The origin of secondary heavy rare earth element enrichment in carbonatites: Constraints from the evolution of the Huanglongpu district, China

The silico-carbonatite dykes of the Huanglongpu area, Lesser Qinling, China, are unusual in that they are quartzbearing, Mo-mineralised and enriched in the heavy rare earth elements (HREE) relative to typical carbonatites. The textures of REE minerals indicate crystallisation of monazite-(Ce), bastnasite-(Ce), parisite-(Ce) and aeschynite-(Ce) as magmatic phases. Burbankite was also potentially an early crystallising phase. Monazite-(Ce) was subsequently altered to produce a second generation of apatite, which was in turn replaced and overgrown by britholite-(Ce), accompanied by the formation of allanite-(Ce). Bastnasite and parisite where replaced by synchysite-(Ce) and rontgenite-(Ce). Aeschynite-(Ce) was altered to uranopyrochlore and then pyrochlore with uraninite inclusions. The mineralogical evolution reflects the evolution from magmatic carbonatite, to more silica-rich conditions during early hydrothermal processes, to fully hydrothermal conditions accompanied by the formation of sulphate minerals. Each alteration stage resulted in the preferential leaching of the LREE and enrichment in the HREE. Mass balance considerations indicate hydrothermal fluids must have contributed HREE to the mineralisation. The evolution of the fluorcarbonate mineral assemblage requires an increase in a(Ca)2+ and a(CO3)2- in the metasomatic fluid (where a is activity), and breakdown of HREE-enriched calcite may have been the FREE source. Leaching in the presence of strong, LREE-selective ligands (Cl-) may account for the depletion in late stage minerals in the LREE, but cannot account for subsequent preferential HREE addition. Fluid inclusion data indicate the presence of sulphate-rich brines during alteration, and hence sulphate complexation may have been important for preferential HREE transport. Alongside HREE-enriched magmatic sources, and enrichment during magmatic processes, late stage alteration with non-LREE-selective ligands may be critical in forming HREE-enriched carbonatites. (C) 2018 The Authors. Published by Elsevier B.V.