Stable Zn isotopes are increasingly used to trace the source of metal pollution in the environment and to gain a better understanding of the biogeochemical cycle of Zn. In this work, we investigated the effect of plants on Zn isotope fractionation in the soil-plant system of the surface horizon of two Zn-rich Technosols (pH 6.73-7.51, total Zn concentration = 9470-56600 mg kg(-1)). In a column experiment, the presence of Agrostis capillaris L. significantly increased the mobilization of Zn from soil to leachate, predominantly as a result of root-induced soil acidification. The zinc isotope compositions of plants and leachates indicated that the Zn uptake by A. capillaris did not fractionate Zn isotopes as compared to the leachates. Within the plant, heavier Zn isotopes were preferentially retained in roots (Δ66Znroot - shoot=+0.24 to +0.40 ‰). More importantly, the Zn released in leachates due to root-induced mobilization was isotopically heavier than the Zn released in the absence of plants (Δ66Zn=+0.16 to +0.18 ‰). This indicates that the rhizosphere activity of A. capillaris mobilized Zn from another pool than the one that spontaneously releases Zn upon contact with the percolating solution. Mobilization of Zn by the roots might thus exert a stronger influence on the Zn isotope composition in the soil solution than the Zn uptake by the plant. This study highlights the key role of the rhizosphere activity in Zn release in soil and demonstrates that stable Zn isotopes provide a useful proxy for the detection of Zn mobilization in soil-plant systems.

A B S T R A C TStable zinc (Zn) isotope fractionation between soil and plant has been used to suggest the mechanisms affecting Zn uptake under toxic conditions. Here, changes in Zn isotope composition in soil, soil solution, root and shoot were studied for ryegrass (Lolium multiflorum L.) and rape (Brassica napus L.) grown on three distinct metal-contaminated soils collected near Zn smelters (total Zn 0.7-7.5%, pH 4.8-7.3). The Zn concentrations in plants reflected a toxic Zn supply. The Zn isotopic fingerprint of total soil Zn varied from À0.05% to +0.26 AE 0.02% (d 66 Zn values relative to the JMC 3-0749L standard) among soils, but the soil solution Zn was depleted in 66 Zn, with a constant Zn isotope fractionation of about À0.1% d 66 Zn unit compared to the bulk soil. Roots were enriched with 66 Zn relative to soil solution (d 66 Zn root À d 66 Zn soil solution = D 66 Zn root-soil solution = +0.05 to +0.2 %) and shoots were strongly depleted in 66 Zn relative to roots (D 66 Zn shoot-root = À0.40 to À0.04 %). The overall d 66 Zn values in shoots reflected that of the bulk soil, but were lowered by 0.1-0.3 % units as compared to the latter. The isotope fractionation between root and shoot exhibited a markedly strong negative correlation (R 2 = 0.83) with transpiration per unit of plant weight. Thus, the enrichment with light Zn isotopes in shoot progressed with increasing water flux per unit plant biomass dry weight, showing a passive mode of Zn transport by transpiration. Besides, the light isotope enrichment in shoots compared to roots was larger for rape than for rye grass, which may be related to the higher Zn retention in rape roots. This in turn may be related to the higher cation exchange capacity of rape roots. Our finding can be of use to trace the biogeochemical cycles of Zn and evidence the tolerance strategies developed by plants in Znexcess conditions.

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