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For many years, our understanding of the behavior of the REE in hydrothermal systems was based on semiempirical estimates involving extrapolation of thermodynamic data obtained at 25°C (Haas et al., 1995;Wood, 1990a). Since then, a substantial body of experimental data has accumulated on the stability of aqueous complexes of the REE. These data have shown that some of the predictions of Haas et al. (1995) are accurate, but others may be in error by several orders of magnitude. However, application of the data in modeling hydrothermal transport and deposition of the REE has been severely hampered by the lack of data on the thermodynamic properties of even the most common REE minerals. The discrepancies between the predictions of Haas et al. (1995) and experimental determinations of the thermodynamic properties of aqueous REE species, together with the paucity of data on the stability of REE minerals, raise serious questions about the reliability of some models that have been proposed for the hydrothermal mobility of these critical metals. In this contribution, we review a body of high-temperature experimental data collected over the past 15 years on the stability of REE aqueous species and minerals. Using this new thermodynamic dataset, we re-evaluate the mechanisms responsible for hydrothermal transport and deposition of the REE. We also discuss the mechanisms that can result in REE fractionation during their hydrothermal transport and deposition. Our calculations suggest that in hydrothermal solutions, the main REE transporting ligands are chloride and sulfate, whereas fluoride, carbonate, and phosphate likely play an important role as depositional ligands. In addition to crystallographic fractionation, which is based on the differing affinity of mineral structures for the REE, our models suggest that the REE can be fractionated hydrothermally due to the differences in the stability of the LREE and HREE as aqueous chloride complexes.

A lthough the rare earth elements have been thought by many to be immobile in hydrothermal fl uids, we have known since the fi rst attempts to separate them in the early nineteenth century that they are soluble in aqueous solutions. Driven by a need to isolate individual REEs for industrial applications, and more recently to explore for them, we have started to develop an understanding of their solubility and speciation in hydrothermal fl uids. This knowledge is allowing us to understand the processes that promote their transport in the Earth's crust, their concentration, and their fractionation.

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