Rare earth mobility as a result of multiple phases of fluid activity in fenite around the Chilwa Island Carbonatite, Malawi

Abstract

Carbonatites are enriched in critical raw materials such as the rare earth elements (REE), niobium, fluorspar and phosphate. A better understanding of their fluid regimes will improve our knowledge of how to target and exploit economic deposits. This study shows that multiple fluid phases penetrated the surrounding fenite aureole during carbonatite emplacement at Chilwa Island, Malawi. The first alkaline fluids formed the main fenite assemblage and later microscopic vein networks contain the minerals of potential economic interest such as pyrochlore in high-grade fenite and RE minerals throughout the aureole. Seventeen samples of fenite rock from the metasomatic aureole around the Chilwa Island carbonatite complex were chosen for study (Natural History Museum, London collection BM1968 P37). In addition to the main fenite assemblage of feldspar and aegirine ± arfvedsonite, riebeckite and richterite, the fenite contains micro-mineral assemblages including apatite, ilmenite, rutile, magnetite, zircon, RE minerals and pyrochlore in vein networks. Petrography using SEM-EDX showed that the RE minerals (monazite, bastnäsite and parisite) formed later than the fenite feldspar, aegirine and apatite and provide evidence of REE mobility into all grades of fenite. Fenite apatite has a distinct negative Eu anomaly (determined by LA-ICP-MS) that is rare in carbonatite-associated rocks and interpreted as related to pre-crystallisation of plagioclase and co-crystallisation with K-feldspar in the fenite. The fenite minerals have consistently higher mid REE/light REE ratios (La/Sm = ~1.3 monazite, ~1.9 bastnäsite, ~1.2 parisite) than their counterparts in the carbonatites (La/Sm = ~2.5 monazite, ~4.2 bastnäsite, ~3.4 parisite). Quartz in the low- and medium-grade fenite hosts fluid inclusions, typically a few µm in diameter, secondary and extremely heterogeneous. Single phase, 2- and 3-phase, single solid and multi solid-bearing examples are present, with 2-phase the most abundant. Calcite, nahcolite, burbankite and barite were found in the inclusions. Decrepitation of inclusions occurred at around 200˚C before homogenisation but melting temperature data indicate that the inclusions contain relatively pure CO2. A minimum salinity of around 24 wt.% NaCl equivalent was determined. Among the trace elements in whole rock analyses, enrichment in Ba, Mo, Nb, Pb, Sr, Th and Y and depletion in Co, Hf and V are common to carbonatite and fenite but enrichment in carbonatitic type elements (Ba, Nb, Sr, Th, Y, and REE) generally increases towards the inner parts of the aureole. A schematic model contains multiple fluid events, related to first and second boiling of the magma, accompanying intrusion of the carbonatites at Chilwa Island, each contributing to the mineralogy and chemistry of the fenite. The presence of distinct RE mineral micro-assemblages in fenite at some distance from carbonatite could be developed as an exploration indicator of REE enrichment.