

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.

(Table 1) Sr, Nd and Os isotopic composition from marine sediments of the Bengal Fan

Sr, Nd, and Os isotopic data are presented for sediments from diverse locations in the Bay of Bengal. These data allow the samples to be divided into three groups, related to their sedimentary contexts. The first group, mainly composed of sediments from the shelf off Bangladesh and the currently active fan, has Sr and Nd characteristics consistent with a dominantly Himalayan source. Their 187Os/188Os ratios (~1.2-1.5) show that the average detrital material delivered by the Ganga-Brahmaputra (G-B) river system is not unusually radiogenic. A large difference in 187Os/188Os ratio exists between these Bengal Fan sediments and Ganga bedloads (187Os/188Os ~2.5, Pierson-Wickmann et al. (2000, doi:10.1016/S0012-821X(00)00003-0)). This difference mainly reflects addition of a less radiogenic Brahmaputra component, though mineralogical sorting and loss of radiogenic Os during transport may also play some role. The second sample group contains sediments from elsewhere in the Bay, particularly those located on the continental slope. They display Os isotopic compositions (0.99-1.11) similar to that of present seawater and higher Os and Re concentrations. These characteristics suggest the presence of a large hydrogenous contribution, consistent with the lower sedimentation rate of these samples. Sr and Nd ratios indicate that a significant fraction of these sediments is derived from erosion of non-Himalayan sources, such as the Indo-Burman range. These observations could be explained by the deflection of sediments from the G-B river system by westward currents in the head of the Bay. The third group contains only one sample, but shows that in addition to a Himalayan source, sediment discharge from Sri Lanka may influence the detrital component in the distal part of the fan. The similarity between the isotopic compositions of the group I R/V Sonne samples and those of Ocean Drilling Program Leg 116 (France-Lanord et al., 1993; Reisberg et al., 1997, doi:10.1016/S0012-821X(00)00003-0) suggests that the material eroding in the Himalayas has been roughly constant since the Miocene. The high Os isotopic ratios of leachates of both Sonne group I and Miocene Leg 116 sediments imply that much of the leachable highly radiogenic Os component was conserved during transport through the estuary or interaction with seawater. In constrast, samples with lower, but still relatively high, sedimentation rates (Sonne groups II and III and Pliocene Leg 116) seem to have significantly adsorbed or exchanged Os and Re with seawater. This suggests that in some cases the Os isotopic ratios of leachates of detrital sediments can be used to constrain the ancient marine Os record, or conversely, to date unfossiliferous sediments.

Comparison of nitrogen isotopic values from different preparation methods

We are writing to comment on the work of Tamburini et al. (2003, doi:10.1029/2000PA000616). During the course of subsequent discussions between the authors and ourselves, it has become clear that the published sedimentary nitrogen isotopic values for Ocean Drilling Program (ODP) Site 724 are in error. Our reanalysis of sediment samples from the same intervals has revealed a significant offset from the original d15N data, requiring a revised assessment of their initial interpretation. The purposes of this comment are to (1) address the origin of these errors; (2) outline a protocol for future validation of nitrogen isotopic analyses; and (3) provide revised interpretations of the sedimentary d15N data in terms of the regional relative contributions of denitrification and nitrogen fixation and mean state of the southwest monsoon. (2) Nitrogen isotopic values measured on late Quaternary sediments at Arabian Sea ODP Site 724 by Tamburini et al. (2003, doi:10.1029/2000PA000616) are inexplicably different from a number of published records of d15N from very nearby on the Oman margin (Altabet et al., 1995, doi:10.1038/373506a0; 1999, doi:10.1029/1999PA900035; 2002, doi:10.1038/415159a; Higginson et al., 2004, doi:10.1016/j.gca.2004.03.015) and elsewhere in the Arabian Sea (Reichart et al., 1998, doi:10.1029/98PA02203). These data were generated using similar instrumentation (elemental analyzer coupled with an isotope ratio mass spectrometer) and analytical methodology to those already published. Concerned by this clear discrepancy, we analyzed aliquots of sediment from the same depth intervals for nitrogen abundance and bulk sedimentary nitrogen isotopes. We have been unable to duplicate the values published by Tamburini et al. (2003, doi:10.1029/2000PA000616 ), even after analysis of multiple replicates and due consideration of natural sediment heterogeneities and postrecovery sample storage.

Nd and Sm isotopic record from fossil fish teeth recovered from ODP Site 177-1090

Neodymium (Nd) isotopes were measured on 181 samples of fossil fish teeth recovered from Oligocene to Miocene sections at Ocean Drilling Program Site 1090 (3700 m water depth) on Agulhas Ridge in the Atlantic sector of the Southern Ocean. A long-term decreasing trend toward less radiogenic Nd isotope compositions dominates the record. This trend is interrupted by shifts toward more radiogenic compositions near the early/late Oligocene boundary and the Oligocene/Miocene boundary. Overall, epsilon-Nd values at Agulhas Ridge are more radiogenic than at other Atlantic locations, and are similar to those at Indian Ocean locations. The pattern of variability is remarkably similar to Nd isotope results from Walvis Ridge (South Atlantic) and Ninetyeast Ridge (Indian Ocean). In contrast, Agulhas Ridge and Maud Rise Nd isotope records do not show similar patterns over this interval. Results from this study indicate that deep water in the Atlantic flowed predominantly from north to south during the Oligocene and Miocene, and that export of Northern Component Water (NCW) to the Southern Ocean increased in the late Oligocene. There is also evidence for efficient exchange of deep waters between the Atlantic sector of the Southern Ocean and the Indian Ocean, although the direction of deep water flow is not entirely clear from these data. The shifts to more radiogenic Nd isotopic compositions most likely represent increases in the flux of Pacific waters through Drake Passage, and the timing of these events reflect development of a mature Antarctic Circumpolar Current (ACC). The relative timing of increased NCW export and ACC maturation support hypotheses that link deep water formation in the North Atlantic to the opening of Drake Passage.

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.

Isotopic ratios and ion composition of massive ground ice on Herschel Island

Herschel Island in the southern Beaufort Sea is a push moraine at the northwestern-most limit of the Laurentide Ice Sheet. Stable water isotope (d18O, dD) and hydrochemical studies were applied to two tabular massive ground ice bodies to unravel their genetic origin. Buried glacier ice or basal regelation ice was encountered beneath an ice-rich diamicton with strong glaciotectonic deformation structures. The massive ice isotopic composition was highly depleted in heavy isotopes (mean d18O: -33 per mil; mean dD: -258 per mil), suggesting full-glacial conditions during ice formation. Other massive ice of unknown origin with a very large d18O range (from -39 to -21 per mil) was found adjacent to large, striated boulders. A clear freezing slope was present with progressive depletion in heavy isotopes towards the centre of the ice body. Fractionation must have taken place during closed-system freezing, possibly of a glacial meltwater pond. Both massive ground ice bodies exhibited a mixed ion composition suggestive of terrestrial waters with a marine influence. Hydrochemical signatures resemble the Herschel Island sediments that are derived from nearshore marine deposits upthrust by the Laurentide ice. A prolonged contact between water feeding the ice bodies and the surrounding sediment is therefore inferred.

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.