Hydrothermal transport and deposition of the rare earth elements by fluorine-bearing aqueous liquids

Abstract

New technologies, particularly those designed to address environmental concerns, have created a great demand for the rare earth elements (REE), and focused considerable attention on the processes by which they are concentrated to economically exploitable levels in the Earth’s crust. There is widespread agreement that hydrothermal fluids played an important role in the formation of the world’s largest economic REE deposit, i.e. Bayan Obo, China. Until recently, many researchers have assumed that hydrothermal transport of the REE in fluorine-bearing ore-forming systems occurs mainly due to the formation of REE-fluoride complexes. Consequently, hydrothermal models for REE concentration have commonly involved depositional mechanisms based on saturation of the fluid with REE minerals due to destabilization of REE-fluoride complexes. Here, we demonstrate that these complexes are insignificant in REE transport, and that the above models are therefore flawed. The strong association of H+ and F− as HF° and low solubility of REE-F solids greatly limit transport of the REE as fluoride complexes. However, this limitation does not apply to REE-chloride complexes. Because of this, the high concentration of Cl− in the ore fluids, and the relatively high stability of REE-chloride complexes, the latter can transport appreciable concentrations of REE at low pH. The limitation also does not apply to sulphate complexes and in some fluids, the concentration of sulphate may be sufficient to transport significant concentrations of REE as sulphate complexes, particularly at weakly acidic pH. This article proposes new models for hydrothermal REE deposition based on the transport of the REE as chloride and sulphate complexes.