Crystallisation sequence of a REE-rich carbonate melt: an experimental approach

Abstract

Carbonatites host Earth’s main REE deposits, with bastnaesite (LREE)CO$_3$F being the main economic REE-bearing mineral. However, bastnaesite mineralisation processes are debated between hydrothermal or magmatic origin. This study aims to assess if bastnaesite can be magmatic, and to characterise the REE behaviour during carbonatite crystallisation. Crystallisation experiments have been performed from 900 to 600 °C at 1 kbar, on a REE-rich calciocarbonatitic composition. REE-bearing calcite is the dominant crystallising mineral, driving the residual melt towards natrocarbonatitic compositions. Both halogens (i.e., Cl and F) and water decrease the temperature of calcite saturation. REE are slightly incompatible with calcite: for all REE, partition coefficients between carbonate melt and calcite are comprised between 1 and 11, and increase with temperature decrease. Britholite (REE, Ca)$_{5}$((Si,P)O$_{4}$)$_3$(F,OH) crystallises at high temperatures (700–900 °C), while pyrochlore (Ca,Na,REE)$_{2}$Nb$_{2}$O$_{6}$(OH,F) crystallises at low temperatures (600–700 °C), as well as REE-rich apatite (600–650 °C). No bastnaesite is found in crystallisation experiments. We thus performed a bastnaesite saturation experiment at 600 °C. The bastnaesite-saturated melt contains 20 wt% of REE: such magmatic saturation is unlikely to happen in nature. Textural evidences imply a Na, Cl, REE-rich fluid at high temperatures and hydrous conditions. We propose that fluids are the main mineralising agent for bastnaesite at hydrothermal stage ($<$600 °C).

Keywords

• Natrocarbonatite
• Carbonatite
• Rare earth elements
• Experimentation
• Crystallisation
• Calcite
• Bastnaesite
• Natrocarbonatite