The transfer of metal and metalloid trace elements (MTEs) from contaminated soil to grapevines is a major issue for grape consumption and for the associated health risks. Based on an isotopic approach, we shed light on the concept of MTE bioavailability. The bioavailable fractions are identified by using the Sr-isotope ratio as a proxy for MTEs. This allows us to differentiate three soil reservoirs: the ‘current available fraction’ in soil water, the ‘reserve available fraction’ stored in mineral phases of the soil fractions, and the ‘non-available fraction’. The reserve available fraction, representing 10 to 60% of bulk soil depending on the MTE, includes the exchangeable, carbonates, humic substance and oxides fractions. The 87Sr/86Sr isotopic signatures of grape berries and vine leaves show an additional source of MTEs, which is imported by foliar uptake and can contribute up to 10% of the MTEs in leaves. In addition, root-uptake and translocation rates show high accumulation rates of Co, Sn and Cu, and low ones for As, Sb, Zn and Cd. A daily intake between 1 and 3 kg of (dry grapes) would reach the benchmark dose level for a 0.5% (BMDL0.5). While such a daily intake of grapes is unreasonable, consumption of other local vegetables and fruit would contribute to the daily intake. Hence, a chronic arsenic exposure is of great concern for human health in mining areas. We outline the importance of geochemical tracers, such as Sr isotopes, when determining the transfer and translocation of MTEs in plants. Our method presents a high-precision evaluation of the bioavailability and bioaccumulation of MTEs, and a better understanding of these processes in plants, thus leading to a better assessment of the environmental risk on human health.