Carbonatitic versus hydrothermal origin for fluorapatite REE-Th deposits: Experimental study of REE transport and crustal “antiskarn” metasomatism

Abstract

Nolans-type ore deposits contain REE and Th mineralization hosted in fluorapatite veins. These veins intrude granulite facies rocks and are surrounded by a diopside selvage. Nolans-type deposits are thought to form by REE, F and P-rich hydrothermal fluids derived from alkali or carbonatitic intrusions. However, REE are not effectively transported in F and P-rich systems. REE ore deposits are commonly hydrothermally overprinted, possibly obscuring the igneous nature of the primary mineralization. We conducted a series of piston cylinder “sandwich” experiments, testing the hydrothermal fluid hypothesis, and a newly suggested process of carbonatite metasomatism. Our results confirm theoretical predictions that REE are hydrothermally immobile in these systems and the experimental phase assemblage is not compatible with the natural rocks. Our results show that fluorapatite can only host several weight percent levels of REE at temperatures higher than ∼600 °C. Below that temperature, a miscibility gap exists between REE-poor fluorapatite and REE-rich silicates such as britholite or cerite. In contrast, experiments reacting P and REE-rich carbonatite with silicate rock above 700 °C closely resemble natural rocks from Nolans-type deposits. Selvage mineralogy is sensitive to the MgO content of the carbonatite. A diopside selvage formed at carbonatite MgO/(CaO+MgO) ≈ 0.2 while wollastonite and forsterite formed at lower and higher ratios, respectively. Phosphate solubility in carbonatites decreases with decreasing MgO contents. As diopside formed, REE-rich fluorapatite preferentially crystallized from the selvage inwards. Thus, carbonatites are effective at simultaneously mobilizing REE, F and P to the site of deposition. Nolans-type deposits are the cumulate residue of this reaction, with the carbonatite liquid migrating elsewhere. At temperatures below 700 °C the carbonatite–silicate reaction additionally formed monticellite, cuspidine and magnesioferrite, resembling a skarn assemblage. Whereas skarns form by infiltration of silicate magmas or related fluids to carbonate rocks, our experiments are the opposite: intrusion of carbonatite into silicate rock. These mid-crustal skarn-like rocks may host elevated ore elements of carbonatitic affinity, such as F, P, Y, REE, Th, Ba, Sr, and Nb. We propose the term “antiskarn” to describe such systems, and suggest they trace the migration of carbonatite liquids through the crust. Hydrothermal reworking, retrogression, or metamorphism of antiskarns may obscure the carbonatitic genesis of the rocks. These metasomatic zones are the crustal equivalent of wehrlites that form by peridotite–carbonatite reaction at mantle depths.