Composition and origin of intermediate solid solutions in the system thorite–xenotime–zircon–coffinite

A comprehensive survey of the accessory-mineral assemblages in Variscan granites of the German Erzgebirge and Pan-African granites from Jordan revealed the occurrence of intermediate solid solutions of the tetragonal thorite–xenotime–zircon–coffinite mineral group with partially novel compositions. These solid solutions preferentially formed in evolved and metasomatically altered, P-poor leucogranites of either I- or A-type affinity. Thorite from the Erzgebirge contained up to 18.8 wt.% Y2O3, 16.1 wt.% ZrO2, and 23.3 wt.% UO2. Xenotime and zircon have incorporated Th in abundances up to 36.3 wt.% and 41.8 wt.% ThO2, respectively. Extended compositional gradation with only minor gaps is confined to hydrated members of this mineral group, and is observed to exist between thorite and xenotime, thorite and coffinite, and Y–HREE-bearing thorite and zircon. Complex, hydrous solid solutions containing elevated abundances of three or more of the endmembers are subordinate. Previously reported intermediate solid solutions between anhydrous zircon and xenotime, and anhydrous zircon and thorite, are not observed and are in conflict with experimental work demonstrating very limited miscibility between anhydrous species of endmember composition. The majority of hydrous intermediate solid solutions in the Th–Y–Zr–U system are likely thermodynamically unstable. Instead, they are probably metastable responses to unusual physico-chemical conditions involving various parameters and conditions, the relative importance of which is incompletely known. Leaching and dissolution of preexisting accessory phases during interaction with F-bearing hydrous fluids enriched in Th, Y(HREE), Zr, and/or U, and common deposition of the various elements at disequilibrium (supersaturation) seems to play a key role, but other processes may be of similar importance. Experimental work involving hydrous conditions and complex systems composed of more than two endmembers are needed to shed light into the stability relations of the chemically uncommon compositions treated in this study.