EXPERIMENTAL DETERMINATION OF REE FRACTIONATION BETWEEN LIQUID AND VAPOUR IN THE SYSTEMS NACL-H2O AND CACL2-H2O UP TO 450 °C

Abstract

Fractionation of selected REE between brine and vapour was experimentally determined using a large-volume rocking Ti-autoclave that allowed quasi-isobaric sampling of liquid-vapour pairs. Samples were extracted along the 350, 400 and 450 °C-isotherms of the H2O-NaCl system, and along the 400 °C isotherm of the CaCl2 system. Total salt concentrations were either 6.6 and 10 wt% NaCl or CaCl2, respectively, and total REE concentrations were about 2 ppm of each REE. Starting pH at room temperature was 1.8, added as HCl. In another series of experiments, REEs were added in amounts of 312 ppm. Here, the starting pH at room temperature was 0.5, added as HNO3:HCl=1:2. Liquid-vapour pairs (L-V) were analysed for REE by ICP-MS methods. L-V-partitioning of REE along a particular isotherm follows broadly the partitioning of the main salt components, NaCl or CaCl2. DREE=REEV/REEL decrease rapidly from the critical point with decreasing pressure (equivalent to increasing salinity of the liquid) as the solvus opens. This is independent of the total amount of the added REE. Log DREE values show approximately linear correlations with decreasing pressure from the critical point to salt-saturated conditions where the L-V curve meets the liquid + vapour + solid boundary. At given P and T, we found a systematic variation of DREE along the La-Lu suite. HREE are enriched in the vapour phase relative to LREE. Fractionation coefficients KD=(HREEV/HREEL)/(LREEV/LREEL) increase linearly with ΔP=Pcrit-P along a particular isotherm. At the 450 °C isotherm, KD (Lu/La) at the critical point (425 bar and 10 wt% NaCl) is 1; about 2.5 at 350 bar (33 wt% NaCl in the liquid); and about 5 if extrapolated to salt-saturation (250 bar and 52 wt% NaCl in the liquid). The REE fractionation behaviour is similar along the CaCl2-H2O solvus boundaries. Existing equations of state and thermodynamic databases of REE species cannot predict this behaviour at L-V-equilibrium conditions. That HREE are preferentially fractionated over LREE into the vapour phase has important petrogenetic consequences. In boiling hydrothermal systems, brines will be depleted in HREE relative to LREE. Isobaric cooling is ineffective for fractionation because the solvus closes and the system eventually shifts into the one-phase field. Fractionation is most effective in systems undergoing isothermal or adiabatic decompression. In an open system, where vapour may escape through cavities, fractionation is probably controlled by a Rayleigh fractionation process, resulting in larger overall fractionation effects. Similar fractionations probably occur during magma degassing at very shallow intrusion levels.