New Data on the Crystal-Chemistry of Metamict Minerals From the Velyka Vyska Syenite Massif (Ukrainian Shield)

Abstract

The structural properties and composition of metamict minerals, namely allanite, chevkinite, and britholite, occurring as inclusions in allanite from feldspar syenites of the Velyka Vyska massif (Korsun-Novomyrgorod pluton, Ukrainian Shield) were investigated by X-ray diffraction and electron probe microanalysis (EPMA). The age of the syenites is 1.7-1.8 Ga, which corresponds to their formation ages within the Ukrainian Shield. X-ray analysis shows that of the original samples of chevkinite and allanite give a broad diffraction peak between 16—28° 2Θ as well as Bragg reflections in the region of the most intense reflections of semimetamict allanite and britholite, indicating the metamict state of chevkinite and the semimetamict state of allanite. The content of radioactive Th found in the chevkinite (0.25-0.33 apfu) is higher compared to its amount in allanite (0.024-0.033 apfu). Calculated unit-cell parameters of the chevkinite and allanite samples showed that their structures underwent significant changes after annealing. There is a slight distortion of the chevkinite unit cell related to a decrease in the a and an increase in b and c edges. A decrease in b and the increase in c in the allanite is caused by a redistribution of cations in the structure and an oxidation of iron, Fe2+ → Fe3+, during heating. Thereby the stability of the allanite structure decreases and it ultimately breaks down. The structural sites A and A2 in chevkinite and allanite are mainly occupied by REEs of the cerium group. The amount of Y is minor. The substitution mechanism А2(REE)3+ + М3М2+ → А2Са2+ + М3М3+(allanite) and M2Fe3+ + M3,4Ti4+↔ M2Fe2+ + M3,4Nb5+ (chevkinite) occur. The M2 site in the structure of chevkinite and M3 in allanite contain more Fe2+ than Fe3+. This leads to a weakening of the bonds in their structures, and a stepwise breakdown and partial or total metamictization of their structures. The britholite inclusions in allanite belong to the Y variety. They were probably formed much later than allanite and chevkinite in the Velyka Vyska massif. According to the EPMA results, namely BSE-images and REE content determinations, allanite and chevkinite formed almost simultaneously.