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  • 1
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2006. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography 21 (2206): PA2002, doi:10.1029/2005PA001203.
    Description: We estimate tropical Atlantic upper ocean temperatures using oxygen isotope and Mg/Ca ratios in well-preserved planktonic foraminifera extracted from Albian through Santonian black shales recovered during Ocean Drilling Program Leg 207 (North Atlantic Demerara Rise). On the basis of a range of plausible assumptions regarding seawater composition at the time the data support temperatures between 33° and 42°C. In our low-resolution data set spanning ~84–100 Ma a local temperature maximum occurs in the late Turonian, and a possible minimum occurs in the mid to early late Cenomanian. The relation between single species foraminiferal δ18O and Mg/Ca suggests that the ratio of magnesium to calcium in the Turonian-Coniacian ocean may have been lower than in the Albian-Cenomanian ocean, perhaps coincident with an ocean 87Sr/86Sr minimum. The carbon isotopic compositions of distinct marine algal biomarkers were measured in the same sediment samples. The δ13C values of phytane, combined with foraminiferal δ13C and inferred temperatures, were used to estimate atmospheric carbon dioxide concentrations through this interval. Estimates of atmospheric CO2 concentrations range between 600 and 2400 ppmv. Within the uncertainty in the various proxies, there is only a weak overall correspondence between higher (lower) tropical temperatures and more (less) atmospheric CO2. The GENESIS climate model underpredicts tropical Atlantic temperatures inferred from ODP Leg 207 foraminiferal δ18O and Mg/Ca when we specify approximate CO2 concentrations estimated from the biomarker isotopes in the same samples. Possible errors in the temperature and CO2 estimates and possible deficiencies in the model are discussed. The potential for and effects of substantially higher atmospheric methane during Cretaceous anoxic events, perhaps derived from high fluxes from the oxygen minimum zone, are considered in light of recent work that shows a quadratic relation between increased methane flux and atmospheric CH4 concentrations. With 50 ppm CH4, GENESIS sea surface temperatures approximate the minimum upper ocean temperatures inferred from proxy data when CO2 concentrations specified to the model are near those inferred using the phytane δ13C proxy. However, atmospheric CO2 concentrations of 3500 ppm or more are still required in the model in order to reproduce inferred maximum temperatures.
    Description: Funding for this research was provided by the U.S. Science Support Program of the JOI, the Andrew W. Mellon Foundation Endowed Fund for Innovative Research, and Deutsche Forschungsgemeinschaft through the DFG-Research Center Ocean Margins.
    Keywords: Cretaceous ; Temperature ; Carbon dioxide
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 2
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    American Geophysical Union
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2006. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 7 (2006): Q11004, doi:10.1029/2005GC001216.
    Description: The Sr/Ca ratio of biogenic carbonate is widely used as a proxy for paleotemperature. This application is supported by empirical calibrations of Sr/Ca as a function of temperature, but it is also known that Sr uptake in calcite gauged by KdSr=(Sr/Ca)calcite/(Sr/Ca)solution is affected by other variables, including bulk precipitation rate (Kd Sr increases with increasing precipitation rate). There are no data from controlled experiments specifically addressing the effect of radial growth rate of individual crystals on Kd Sr. For this reason, we conducted two series of experiments to explore Sr partitioning at varying growth rates: (1) growth from a CaCl2–NH4Cl–SrCl2 solution by diffusion of CO2 from an ammonium carbonate source (“drift” experiments) and (2) “drip” precipitation of calcite on a substrate, using a steady flow of CaCl2–SrCl2 and Na2CO3 solutions, mixed just before passage through a tube and dripped onto a glass slide precoated with calcite (“cave-type” experiments). The growth rates of individual crystals were determined by periodic monitoring of crystal size through time or, roughly, by comparison of the final size with the duration of the experiment. Electron microprobe analyses across sectioned crystals grown in the drift experiments show that the concentration of Sr is high in the center (where radial growth rates are highest) and decreases systematically toward the edge. The center-to-edge drop in Sr concentration is a consequence of the slowing radial growth rate as individual crystals become larger. In general, high crystal growth rate (V) enhances Sr uptake in calcite due to a type of kinetic disequilibrium we refer to as “growth entrapment.” The apparent Kd Sr ranges from 0.12 to 0.35 as V increases from 0.01 nm/s to 1 μm/s at 25°C.
    Description: This work was supported by the National Science Foundation through grants EAR-9804794 and EAR-0337481 to E. B. Watson.
    Keywords: Calcite ; Partitioning ; Fluid ; Growth rate ; Strontium ; Temperature
    Repository Name: Woods Hole Open Access Server
    Type: Article
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