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18Analyses of stable metal isotope ratios constitute a novel tool to improve understanding of 19 biogeochemical processes in soil-plant systems. In this study, we used such measurements 20 to assess Cd uptake and transport in wheat grown on three agricultural soils under 21 controlled conditions. Isotope ratios of Cd were determined in the bulk C and A horizons, in 22 the Ca(NO 3 ) 2 extractable Cd soil pool and in roots, straw and grains. The Ca(NO 3 ) 2 23 extractable Cd was isotopically heavier than the Cd in the bulk A horizon (Δ

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.

The application of mineral phosphate (P) fertilizers leads to an unintended Cd input into agricultural systems, which might affect soil fertility and quality of crops. The Cd fluxes at three arable sites in Switzerland were determined by a detailed analysis of all inputs (atmospheric deposition, mineral P fertilizers, manure, and weathering) and outputs (seepage water, wheat and barley harvest) during one hydrological year. The most important inputs were mineral P fertilizers (0.49 to 0.57 g Cd ha yr) and manure (0.20 to 0.91 g Cd ha yr). Mass balances revealed net Cd losses for cultivation of wheat (-0.01 to -0.49 g Cd ha yr) but net accumulations for that of barley (+0.18 to +0.71 g Cd ha yr). To trace Cd sources and redistribution processes in the soils, we used natural variations in the Cd stable isotope compositions. Cadmium in seepage water (δCd = 0.39 to 0.79‰) and plant harvest (0.27 to 0.94‰) was isotopically heavier than in soil (-0.21 to 0.14‰). Consequently, parent material weathering shifted bulk soil isotope compositions to lighter signals following a Rayleigh fractionation process (ε ≈ 0.16). Furthermore, soil-plant cycling extracted isotopically heavy Cd from the subsoil and moved it to the topsoil. These long-term processes and not anthropogenic inputs determined the Cd distribution in our soils.

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