Sr, C and O isotope ratios of Neogene sediments from DSDP Hole 38-341, Voring Plateau

The Neogene sediments from DSDP site 341 on the Voring Plateau, Norwegian Sea, contain a thin glauconitic pellet-bearing subunit, which separates underlying pelagic clays from overlying glacial-marine sediments. Oxygen isotope measurements of benthic foraminifera show a delta18O shift of + 1? during deposition of this subunit, probably a combined effect of a drop in bottom water temperature and a rise in seawater delta18O. The chronology of this sedimentological and O isotope transition is, however, poorly constrained by fossil evidence. Rb-Sr dating of glauconitic pellets indicates that the lower part of the glauconitic subunit was deposited 11.6 +/- 0.2 Ma ago. Further geochronological evidence, derived from the Sr and C isotopic compositions of foraminifera compared with known seawater-time variations, indicates that the lower pelagic clays are early to middle Miocene, deposited at a mean rate of ~15 m/Ma. The glauconitic subunit contains part of the middle Miocene and probably all of the late Miocene in a condensed sequence with a very low mean depositional rate (~0.2 m/Ma). The overlying glacial marine sediments are probably Pliocene, with a high mean rate of deposition, ~45 m/Ma. This is the first application of C, O and Sr isotopic stratigraphy combined with Rb-Sr dating of glauconitic minerals, and it illustrates the applications of this integrated approach in geochronology.

Mg/Ca, Sr/Ca and Ca isotope ratios in benthonic foraminifers of surface sediment samples

We analysed Mg/Ca, Sr/Ca and Ca isotope ratios of benthonic foraminifers from sediment core tops retrieved during several research cruises in the Atlantic Ocean, in order to improve the understanding of isotope fractionation and element partitioning resulting from biomineralisation processes and changes in ambient conditions. Species include foraminifers secreting tests composed of hyaline low magnesium calcite, porcelaneous high magnesium calcite as well as aragonite. Our results demonstrate systematic isotope fractionation and element partitioning patterns specific for these foraminiferal groups. Calcium isotope fractionation is similar in porcelaneous and hyaline calcite tests and both groups demonstrate the previously described anomaly with enrichment of heavy isotopes around 3 - 4 °C (Gussone and Filipsson, 2010). Calcium isotope ratios of the aragonitic species Hoeglundina elegans, on the other hand, are about 0.4 per mil lighter compared to the calcitic species, which is in general agreement with stronger fractionation in inorganic aragonite compared to calcite. However, the low and strongly variable Sr content suggests additional processes during test formation, and we propose that transmembrane ion transport or a precursor phase to aragonite may be involved. Porcelaneous tests, composed of high Mg calcite, incorporate higher amounts of Sr compared to hyaline low Mg calcite, in agreement with inorganic calcite systematics, but also porcelaneous tests with reduced Mg/Ca show high Sr/Ca. While calcium isotopes, Sr/Ca and Mg/Ca in benthonic foraminifers primarily appear to fractionate and partition with a dominant inorganic control, d44/40Ca temperature and growth rate dependencies of benthonic foraminifer tests favour a dominant contribution of light Ca by transmembrane transport relative to unfractionated seawater Ca to the calcifying fluid, thus controlling the formation of foraminiferal d44/40Ca and Sr/Ca proxy signals.

Trace element abundances and Sr and Nd isotope compositions in bulk sediments from DSDP Legs 6 and 20

Rare earth element and Nd isotopic data for ten representative samples of Lower Cretaceous to Miocene pelagic sediments from the western Pacific indicate a wide range of compositions for sediments being subducted beneath the Mariana and Volcano arcs. All samples are enriched in light rare earth elements and show negative Eu and Ce anomalies. The values of e-Nd range from +0.6 to -7.3. These data are used to calculate the Bulk Western Pacific Sediment (BWPS), which is characterized by low Sr/Nd (10), Ba/La (13), and e-Nd (-5.2) and high 87Sr/86Sr (0.7078) compared to that of Mariana and Volcano arc lavas. This composite sediment is used to refine a mixing model for the origin of Mariana and Volcano arc melts. Some lavas from the northern Mariana Arc have Ba/La higher than that of BWPS, which indicates that a third component is required. The high Ba/La in the mantle source for these lavas is interpreted to result from multiple episodes of fluid fractionation. The mixing model indicates that a minor amount of sediment and a low proportion of metasomatic fluid fluxes the mantle source at a late stage when the subarc mantle is already highly metasomatized. This model also suggests that the mantle source for arc melts is affected more by metasomatic fluids than by melting or bulk mixing of sediments.

