Description: Modern analogs are an essential part of palaeoclimate studies, because they provide the basis for the understanding of geochemical signatures of fossils. Ostreoids are common in many sedimentary sequences and because of their fast growth, high temporal resolution sampling of past seasonal variability is possible. Here, two shell structures of modern Giant Pacific Oysters (Crassostrea gigas), the chalky substance and foliate layers, have been sampled for trace element distributions (Mg, Sr, Mn) and stable isotope variability (C, O, Ca). Oxygen isotopes exhibit a clear seasonal signature. Mean carbon isotope values of different oysters agree within 0.1‰, but ontogenic variability is complicated by shell growth patterns and potential small vital effects. The calcium isotope ratios are found to be constant throughout ontogeny within analytical precision at a value of δ44/40Ca = 0.68 ± 0.16‰ (2 sd) SRM–915a which is consistent with other bivalve species. Calcium isotope ratios in oyster shell material might thus be a possible proxy for palaeo seawater calcium isotope ratios. Element/Ca ratios are significantly higher in the chalky substance than in the foliate layers and especially high Sr/Ca and Mn/Ca ratios are observed for the first growth season of the oysters. Mg/Ca ratios in the chalky substance show a negative correlation with δ18O values, compatible with a temperature dependence, whereas this correlation is absent in the foliate layers. Seasonal changes of Sr/Ca are controlled by metabolic processes, whereas for Mn/Ca an additional environmental control is evident.

Description: We report delta Ca-44/40((SRM 915a)) values for eight fused MPI-DING glasses and the respective original powders, six USGS igneous rock reference materials, the U-Th disequilibria reference material TML, IAEA-CO1 (Carrara marble) and several igneous rocks (komatiites and carbonatites). Sample selection was guided by three considerations: (1) to address the need for information values on reference materials that are widely available in support of interlaboratory comparison studies; (2) support the development of in situ laser ablation and ion microprobe techniques, which require isotopically homogenous reference samples for ablation; and (3) provide Ca isotope values on a wider range of igneous and metamorphic rock types than is currently available in the scientific literature. Calcium isotope ratios were measured by thermal ionisation mass spectrometry in two laboratories (IFM-GEOMAR and Saskatchewan Isotope Laboratory) using Ca-43/Ca-48- and Ca-42/Ca-43-double spike techniques and reported relative to the calcium carbonate reference material NIST SRM 915a. The measurement uncertainty in both laboratories was better than 0.2 parts per thousand at the 95% confidence level. The impact of different preparation methods on the delta Ca-44/40((SRM 915a)) values was found to be negligible. Except for ML3-B, the original powders and the respective MPI-DING glasses showed identical delta Ca-44/40((SRM 915a)) values; therefore, possible variations in the Ca isotope compositions resulting from the fusion process are excluded. Individual analyses of different glass fragments indicated that the glasses are well homogenised on the mm scale with respect to Ca. The range of delta Ca-44/40((SRM 915a)) values in the igneous rocks studied was larger than previously observed, mostly owing to the inclusion of ultramafic rocks from ophiolite sections. In particular, the dunite DTS-1 (1.49 +/- 0.06 parts per thousand) and the peridotite PCC-1 (1.14 +/- 0.07 parts per thousand) are enriched in Ca-44 relative to volcanic rocks (0.8 +/- 0.1 parts per thousand). The Carrara marble (1.32 +/- 0.06 parts per thousand) was also found to be enriched in Ca-44 relative to the values of assumed precursor carbonates (〈 0.8 parts per thousand). These findings suggest that the isotopes of Ca are susceptible to fractionation at high temperatures by, as yet, unidentified igneous and metamorphic processes.