(Table 1) Uranium at DSDP Hole 69-504B pore water

Basalt formation waters collected from Hole 504B at sub-basement depths of 194, 201, 365, and 440 meters show inverse linear relationships between 87Sr/86Sr and Ca, 87Sr/86Sr and Sr, and K and Ca. If the Ca content of a fully reacted formation water end-member is assumed to be 1340 ppm, the K, Sr, and 87Sr/86Sr values for the end-member are 334 ppm, 7.67 ppm, and 0.70836, respectively. With respect to contemporary seawater at Hole 504B, K is depleted by 13%, Sr is enriched by 2.7%, and 87Sr/86Sr is depleted by 0.8%. The Sr/Ca ratio of the formation water (0.0057) is much lower than that of seawater (0.018) but is similar to the submarine hot spring waters from the Galapagos Rift and East Pacific Rise and to geothermal brines from Iceland. At the intermediate temperatures represented by the Hole 504B formation waters (70°-105°C), the interaction between seawater and the ocean crust produces large solution enrichments in Ca, the addition of a significant basalt Sr isotope component accompanied by only a minor elemental Sr component, and the removal from solution of seawater K. The Rb, Cs, and Ba contents of the formation waters appear to be affected by contamination, possibly from drilling muds.

Geochemical analyses and Delta47 values in shallow water corals

Geochemical variations in shallow water corals provide a valuable archive of paleoclimatic information. However, biological effects can complicate the interpretation of these proxies, forcing their application to rely on empirical calibrations. Carbonate clumped isotope thermometry (Delta47) is a novel paleotemperature proxy based on the temperature dependent "clumping" of 13C-18O bonds. Similar ?47-temperature relationships in inorganically precipitated calcite and a suite of biogenic carbonates provide evidence that carbonate clumped isotope variability may record absolute temperature without a biological influence. However, large departures from expected values in the winter growth of a hermatypic coral provided early evidence for possible Delta47 vital effects. Here, we present the first systematic survey of Delta47 in shallow water corals. Sub-annual Red Sea Delta47 in two Porites corals shows a temperature dependence similar to inorganic precipitation experiments, but with a systematic offset toward higher Delta47 values that consistently underestimate temperature by ~8 °C. Additional analyses of Porites, Siderastrea, Astrangia and Caryophyllia corals argue against a number of potential mechanisms as the leading cause for this apparent Delta47 vital effect including: salinity, organic matter contamination, alteration during sampling, the presence or absence of symbionts, and interlaboratory differences in analytical protocols. However, intra- and inter-coral comparisons suggest that the deviation from expected Delta47 increases with calcification rate. Theoretical calculations suggest this apparent link with calcification rate is inconsistent with pH-dependent changes in dissolved inorganic carbon speciation and with kinetic effects associated with CO2 diffusion into the calcifying space. However, the link with calcification rate may be related to fractionation during the hydration/hydroxylation of CO2 within the calcifying space. Although the vital effects we describe will complicate the interpretation of Delta47 as a paleothermometer in shallow water corals, it may still be a valuable paleoclimate proxy, particularly when applied as part of a multi-proxy approach.