Stable and radiogenic isotope ratios in pore waters from ODP Leg 127 sites

Interstitial waters from four sites of the Japan Sea (794 to 797) have been analyzed for stable isotopes (delta D, delta11B, delta18O, and delta34S) and 87Sr/86Sr, besides major and minor ions. The isotopic composition is dominated by organic matter degradation, alteration of ash layers and volcaniclastic sands, silica transformation (opal A/CT), and basement alteration. Organic matter degradation and corresponding sulfate reduction leads to 32S depletion and is dependent upon sedimentation rate. The remaining sulfate reservoir is characterized by very "heavy" delta34S ratios, up to +93 ? (rel. CDT = Canyon Diabolo Troilite). "Barite fronts," which may develop in such sediments, should also be characterized by very "heavy" sulfur isotopes. The alteration of volcaniclastic material in the Quaternary sections influences the delta18O (-1.5 ? shift) and delta11B (desorption and later adsorption of "labile"11B). A pronounced positive delta11B anomaly at Site 795 represents the depth range of preferential 10B uptake by alteration products of the ash layers. At Site 796 delta D, delta11B, and 87Sr/86Sr are severely affected by alteration processes of volcaniclastic sands. The opal A/CT transformation may influence the oxygen isotopes and serves as a potential source for B, which is liberated at this interval at Site 795. This positive B anomaly is not reflected in the delta11B profile. Basement alteration processes dominate the sedimentary sequence below the opal A/CT transition, which serves as a chemical and physical boundary. The decreases in delta D and delta18O are probably related to a "paleo ocean water reservoir" situated in the permeable Layer II of the oceanic crust, as is indicated by the positive correlation between these two parameters. Besides Mg, alkalies and delta18O basement rocks also serve as a sink for 11 B (Site 795) and are the source for the Ca and Sr increases, as is documented by the less radiogenic 87Sr/86Sr ratio. 87Sr/86Sr ratios for the lowermost pore waters from Site 795 (0.70529) are comparable to those from volcaniclastic rocks from the "Green Tuff' region (0.704 to 0.706) and oil field brines from the Niigata Oil Field.

Gas composition, concentration and stable isotope ratios (Table 2, 3, 4)

The deployment of CCS (carbon capture and storage) at industrial scale implies the development of effective monitoring tools. Noble gases are tracers usually proposed to track CO2. This methodology, combined with the geochemistry of carbon isotopes, has been tested on available analogues. At first, gases from natural analogues were sampled in the Colorado Plateau and in the French carbogaseous provinces, in both well-confined and leaking-sites. Second, we performed a 2-years tracing experience on an underground natural gas storage, sampling gas each month during injection and withdrawal periods. In natural analogues, the geochemical fingerprints are dependent on the containment criterion and on the geological context, giving tools to detect a leakage of deep-CO2 toward surface. This study also provides information on the origin of CO2, as well as residence time of fluids within the crust and clues on the physico-chemical processes occurring during the geological story. The study on the industrial analogue demonstrates the feasibility of using noble gases as tracers of CO2. Withdrawn gases follow geochemical trends coherent with mixing processes between injected gas end-members. Physico-chemical processes revealed by the tracing occur at transient state. These two complementary studies proved the interest of geochemical monitoring to survey the CO2 behaviour, and gave information on its use.

Stable oxygen and carbon isotope ratios of foraminifera from Oligocene to Miocene sediments of DSDP Hole 39-354 from Ceara Rise, West Altlantic (Table 1)

The oxygen- and carbon-isotope compositions of planktic and benthic foraminifera and calcareous nannofossils from Middle Oligocene-Early Miocene Equatorial Atlantic sediments (DSDP Site 354) indicate two important paleoceanographic changes, in the Late Oligocene (foraminiferal Zone P.21) and in the Early Miocene (foraminiferal Zone N.5). The first change, reflected by a delta18O increase of 1.45? in Globigerina venezuelana, affected only intermediate pelagic and not surface, deep or bottom waters. The second change affected surface and intermediate waters, whereas deep and bottom waters showed only minor fluctuations. In the case of the former the isotope effect of the moderate ice accumulation on the Antarctic continent is amplified in the Equatorial Atlantic by changes in the circulation pattern. The latter paleoceanographic change, reflected by a significant increase in 18O in both planktic and benthic forms (about 1.0? and 0.5?, respectively), may have been caused by ice volume increase and temperature decrease. Both oxygen- and carbon-isotope compositions indicate a marked depth-habitat stratification for planktic foraminifera and calcareous nannofossils. Three different dwelling groups are recognized: shallow Globigerinoides, Globoquadrina dehiscens, Globorotalia mayeri and nannofossils; intermediate Globigerina venezuelana; and deep Catapsydrax dissimilis. The comparison of foraminifera and calcareous nannofossils suggests that the isotopic compositions of nannofossils are generally controlled by the same parameters which control the isotopic composition of shallow-dwelling foraminifera, but the former are more enriched in 18O.

