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.

O, C and Sr isotopic data for plankton and benthic foraminifera from DSDP Legs 26, 32, 36, and 71 sediments

A detailed d18O and d13C stratigraphy has been generated from analysis of well-preserved Albian - Early Maastrichtian foraminifera from Deep Sea Drilling Project (DSDP) Sites 511 and 327 (Falkland Plateau; ~58°S - 62°S paleolatitude) in the southern South Atlantic, and Cenomanian and Coniacian - Santonian foraminifera from DSDP Site 258 (Naturaliste Plateau; ~58°S paleolatitude) in the southern Indian Ocean. These results, when combined with previously published Maastrichtian stable isotope data from Ocean Drilling Program (ODP) Site 690 (Weddell Sea, ~65°S paleolatitude), provide new insight into the climatic and oceanographic history of the southern high latitudes during Middle-Late Cretaceous time. The planktonic foraminifer d18O curves reveal a gradual warming of surface waters from the Albian through the Cenomanian followed by extremely warm surface waters from the Turonian through the early Campanian. Long-term cooling of surface waters began in the late early Campanian and continued through the end of the Maastrichtian. The benthic foraminifer d18O record generally parallels changes in the oxygen isotopic curves defined by shallow-dwelling planktonic foraminifera. The vertical oxygen and carbon isotopic gradients were relatively low during the Albian - Cenomanian, high from the Turonian - Early Campanian, and then low during the late Campanian and Maastrichtian.

Mineralogy ol late Quaternary marine sediments from the West and East Greenland shelves offshore from early Tertiary basalt outcrops

We use quantitative X-ray diffraction to determine the mineralogy of late Quaternary marine sediments from the West and East Greenland shelves offshore from early Tertiary basalt outcrops. Despite the similar basalt outcrop area (60 000-70 000 km**2), there are significant differences between East and West Greenland sediments in the fraction of minerals (e.g. pyroxene) sourced from the basalt outcrops. We demonstrate the differences in the mineralogy between East and West Greenland marine sediments on three scales: (1) modern day, (2) late Quaternary inputs and (3) detailed down-core variations in 10 cores from the two margins. On the East Greenland Shelf (EGS), late Quaternary samples have an average quartz weight per cent of 6.2 ± 2.3 versus 12.8 ± 3.9 from the West Greenland Shelf (WGS), and 12.02 ± 4.8 versus 1.9 ± 2.3 wt% for pyroxene. K-means clustering indicated only 9% of the samples did not fit a simple EGS vs. WGS dichotomy. Sediments from the EGS and WGS are also isotopically distinct, with the EGS having higher eNd (-18 to 4) than those from the WGS (eNd = -25 to -35). We attribute the striking dichotomy in sediment composition to fundamentally different long-term Quaternary styles of glaciation on the two basalt outcrops.

Thallium concentrations and isotope composition of MORB glasses and altered oceani crust from DSDP/ODP Hole 504B and DSDP Hole 52-417D

Hydrothermal fluids expelled from the seafloor at high and low temperatures play pivotal roles in controlling seawater chemistry. However, the magnitude of the high temperature water flux of mid-ocean ridge axes remains widely disputed and the volume of low temperature vent fluids at ridge flanks is virtually unconstrained. Here, we determine both high and low temperature hydrothermal fluid fluxes using the chemical and isotopic mass balance of the element thallium (Tl) in the ocean crust. Thallium is a unique tracer of ocean floor hydrothermal exchange because of its contrasting behavior during seafloor alteration at low and high temperatures and the distinctive isotopic signatures of fresh and altered MORB and seawater. The calculated high temperature hydrothermal water flux is (0.17-2.93)*10**13 kg/yr with a best estimate of 0.72*10**13 kg/yr. This result suggests that only about 5 to 80% of the heat available at mid-ocean ridge axes from the crystallization and cooling of the freshly formed ocean crust, is released by high temperature black smoker fluids.The residual thermal energy ismost likely lost via conduction and/or through the circulation of intermediate temperature hydrothermal fluids that do not alter the chemical budgets of Tl in the ocean crust. The Tl-based calculations indicate that the low temperature hydrothermal water flux at ridge flanks is (0.2-5.4)*10**17 kg/yr. This implies that the fluids have an average temperature anomaly of only about 0.1 to 3.6 °C relative to ambient seawater. If these low temperatures are correct then both Sr and Mg are expected to be relatively unreactive in ridge-flank hydrothermal systems and this may explain why the extent of basalt alteration that is observed for altered ocean crust appears insufficient to balance the oceanic budgets of 87Sr/86Sr and Mg.

Pleistocene-Pliocene strontium-isotope ratios of ODP Site 107-653 (Table 1)

Strontium isotopic determinations were made on samples from the Pliocene-Pleistocene sequence recovered at ODP Hole 653A, the proposed "deep-sea type section" for the Mediterranean region. Biostratigraphic correlations can be combined with the patterns of variations in the 87Sr/86Sr values to delineate the following: (1) the earliest Pliocene (MP11 to basal MP12 zones) is distinguished by fluctuations in the ratio, probably related to the unstable paleoceanographic conditions following the Zanclean flooding and initial in-filling of the Mediterranean after the Messinian desiccation, (2) during most of the Pliocene between approximately 4.5 and 2.4 Ma (MP12 to MP15 zones) the 87Sr/86Sr values remain relatively constant, producing a plateau in the strontium isotope-depth curve for this period, and (3) beginning at approximately 2.4 Ma (across the MP15/MP16 boundary) and continuing into the latest Pleistocene, the 7Sr/86Sr values increase significantly but show fluctuations that have both positive and negative slopes. The presence of a plateau in the curve generated for the Mediterranean type section duplicates in greater detail the late Neogene results reported by DePaolo (1986, doi:10.1130/0091-7613(1986)14<103:DROTNS>2.0.CO;2). The virtual lack of change in the ratio between 4.5 and 2.4 Ma essentially eliminates strontium isotopes as a high-resolution correlation method for this period. The fluctuations in the ratio beginning at 2.4 Ma may be a reflection of major climatic changes occurring in the latest Pliocene-Pleistocene. The relationship between glacial-interglacial cycles and seawater 87Sr/86Sr values suggested by DePaolo (1986) and Capo and DePaolo (1987) is uncertain but should be tested as significant increases and decreases in 87Sr/86Sr of seawater have apparently occurred since 2.4 Ma.