Isotopic composition of carbonates from the Logachev Hydrothermal Field, MAR 14°45'N

We investigate the Logatchev Hydrothermal Field at the Mid-Atlantic Ridge, 14°45' N to constrain the calcium isotope hydrothermal flux into the ocean. During the transformation of seawater to a hydrothermal solution, the Ca concentration of pristine seawater ([Ca]_SW) increases from about 10 mM to about 32 mM in the hydrothermal fluid endmember ([Ca]_HydEnd) and thereby adopts a d44/40Ca_HydEnd of -0.95+/-0.07 per mil relative to seawater (SW) and a 87Sr/86Sr isotope ratio of 0.7034(4). We demonstrate that d44/40Ca_HydEnd is higher than that of the bedrock at the Logatchev field. From mass balance calculations, we deduce a d44/40Ca of -1.17+/-0.04 per mil (SW) for the host-rocks in the reaction zone and -1.45+/-0.05 per mil (SW) for the isotopic composition of the entire hydrothermal cell of the Logatchev field. The values are isotopically lighter than the currently assumed d44/40Ca for Bulk Earth of -0.92+/-0.18 per mil (SW) [Skulan J., DePaolo D. J. and Owens T. L. (1997) Biological control of calcium isotopic abundances in the global calcium cycle. Geochim. Cosmochim. Acta 61,(12) 2505-2510] and challenge previous assumptions of no Ca isotope fractionation between hydrothermal fluid and the oceanic crust [Zhu P. and Macdougall J. D. (1998) Calcium isotopes in the marine environment and the oceanic calcium cycle. Geochim. Cosmochim. Acta 62,(10) 1691-1698; Schmitt A. -D., Chabeaux F. and Stille P. (2003) The calcium riverine and hydrothermal isotopic fluxes and the oceanic calcium mass balance. Earth Planet. Sci. Lett. 6731, 1-16]. Here we propose that Ca isotope fractionation along the fluid flow pathway of the Logatchev field occurs during the precipitation of anhydrite. Two anhydrite samples from the Logatchev Hydrothermal Field show an average fractionation of about D44/40Ca = -0.5 per mil relative to their assumed parental solutions. Ca isotope ratios in aragonites from carbonate veins from ODP drill cores indicate aragonite precipitation directly from seawater at low temperatures with an average d44/40Ca of -1.54+/-0.08 per mil (SW). The relatively large fractionation between the aragonite precipitates and seawater in combination with their frequent abundance in weathered mafic and ultramafic rocks suggest a reconsideration of the marine Ca isotope budget, in particular with regard to ocean crust alteration.

(Table 2) Radiocarbon ages of eastern equatorial Pacific sediment cores

We use planktonic oxygen isotope (d18O) records spanning the last 30,000 years (kyr) to constrain the magnitude and spatial pattern of glacial cooling in the upwelling environment of the eastern equatorial Pacific (EEP). Fourteen new downcore d18O records were obtained from surface-dwelling planktonic foraminifera Globigerinoides sacculifer and Globigerinoides ruber in eight cores from the upwelling tongue of the EEP. All sites have sedimentation rates exceeding 5 cm/kyr and, with one exception, lie above the modern depth of the foraminiferal lysocline. Sites directly underlying the cool band of upwelling immediately south of the equator record mean late Holocene (LH)-Last Glacial Maximum (LGM) d18O amplitudes ranging between 1.0 and 1.3 per mil. We estimate that mean sea surface temperatures (SST) in this region during the LGM were on average 1.5 ± 0.5°C lower than the LH. Larger d18O amplitudes are observed in sites north of the equator, indicating a spatial pattern of reduced meridional SST gradient across the equator during the LGM. This result is supported by comparison of Mg/Ca SST reconstructions from two sites straddling the equator. We interpret the reduction of this gradient during the LGM as evidence for a less intense cold tongue-Intertropical Convergence Zone (ITCZ) frontal system, a more southerly position of the ITCZ, and weaker southeast equatorial trades in the EEP.