Stable and strontium isotope ratios and age determination of ODP Site 130-803

Stratigraphic information from strontium, oxygen, and carbon isotopic ratios has been integrated with diatom and planktonic foraminifer datums to refine the Oligocene to early Miocene chemostratigraphy of Site 803. The Sr isotope results are based on analyses of mixed species of planktonic foraminifer and bulk carbonate samples. 87Sr/86Sr ratios of bulk carbonate samples are, in most cases, less radiogenic than contemporaneous seawater. Estimated sediment ages based on planktonic foraminifer 87Sr/86Sr ratios, using the Sr-isotope-age relation determined by Hess and others in 1989, are in moderately good agreement with the biostratigraphic ages. Chronological resolution is significantly enhanced with the correlation of oxygen and carbon isotope records to those of the standard Oligocene section tied to the Geomagnetic Polarity Time Scale at Site 522. Ages revised by this method and other published ages of planktonic foraminifer datums are used to revise the Oligocene stratigraphy of Site 77 to correlate the stable isotope records of Sites 77 and 803. Comparison of the Cibicidoides stable isotope records of Sites 77 and 574 with paleodepths below 2500 m in the central equatorial Pacific, and Site 803 at about 2000-m paleodepth in the Ontong Java Plateau reveals inversions in the vertical d18O gradient at several times during the Oligocene and in the early Miocene. The shallower water site had significantly-higher d18O values than the deeper water sites after the earliest Oligocene 18O enrichment and before 34.5 Ma, in the late Oligocene from 27.5 to at least 25 Ma, and in the early Miocene from 22.5 to 20.5 Ma. It is not possible to ascertain if the d18O inversion persisted during the Oligocene/Miocene transition because the deeper sites have hiatuses spanning this interval. We interpret this pattern to reflect that waters at about 2000 m depth were cold and may have formed from mixing with colder waters originating in northern or southern high-latitude regions. The deeper water appear to have been warmer and may have been a mixture with warm saline waters from mid- or low-latitude regions. No apparent vertical d13C gradient is present during the Oligocene, suggesting that the age difference of these water masses was small.

Stable carbon and oxygen isotope ratios of Miocene to Recent foraminifera from the Rio Grande Rise, South Atlantic

Miocene to Recent species of planktic foraminifera in the Globorotalia (Globoconella) lineage evolved entirely within the thermocline. All species are most abundant within subtropical-temperate watermasses throughout their history. The near stasis in distribution within the thermocline and the subtropical convergence suggests the major morphological changes in Globorotalia (Globoconella) may have occurred through habitat subdivision rather than by vicariant shifts into new watermasses. At the Rio Grande Rise, in the South Atlantic, modern G. inflata is 0.66-0.84? more positive for delta18O than the most enriched coexisting Globigerinoides sacculifer and probably grows in the mid thermocline deeper than 325 m. All extinct globoconellid species have mean delta18O ratios 0.5-0.8? more positive than Globigerinoides trilobus and G. sacculifer and probably lived within the thermocline as well. Major events in skeletal evolution are poorly correlated with changes in delta18O in this group. These include evolutionary transitions to compressed, smooth-walled tests and acquisition of keels. In addition, morphological reversals from the umbilically-inflated G. conomiozea to biconvex G. pliozea and to unkeeled G. puncticulata occur in the absence of changes in delta18O signature. Instead, the ranges of delta18O between different species almost completely overlap once corrected for temporal changes in delta18O of sea water. Foraminifera morphologies have been widely considered to evolve in response to changes in watermasses or depth habitats. However, the variety of skeletal shapes in the globoconellid lineage apparently are not adaptations to a progressive radiation from the surface mixed layer into deeper waters.

Ages and stable isotope ratios from speleothem calcite from Cold Water Cave, Iowa

High-precision uranium-thorium mass spectrometric chronology and 18O-13C isotopic analysis of speleothem calcite from Cold Water Cave in northeast Iowa have been used to chart mid-Holocene climate change. Significant shifts in d18O and d13C isotopic values coincide with well-documented Holocene vegetation changes. Temperature estimates based on 18O/16O ratios suggest that the climate warmed rapidly by about 3°C at 5900 years before present and then cooled by 4°C at 3600 years before present. Initiation of a gradual increase in ?d13C at 5900 years before present suggests that turnover of the forest soil biomass was slow and that equilibrium with prairie vegetation was not attained by 3600 years before present.

