Mechanisms of bastnasite formation: replacement of calcite by rare earth carbonates.

<div> <p>The interaction of rare earth bearing (La, Nd, Dy) aqueous solutions with calcite crystals at was studied at ambient and hydrothermal conditions (25-220 °C) and resulted in the solvent-mediated surface precipitation and subsequent pseudomorphic mineral replacement of calcite by rare earth carbonates. Calcite grains were replaced from their periphery inwards, and the newly formed REE-bearing carbonates follow the crystallisation sequence lanthanite [REE<sub>2</sub>(CO<sub>3</sub>)<sub>3</sub>·8H<sub>2</sub>O] → kozoite [orthorhombic REECO<sub>3</sub>(OH)] → hydroxylbastnasite [hexagonal REECO<sub>3</sub>(OH)]. The specific rare earth involved in these processes and the temperature have a significant role in the polymorph selection, crystallisation pathways and kinetics of mineral replacement. La- and Nd-bearing kozoite, grows oriented onto the calcite surface, forming an epitaxy, due to their structural similarities. This phase forms elongated crystals on [100], with the {011} and {0-11} as major forms. The epitaxial relationship is (104) [010]<sub>cc </sub>║(001) [100]<sub>koz</sub> and is strongly dependent on the ionic radius of the rare earth in the structure of kozoite. These results have strong implications for the understanding of mineralisation reactions occurring in REE-bearing carbonatite deposits, the most important resources of rare earths in the world.</p> </div>

Extreme chemical conditions of crystallisation of Umbrian Melilitolites and wealth of rare, late stage/hydrothermal minerals

Melilitolites of the Umbria Latium Ultra-alkaline District display a complete crystallisation sequence of peculiar, late-stage mineral phases and hydrothermal/cement minerals, analogous to fractionated mineral associations from the Kola Peninsula. This paper summarises 20 years of research which has resulted in the identification of a large number of mineral species, some very rare or completely new and some not yet classified. The progressive increasing alkalinity of the residual liquid allowed the formation of Zr-Ti phases and further delhayelitemacdonaldite mineral crystallisation in the groundmass. The presence of leucite and kalsilite in the igneous assemblage is unusual and gives a kamafugitic nature to the rocks. Passage to non-igneous temperatures (T<600 °C) is marked by the metastable reaction and formation of a rare and complex zeolite association (T<300 °C). Circulation of low-temperature (T<100 °C) K-Ca-Ba-CO2-SO2-fluids led to the precipitation of sulphates and hydrated and/or hydroxylated silicate-sulphate-carbonates. As a whole, this mineral assemblage can be considered typical of ultra-alkaline carbonatitic rocks.

Xenocrystic richterite in an olivine-nephelinite: destabilisation and diffusion phenomena

A partly destabilised Na-richterite has been found in an olivine-nephelinite from Morocco. The riehterite crystal (600 × 420 μm) is surrounded by a reaction zone (400-700 μm) of K- and Si-rich glass containing small (<50 μm) olivine (Fo80-83%) and endiopside crystals. Outwards, another zone is formed of normal magmatic minerals and circumscribes the original crystal, indicating that the destabilisation event took place at the end of the crystallisation sequence. Estimated ascent time of about 100 hours would have completely decomposed an isolated richterite crystal, which suggests that the amphibole was originally included in a xenolith. A mass-balance calculation shows that the fichterite isovolumic decomposition was accompanied by exchanges with the magma. The loss of Na from the reaction zone and the gain of AI from the magma allowed the precipitation of an analcime-rich zone observed around the destabilised amphibole and the concentration of K in the reaction zone glass. Compositional variations, Fe and Ti increase and Mg, Ca and F decrease at the richterite edge are interpreted as the result of a diffusion process. No alkali gradients are observed. The diffusion phenomenon lasted less than 100 hours and ceased to be operative at a temperature of 900-950°C i.e. just below the solidus temperature. Diffusion coefficients for the amphibole are proposed: e.g 10−9 cm2 s−1 for K2O and 10−10 for FeO at 900°C