Stable isotope fractionation of zinc and cadmium in soil-plant system: A review

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Stable isotope fractionation provides a useful tool for tracing the transfer of zinc (Zn) and cadmium (Cd) in the soil-plant system. Isotope fractionation processes include equilibrium fractionation, e.g. dissolution, complexation, precipitation, and kinetic fractionation, e.g. diffusion and evaporation. Therefore, isotope fractionation of metallic element can be used to study the mechanisms of metal translocation in biogeochemical cycling. With the development of multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS), Zn and Cd isotopic composition in soil and plant samples can be accurately measured. The determination of Zn and Cd stable isotope ratios usually includes sample digestion, purification and mass discrimination correction. In the soil-plant system, plants are generally enriched with heavy Zn isotopes in comparison to soils, while roots are enriched with heavy Zn isotopes in comparison to shoots. For Cd, shoots are likely to be isotopically heavier than roots. The transport processes of Zn/Cd in the soil-plant system mainly involve transport in rhizosphere, root uptake and transport within plants. The adsorption and desorption of Zn/Cd by soil minerals can affect the metal mobility and the isotope fractionation between soil solid phases and soil solution. Heavy Zn isotopes are likely to be complexed, while light Zn isotopes are more mobile in soil solution. Conversely, soil minerals tend to adsorb light Cd isotopes, thereby resulting in an enrichment with heavy isotopes in the soil solution. Among the rhizospheric processes, the secretion of root exudates and the changes in pH also have an impact on the speciation and translocation of heavy metals, which lead to the release of heavy Zn isotopes into soil solution. Root uptake process is of pivotal importance for the determination of the isotopic composition of the whole plant. The diffusion of Zn2+ from the soil solution to the root surface leads to a light isotopes enrichment in plant. Heavy Zn isotopes are preferentially chelated or precipitated in the root apoplast. During the transport across the root cell membranes, the low-affinity transport leads to an enrichment with light isotopes in plant, while the high-affinity transport generates little or no isotope fractionation. Specific transporter of Cd in roots has never been found yet. Therefore, Cd may be took up mainly through low-affinity transport systems and thus be enriched in light isotopes in plants. The isotope fractionation between roots and shoots is related to the sequestration of Zn/Cd in roots and the xylem transport processes. The functional groups containing oxygen and nitrogen of organic acids in plant roots tend to chelate heavy Zn isotopes, with subsequent compartmentation in root vacuoles. The light Zn isotopes could be then loaded by the xylem and transferred to the aboveground parts. Interestingly, the intensity of isotope fractionation is mainly related to the transport distance in the xylem. Contrary to Zn, light Cd isotopes mainly bind to the thiol groups in roots, leading to the enrichment in heavy isotopes in shoots. The different behaviors between Zn and Cd in isotope fractionation in the soil-plant system could reflect the distinct accumulation and tolerance mechanisms of plants in response to Zn or Cd stress.