The recently defined arctite supergroup contains nine mineral members defined as hexagonal intercalated antiperovskites, most of which have been found in pyrometamorphic rocks of the Hatrurim Complex, Israel. Three members of this supergroup: nabimusaite, gazeevite and zadovite, were identified for the first time in altered carbonate–silicate xenoliths from the Caspar and Scherer quarries, Bellerberg volcano in Germany. Present work focuses on the chemical, structural and spectroscopic investigation of these minerals and their correlation with holotype counterparts. The apparent differences are mainly related to the chemical composition, types of substitution in the tetrahedral and antiperovskite layers within the crystal structure, and position of bands in the Raman spectra. In the Bellerberg volcano xenoliths, the crystallisation of nabimusaite and gazeevite is caused by high-temperature alteration of early mineral associations (clinker-like phases) and their reaction with melt or gas generated by volcanic activity. In turn, the formation of zadovite is related to the Ba-rich silicate melt that filled the intergranular space between the rock-forming minerals.

Zadovite, BaCa6[(SiO4)(PO4)](PO4)2F (R3m, a = 7.0966(1) Å, c = 25.7284(3), V = 1122.13(3) Å3, Z = 3) and aradite, BaCa6[(SiO4)(VO4)] (VO4)2F (R3m, a = 7.1300(1), c = 26.2033(9) Å, V = 1153.63(6) Å3, Z = 3) are two new mineral species of a novel modular structure type related closely to the structure of nabimusaite, KCa12(SiO4)4(SO4)2O2F. Both minerals occur in paralavas enclosed in pyrometamorphic rocks of the Hatrurim Complex, Negev desert, Israel. Zadovite and aradite are colourless, transparent with a white streak, have a vitreous lustre and an uneven fracture. Both minerals are uniaxial (–) with refractive indices (589 nm) ω = 1.711(2), ε = 1.708(2) (zadovite) and ω = 1.784(3), ε = 1.780(3) (aradite). The zadovite structure type comprises two tetrahedral sites, which may host a broad compositional range of atoms such as Si, P, V and S. Results of electron microprobe analyses show a correlation between excess Si4+ and S6+ contents, suggesting the substitution scheme 2(P,V)5+ = Si4+ + S6+ at the tetrahedral sites. This points to the possibility of new minerals isostructural with zadovite with end-member formulae BaCa6(SiO4)2[(PO4)(SO4)]F, BaCa6(SiO4)2[(VO4)(SO4)]F, BaCa6[(SiO4)1.5(SO4)0.5](PO4)2F and BaCa6[(SiO4)1.5(SO4)0.5](VO4)2F. The Raman spectra of aradite and zadovite reflect the varying PO4 (e.g. change of band intensity at ∼1031 cm–1) and VO4 contents (e.g. change of band intensity at ∼835 cm–1). The presence of SO4 leads to an additional Raman band at ∼997 cm–1. The structure of zadovite-series minerals belonging to the nabimusaite group is characterized by a 1:1 alternation of antiperovskite-like {[FCa6](TO4)2}4+ modules and Ba(TO4)2–4 modules.