(Appendix) Petrographic information, trace element and Sr isotope ratios of Pito Deep samples

Fluid flow through the axial hydrothermal system at fast spreading ridges is investigated using the Sr-isotopic composition of upper crustal samples recovered from a tectonic window at Pito Deep (NE Easter microplate). Samples from the sheeted dike complex collected away from macroscopic evidence of channelized fluid flow, such as faults and centimeter-scale hydrothermal veins, show a range of 87Sr/86Sr from 0.7025 to 0.7030 averaging 0.70276 relative to a protolith with 87Sr/86Sr of ~0.7024. There is no systematic variation in 87Sr/86Sr with depth in the sheeted dike complex. Comparison of these new data with the two other localities that similar data sets exist for (ODP Hole 504B and the Hess Deep tectonic window) reveals that the extent of Sr-isotope exchange is similar in all of these locations. Models that assume that fluid-rock reaction occurs during one-dimensional (recharge) flow lead to significant decreases in the predicted extent of isotopic modification of the rock with depth in the crust. These model results show systematic misfits when compared with the data that can only be avoided if the fluid flow is assumed to be focused in isolated channels with very slow fluid-rock exchange. In this scenario the fluid at the base of the crust is little modified in 87Sr/86Sr from seawater and thus unlike vent fluids. Additionally, this model predicts that some rocks should show no change from the fresh-rock 87Sr/86Sr, but this is not observed. Alternatively, models in which fluid-rock reaction occurs during upflow (discharge) as well as downflow, or in which fluids are recirculated within the hydrothermal system, can reproduce the observed lack of variation in 87Sr/86Sr with depth in the crust. Minimum time-integrated fluid fluxes, calculated from mass balance, are between 1.5 and 2.6 * 10**6 kg/m**2 for all areas studied to date. However, new evidence from both the rocks and a compilation of vent fluid compositions demonstrates that some Sr is leached from the crust. Because this leaching lowers the fluid 87Sr/86Sr without changing the rock 87Sr/86Sr, these mass balance models must underestimate the time-integrated fluid flux. Additionally, these values do not account for fluid flow that is channelized within the crust.

Isotope ratios of sediments from DSDP Hole 47-397 (Table 1)

We report the Sr, Nd and Pb isotopic compositions (1) of 66 lava flows and dikes spanning the circa 15 Myr subaerial volcanic history of Gran Canaria and (2) of five Miocene through Cretaceous sediment samples from DSDP site 397, located 100 km south of Gran Canaria. The isotope ratios of the Gran Canaria samples vary for 87Sr/86Sr: 0.70302-0.70346, for 143Nd/144Nd: 0.51275-0.51298, and for 206Pb/204Pb: 18.76-20.01. The Miocene and the Pliocene-Recent volcanics form distinct trends on isotope correlation diagrams. The most SiO2-undersaturated volcanics from each group have the least radiogenic Sr and most radiogenic Pb, whereas evolved volcanics from each group have the most radiogenic Sr and least radiogenic Pb. In the Pliocene-Recent group, the most undersaturated basalts also have the most radiogenic Nd, and the evolved volcanics have the least radiogenic Nd. The most SiO2-saturated basalts have intermediate compositions within each age group. Although the two age groups have overlapping Sr and Nd isotope ratios, the Pliocene-Recent volcanics have less radiogenic Pb than the Miocene volcanics. At least four components are required to explain the isotope systematics of Gran Canaria by mixing. There is no evidence for crustal contamination in any of the volcanics. The most undersaturated Miocene volcanics fall within the field for the two youngest and westernmost Canary Islands in all isotope correlation diagrams and thus appear to have the most plume-like (high 238U/204Pb) HIMU-like composition. During the Pliocene-Recent epochs, the plume was located to the west of Gran Canaria. The isotopic composition of the most undersaturated Pliocene-Recent volcanics may reflect entrainment of asthenospheric material (with a depleted mantle (DM)-like composition), as plume material was transported through the upper asthenosphere to the base of the lithosphere beneath Gran Canaria. The shift in isotopic composition with increasing SiO2-saturation in the basalts and degree of differentiation for all volcanics is interpreted to reflect assimilation of enriched mantle (EM1 and EM2) in the lithosphere beneath Gran Canaria. This enriched mantle may have been derived from the continental lithospheric mantle beneath the West African Craton by thermal erosion or delamination during rifting of Pangaea. This study suggests that the enriched mantle components (EM1 and EM2) may be stored in the shallow mantle, whereas the HIMU component may have a deeper origin.

Age determination and stable isotope ratios of sediment core RC11-83

The Southern Ocean is perhaps the only region where fluctuations in the global influence of North Atlantic Deep Water (NADW) can be monitored unambiguously in single deep-sea cores. A carbon isotope record from benthic foraminifera in a Southern Ocean core reveals large and rapid changes in the flux of NADW during the last deglaciation, and an abrupt increase in the NADW production rate which immediately preceded large-scale melting of the Northern Hemisphere ice sheets. This sudden strengthening of the NADW thermoha-line cell provides strong evidence for the importance of NADW in glacial-interglacial climate change.