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We present strontium (Sr) isotope ratios that, unlike traditional 87 Sr/ 86 Sr data, are not normalized to a fixed 88 Sr/ 86 Sr ratio of 8.375209 (defined as d 88/86 Sr = 0 relative to NIST SRM 987). Instead, we correct for isotope fractionation during mass spectrometry with a 87 Sr-84 Sr double spike. This technique yields two independent ratios for 87 Sr/ 86 Sr and 88 Sr/ 86 Sr that are reported as ( 87 Sr/ 86 Sr*) and (d 88/86 Sr), respectively. The difference between the traditional radiogenic ( 87 Sr/ 86 Sr normalized to 88 Sr/ 86 Sr = 8.375209) and the new 87 Sr/ 86 Sr* values reflect natural mass-dependent isotope fractionation. In order to constrain glacial/interglacial changes in the marine Sr budget we compare the isotope composition of modern seawater (( 87 Sr/ 86 Sr*, d 88/86 Sr) Seawater ) and modern marine biogenic carbonates (( 87 Sr/ 86 Sr*, d 88/86 Sr) Carbonates ) with the corresponding values of river waters (( 87 Sr/ 86 Sr*, d 88/86 Sr) River ) and hydrothermal solutions (( 87 Sr/ 86 Sr*, d 88/86 Sr) HydEnd ) in a triple isotope plot. The measured ( 87 Sr/ 86 Sr*, d 88/86 Sr) River values of selected rivers that together account for $18% of the global Sr discharge yield a Sr flux-weighted mean of (0.7114 (8), 0.315(8)&). The average ( 87 Sr/ 86 Sr*, d 88/86 Sr) HydEnd values for hydrothermal solutions from the Atlantic Ocean are (0.7045(5), 0.27(3)&). In contrast, the ( 87 Sr/ 86 Sr*, d 88/86 Sr) Carbonates values representing the marine Sr output are (0.70926(2), 0.21(2)&). We estimate the modern Sr isotope composition of the sources at (0.7106(8), 0.310(8)&).The difference between the estimated ( 87 Sr/ 86 Sr*, d 88/86 Sr) input and ( 87 Sr/ 86 Sr*, d 88/86 Sr) output values reflects isotope disequilibrium with respect to Sr inputs and outputs. In contrast to the modern ocean, isotope equilibrium between inputs and outputs during the last glacial maximum (10-30 ka before present) can be explained by invoking three times higher Sr inputs from a uniquely "glacial" source: weathering of shelf carbonates exposed at low sea levels. Our data are also consistent with the "weathering peak" hypothesis that invokes enhanced Sr inputs resulting from weathering of postglacial exposure of abundant fine-grained material.

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We report δ44/40Ca(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 43Ca/48Ca‐ and 42Ca/43Ca‐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‰ at the 95% confidence level. The impact of different preparation methods on the δ44/40Ca(SRM 915a) values was found to be negligible. Except for ML3‐B, the original powders and the respective MPI‐DING glasses showed identical δ44/40Ca(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 δ44/40Ca(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‰) and the peridotite PCC‐1 (1.14 ± 0.07‰) are enriched in 44Ca relative to volcanic rocks (0.8 ± 0.1‰). The Carrara marble (1.32 ± 0.06‰) was also found to be enriched in 44Ca relative to the values of assumed precursor carbonates (< 0.8‰). These findings suggest that the isotopes of Ca are susceptible to fractionation at high temperatures by, as yet, unidentified igneous and metamorphic processes.