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.

Table 1. Pressure, temperature and isotope ratios between H2O and CO2 for all experiments

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on d13C values of CO2 to trace the migration of injected CO2 in the subsurface. More recently the use of d18O values of both CO2 and reservoir fluids has been proposed as a method for quantifying in situ CO2 reservoir saturations due to O isotope exchange between CO2 and H2O and subsequent changes in d18OH2O values in the presence of high concentrations of CO2. To verify that O isotope exchange between CO2 and H2O reaches equilibrium within days, and that d18OH2O values indeed change predictably due to the presence of CO2, a laboratory study was conducted during which the isotope composition of H2O, CO2, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50°C and up to 19 MPa) and varying CO2 pressures. Conditions typical for the Pembina Cardium CO2 Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that d18O values of CO2 were on average 36.4±2.2 per mil (1 sigma, n=15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5 per mil for the experimental temperatures of 50°C. By using 18O enriched water for the experiments it was demonstrated that changes in the d18O values of water were predictably related to the fraction of O in the system sourced from CO2 in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO2 is related to the total volumetric saturation of CO2 and water as a fraction of the total volume of the system, it is concluded that changes in d18O values of reservoir fluids can be used to calculate reservoir saturations of CO2 in CCS settings given that the d18O values of CO2 and water are sufficiently distinct.

Stable isotope ratios and geochemical composition of authigenic carbonates from ODP Sites 186-1150 and 186-1151

Several carbonaceous layers or fragments were recovered from sediments of Sites 1150 and 1151 on the deep-sea terrace of the Japan Trench during Leg 186. The X-ray diffraction analysis (XRD) data indicate that these are predominantly dolomitic. In this study, carbon and oxygen isotopes of these carbonates recovered at Sites 1150 and 1151 are presented. The oxygen isotope ratios of the dolomites analyzed range from +0.4 per mil to +4.1 per mil vs. Peedee formation belemnite (PDB) and those of calcites from +0.6 per mil to +2.8 per mil PDB. The isotopic composition of carbon varies from -7.0 per mil to +12.3 per mil PDB in dolomite and from -13.4 per mil to -24.1 per mil PDB in calcite. The wide range of carbon isotopic compositions indicates that the carbonate samples were formed by the decomposition of organic matter through reactions such as oxidation, sulfate reduction, and methane formation during diagenesis.

Benthic foraminiferal Mg/Ca ratios

Core-top samples from different ocean basins have been analyzed to refine our current understanding of the sensitivity of benthic foraminiferal calcite magnesium/calcium (Mg/Ca) to bottom water temperatures (BWT). Benthic foraminifera collected from Hawaii, Little Bahama Bank, Sea of Okhotsk, Gulf of California, NE Atlantic, Ceara Rise, Sierra Leone Rise, the Ontong Java Plateau, and the Southern Ocean covering a temperature range of 0.8 to 18°C were used to revise the Cibicidoides Mg/Ca-temperature calibration. The Mg/Ca-BWT relationship of three common Cibicidoides species is described by an exponential equation: Mg/Ca = 0.867 ± 0.049 exp (0.109 ± 0.007 * BWT) (stated errors are 95% CI). The temperature sensitivity is very similar to a previously published calibration. However, the revised calibration has a significantly different preexponential constant, resulting in different predicted absolute temperatures. We attribute this difference in the preexponential constant to an analytical issue of accuracy. Some genera, notably Uvigerina, show apparently lower temperature sensitivity than others, suggesting that the use of constant offsets to account for vital effects in Mg/Ca may not be appropriate. Downcore Mg/Ca reproducibility, as determined on replicate foraminiferal samples, is typically better than 0.1 mmol/mol (2 S.E.). Thus, considering the errors associated with the Cibicidoides calibration and the downcore reproducibility, BWT may be estimated to within ±1°C. Application of the revised core-top Mg/Ca-BWT data to Cenozoic foraminiferal Mg/Ca suggests that seawater Mg/Ca was not more than 35% lower than today in the ice-free ocean at 50 Ma.

Sand fraction, foraminifer isotopic composition and foraminifer element ratios of ODP Site 198-1209 sediments, Shatsky Rise

Stable oxygen and carbon isotope measurements (d18O and d13C) of planktonic and benthic foraminifers were conducted to assess the temperature history and circulation patterns over Shatsky Rise during the Paleocene and Eocene. A record of Mg/Ca for benthic foraminifers was also constructed in order to better determine the relative influence of temperature, salinity, and/or ice volume upon the benthic d18O record. Isotopic analyses were carried out on several planktonic taxa (Acarinina, Morozovella, Globigerinatheka, Praemurica, and Subbotina) as well as several benthic taxa (Nuttalides, Oridorsalis, Cibicidoides, Gavelinella, and Lenticulina). Elemental analyses were restricted to three benthic taxa: Nuttalides, Oridorsalis, and Gavelinella. All specimens were derived from the composite sediment section recovered from Ocean Drilling Program Site 1209 on the Southern High of Shatsky Rise.