Prediction of Gibbs free energies of formation of minerals of the alunite supergroup

A method for the prediction of Gibbs free energies of formation for minerals belonging to the alunite family is proposed, based on an empirical parameter Δ_GO⁼ M^z+(c) characterizing the oxygen affinity of the cation M^z+. The Gibbs free energy of formation from constituent oxides is considered as the sum of the products of the molar fraction of an oxygen atom bound to any two cations, multiplied by the difference of oxygen affinity Δ_GO⁼ M^z+(c) between any two consecutive cations. The Δ_GO⁼ M^z+(c) value, using a weighing scheme involving the electronegativity of a cation in a specific site (12-fold coordination site, octahedral and tetrahedral) is assumed to be constant. It can be calculated by minimizing the difference between experimental Gibbs free energies (determined from solubility measurements) and calculated Gibbs free energies of formation from constituent oxides. Results indicate that this prediction method gives values within 0.5% of the experimentally measured values. The relationships between Δ_GO⁼ M^z+(alunite) corresponding to the electronegativity of a cation in either dodecahedral sites, octahedral sites or tetrahedral sites and known as Δ_GO⁼ M^z+(aq) were determined, thereby allowing the prediction of the electronegativity of rare earth metal ions and trivalent ions in dodecahedral sites and highly charged ions in tetrahedral sites. This allows the prediction of Gibbs free energies of formation of any minerals of the alunite supergroup (bearing various ions located in the dodecahedral and tetrahedral sites). Examples are given for hydronium jarosite and hindsalite, and the results appear excellent when compared to experimental values.     

Evolution of the REE mineralogy in HP–LT metapelites of the Sebtide complex, Rif, Morocco: Monazite stability and geochronology

REE mineralogy was characterized at the micrometer scale (using scanning electron microscopy) in the four tectono-metamorphic units of the Beni Mzala window, Sebtide Complex, Internal Rif, Morocco, which sample a HP-LT metamorphic gradient from subgreenschist to blueschist/eclogite facies. These tectonic units are composed of garnet-free metapelites (and associated synmetamorphic veins) from the same homogeneous aluminium-rich and calcium-poor protolith. In that context, mineralogical differences between units are assumed to result from contrasted pressure and temperature histories. Light REE-bearing Al-phosphates of the crandallite group with florencite-rich composition and variable goyazite content are the dominant LREE minerals in the lowest-grade units, Tizgarine (300 °C, 3 kbar as peak conditions) and Boquete de Anjera (350 °C, 10 kbar). In the latter unit, metamorphic florencite is associated with MREE-rich monazite. In the schist of the highest-grade units, Beni Mzala 2 (420–450 °C, 12 kbar) and Beni Mzala 1 (550 °C, 16 kbar), associations of allanite-rich epidote and synchisite (a LREE-fluorocarbonate) are found whereas florencite and monazite are no longer observed. At the wall of the quartz–kyanite veins, retrograde monazite-(Ce) with grain size of 20 to 50 μm is the only LREE-bearing mineral. Th–Pb and U–Pb SIMS data on some of these grains yield ages of 21.3 ± 1.7 Ma and 20.9 ± 2.1 Ma, respectively, consistent with previous K–Ar ages obtained on retrograde clay–mica mixtures in rocks from the same locality. The identification of a stability field for monazite in high-pressure aluminous metapelites with an upper thermal-limit below 450 °C as well as the derivation of meaningful U–Pb and Th–Pb SIMS ages demonstrates the monazite potential for dating HP-LT metapelites. However, since, under these conditions, monazite growth occurs below its admitted closure-temperature, these ages must be interpreted on the basis of monazite textural relationships.