The Cenozoic Ambohimirahavavy alkaline complex in Madagascar consists of several syenitic to granitic intrusions (24.2 ± 0.6 Ma) the largest of which, the Ampasibitika intrusion, is characterized by the presence in its outer flanks of late peralkaline granitic dikes intruding mudstone and limestone of the Isalo Group. A network of dikelets and veinlets propagates from these dikes, intruding along bedding or obliquely to bedding. At the contact between the dikes and dikelets and a limestone, a reaction zone enriched in rare metals, dominated by calc-silicate minerals such diopside and andradite-grossular, forms a rare example of skarn resulting from peralkaline igneous activity.
Much of the rare-metal mineralization (REE, Zr, Nb, Th, Sn, and Ti) occurs as secondary phases in the dikelets and skarn. In the dikelets and endoskarn, high field strength element (HFSE)-rich phases consist mainly of zircon, bastnäsite-(Ce), and Ca-REE-, and Ca-HFSE-rich phases in pseudomorphs after aegirine-augite. In the exoskarn, the main HFSE-rich phases are bastnäsite-(Ce), zircon, pyrochlore, Nb-rich titanite, and an unidentified F-rich Ca-zirconosilicate finely disseminated in a matrix composed of calcite, diopside, andradite, phlogopite, quartz, fluorite, and fluorapatite. The secondary zircon is characterized by a low Zr content and by the presence of REE, Ca, Al, and Fe.
Three types of primary fluid inclusions were observed in dikelets and skarn in quartz, calcite, and diopside:
liquid-rich inclusions (L-V) (20 to 40 vol % vapor) occur in all three minerals and homogenize to liquid;
vapor-rich inclusions (V) (>90 vol % vapor) occur in diopside and quartz, and homogenize to vapor; and
halite-bearing L-V inclusions (L-V-H) occur in diopside and quartz, and homogenize either by disappearance of the vapor bubble or by halite dissolution. The L-V inclusions have low to intermediate salinity and homogenize at temperatures ranging from 200° to 380°C. The V inclusions have low salinity and homogenize at higher temperature (350°–395°C). The L-V-H inclusions mainly contain NaCl (35–45 wt % NaCl equiv), and homogenize by three modes, namely, bubble disappearance (mode A), halite dissolution (mode B), and simultaneous bubble and halite disappearance (mode C); the homogenization temperatures range from 260° to 380°C.
We propose a model in which rare metals were transported by a Cl−, F− and HFSE-rich orthomagmatic fluid exsolved at 400° to 450°C and about 20 MPa. At these conditions, the fluid was in the two-phase region and vapor dominated. The rare metals were deposited as a result of the interaction of this fluid with limestone and mixing with an external fluid. This interaction/mixing buffered the orthomagmatic fluid to higher pH and lower temperature, resulting in the destabilization of REE-chloride complexes and deposition of fluorocarbonate minerals in the limestone; Zr and Nb, which were likely transported as hydroxyl-fluoride complexes, precipitated as zircon and pyrochlore due to deposition of fluorite and a consequent decrease in fluoride activity.