NdPO4 solubility and aqueous Neodymium speciation in supercritical fluids: An experimental study at 500–700 °C and 1.7 kbar

Abstract

A key aspect in the formation of rare earth elements (REE) deposits is the role of REE transport as aqueous REE complexes in supercritical hydrothermal solutions, where the nature of the aqueous complex is controlled by solution composition, temperature and pressure. Despite chloride being considered as one of the most abundant transporting ligands in magmatic-hydrothermal fluids, experimental investigations on the stability of aqueous REE chloride complexes are scarce above 300 °C. In this study, synthetic NdPO4 crystals were reacted with non-saline and saline (0, 0.05 and 0.5 mNaCl), acidic (0.01 mHCl) aqueous solutions in a series of solubility experiments conducted at 500 − 700 °C and 1.7 kbar, where the solubilities were determined using a stable Nd isotope (145Nd isotope spike) dilution technique. NdPO4 solubility ranges between 28 ppm and 10,858 ppm, where solubility increases with both temperature and salinity. At 500 °C, log mNdPO4 increases from −3.93 to −1.60 and there is a strong correlation between NdPO4 solubility and NaCl concentrations (slope of 1.2 ± 0.3), indicating stabilization of the Nd chloride aqueous complexes with a stoichiometry corresponding to NdCl2+. At 600 °C, this correlation is weaker (slope of 0.4, log mNdPO4 increases from −2.63 to −1.88) indicating the stabilization of both Nd chloride and hydroxyl species controlling solubility. At 700 °C, NdPO4 solubility is largely independent of NaCl concentration indicating that solubility is controlled by Nd hydroxyl complexes, where stoichiometry suggests the neutral Nd(OH)30 species is dominant. The solubility product (Ksp) of NdPO4 is derived from experimental data with the relation: log Ksp = -41.81 – 0.057T – 20987/T, with T temperature in Kelvin. Comparison of the measured Nd phosphate solubility to thermodynamic predictions using the available Helgeson-Kirkham-Flowers equation of state parameters for aqueous Nd complexes indicate that predictions are up to three orders of magnitude lower compared to experimental observations. This discrepancy is most pronounced in saline solutions, suggesting that thermodynamic properties of the REE chloride species in supercritical fluids require revision. Numerical simulations of fluid-rock interaction between acidic, saline fluids and a Strange Lake felsic mineral assemblage demonstrates that NdPO4 solubility predictions from models are four to six orders of magnitude lower than those calculated based on empirical fits from experiments, which suggests that acidic, saline fluids may play an important role in mobilizing large amounts of light REE from 450 to 700 °C.