Description: Oxygen isotope values of the extant Caribbean coralline sponge Ceratoporella nicholsoni are compared with published temperatures and δ18O of water calculated from salinities. The measured values from aragonitic sponge skeletons have a mean offset of 1.0 ± 0.1‰ from calculated calcite equilibrium values (αaragonite-calcite = 1.0010). This is in good agreement with published values from synthetic aragonite. They further agree with published near-equilibrium oxygen isotope values of temperate and cold water molluscs and foraminifera extrapolated to the temperature range of the coralline sponges. These results and the mode of skeleton formation of Ceratoporella nicholsoni suggest that these sponges precipitate aragonite close to isotopic equilibrium. The temperature dependence of oxygen isotopic fractionation between the aragonite of Ceratoporella nicholsoni and water is only roughly constrained by the available data, due to the narrow temperature range of the Caribbean reef sites. However, as the data suggest oxygen isotopic equilibrium, we can calculate a well constrained temperature equation combining temperate and cold water equilibrium values from molluscs and foraminifera with our sponge data: Full-size image (〈1 K) and Full-size image (〈1 K).

Description: Calcium isotope fractionation was measured on skeletal aragonite and calcite from different marine biota and on inorganic calcite. Precipitation temperatures ranged from 0 to 28°C. Calcium isotope fractionation shows a temperature dependence in accordance with previous observations: 1000 · ln(αcc) = −1.4 + 0.021 · T (°C) for calcite and 1000 · ln(αar) = −1.9 + 0.017 · T (°C) for aragonite. Within uncertainty the temperature slopes are identical for the two polymorphs. However, at all temperatures calcium isotopes are more fractionated in aragonite than in calcite. The offset in δ44/40Ca is about 0.6‰. The underlying mechanism for this offset may be related to the different coordination numbers and bond strengths of the calcium ions in calcite and aragonite crystals, or to different Ca reaction behavior at the solid-liquid interface. Recently, the observed temperature dependence of the Ca isotope fractionation was explained quantitatively by the temperature control on precipitation rates of calcium carbonates in an experimental setting (Lemarchand et al., 2004). We show that this mechanism can in principle also be applied to CaCO3 precipitation in natural environments in normal marine settings. Following this model, Ca isotope fractionation in marine Ca carbonates is primarily controlled by precipitation rates. On the other hand the larger Ca isotope fractionation of aragonite compared to calcite can not be explained by different precipitation rates. The rate control model of Ca isotope fractionation predicts a strong dependence of the Ca isotopic composition of carbonates on ambient CO32− concentration. While this model is in general accordance with our observations in marine carbonates, cultured specimens of the planktic foraminifer Orbulina universa show no dependence of Ca-isotope fractionation on the ambient CO32− concentration. The latter observation implies that the carbonate chemistry in the calcifying vesicles of the foraminifer is independent from the ambient carbonate ion concentration of the surrounding water.