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

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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Remobilization of zinc (Zn) from shoot to grain contributes significantly to Zn grain concentrations and thereby to food quality. On the other hand, strong accumulation of cadmium (Cd) in grain is detrimental for food quality. Zinc concentrations and isotope ratios were measured in wheat shoots (Triticum aestivum) at different growth stages to elucidate Zn pathways and processes in the shoot during grain filling. Zinc mass significantly decreased while heavy Zn isotopes accumulated in straw during grain filling (Δ Zn = 0.21-0.31‰). Three quarters of the Zn mass in the shoot moved to the grains, which were enriched in light Zn isotopes relative to the straw (Δ Zn -0.21 to -0.31‰). Light Zn isotopes accumulated in phloem sinks while heavy isotopes were retained in phloem sources likely because of apoplastic retention and compartmentalization. Unlike for Zn, an accumulation of heavy Cd isotopes in grains has previously been shown. The opposing isotope fractionation of Zn and Cd might be caused by distinct affinities of Zn and Cd to oxygen, nitrogen, and sulfur ligands. Thus, combined Zn and Cd isotope analysis provides a novel tool to study biochemical processes that separate these elements in plants.

The supplementation of Zn to farm animal feed and the excretion via manure leads to an unintended Zn input to agricultural systems, which might compromise the long-term soil fertility. The Zn fluxes at three grassland sites in Switzerland were determined by a detailed analysis of relevant inputs (atmospheric deposition, manure, weathering) and outputs (seepage water, biomass harvest) during one hydrological year. The most important Zn input occurred through animal manure (1,076 to 1,857 g ha-1 yr-1) and Zn mass balances revealed net Zn accumulations (456 to 1,478 g ha-1 yr-1). We used Zn stable isotopes to assess the importance of anthropogenic impacts and natural long-term processes on the Zn distribution in soils. Soil-plant cycling and parent material weathering were identified as the most important processes, over the entire period of soil formation (13,700 years), while the soil pH strongly affected the direction of Zn isotopic fractionation. Recent anthropogenic inputs of Zn only had a smaller influence compared to the natural processes of the past 13,700 years. However, this will probably change in the future, as Zn stocks in the 0-20 cm layer will increase by 22% to 68% in the next 100 years, if Zn inputs remain on the same level as today.