The new mineral nabimusaite, KCa12(SiO4)4(SO4)2O2F (R3m, a = 7.1905(4), c = 41.251(3) Å, V = 1847.1(2) Å3, Z = 3), has been discovered in larnite-ye' elimite nodules of pyrometamorphic rocks of the Hatrurim Complex. Nabimusaite is colourless, transparent with a white streak, has a vitreous lustre and does not show luminescence. It is brittle, but shows pronounced parting and imperfect cleavage along (001). Nabimusaite is uniaxial (–), ω = 1.644(2), ε = 1.640(2) (589 nm), nonpleochroic, Mohs' hardness is ∼5 and the calculated density is 3.119 g cm–3. The crystal structure has been solved and refined to R1 = 0.0416. Its artificial analogue is known. The nabimusaite structure may be derived from that of hatrurite, also known as the clinker phase 'alite' (C3S = Ca3SiO5), and is built up by an intercalation of three positively charged hatrurite-like modules of composition [Ca12(SiO4)4O2F]3+ with inserted modules of [K(SO4)2]3–. The hatrurite-like modules in nabimusaite are characterized by octahedrally coordinated anion sites and tetrahedrally coordinated cation sites. The structure is representative of the intercalated antiperovskite type. In contrast to its synthetic analogue, nabimusaite is P-bearing. The shortened bond T–O lengths for one tetrahedral site indicates P preference at the Si2 site, located at the border of the hatrurite-like modules. Significant variations of isomorphous substitutions in nabimusaite suggest the possibility of other isostructural minerals occurring in Nature. It also seems likely that nabimusaite could serve as a prototype for new advanced synthetic materials, given the discovery of two other new minerals in the Hatrurim Complex with related modular structures, placed in the nabimusaite group. These are zadovite and aradite, as described in a companion paper (Galuskin et al., 2015a).The mineral assemblage and paragenesis of nabimusaite suggests that nabimusaite formed as a result of the reaction of potassium-enriched, sulfate-bearing melt with larnite and ellestadite. This contradicts the isochemical model that pyrometamorphic rocks of the Hatrurim Complex formed relatively fast in a practically dry system.

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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.

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The new mineral gazeevite, BaCa6(SiO4)2(SO4)2O (R3m, a = 7.1540(1), c = 25.1242(5) Å, V = 1113.58(3) Å3, Z = 3), was found in an altered xenolith in rhyodacites ofthe Shadil-Khokh volcano, Southern Ossetia and at three localities in larnite pyrometamorphic rocks of the Hatrurim Complex; Nahal Darga and Jabel Harmun, Judean Mountains, Palestinian Autonomy, and Har Parsa, Negev Desert, Israel. Larnite, fluorellestadite–fluorapatite, srebrodolskite–brownmilleriteand mayenite-supergroup minerals are the main minerals commonly associated with gazeevite. Gazeevite is isostructural with zadovite and aradite; the 1:1 type AB6(TO4)2(TO4)2W, occurs together with the structurallyrelated minerals of the nabimusaite series, 3:1 type AB12(TO4)4(TO4)2W3, where A = Ba, K, Sr...; B = Ca, Na...; T = Si, P, V5+, S6+, Al...; W = O2–,F–. Single antiperovskite layers {[WB6](TO4)2} in the structure type of gazeevite–zadovite and triple {[W3B12](TO4)4} layers in arctite–nabimusaite areintercalated with single A(TO4) layers. These minerals with an interrupted antiperovskite structure are characterized by a modular layered structure derived from hatrurite, Ca3(SiO4)O. Gazeevite is colourless, transparent, with a white streakand vitreous lustre. Gazeevite is brittle, shows pronounced parting and imperfect cleavage on {001}; it is uniaxial (–), ω = 1.640(3), ε = 1.636(2) (λ = 589 nm) and nonpleochroic; Mohs' hardness is ∼4.5, VHN50 = 417 kg mm–2. The calculateddensity is = 3.39 g cm–3. The main lines of the calculated powder X-ray diffraction pattern are as follows (d(Å)/I/hkl): 3.58/100/110, 3.07/91/021, 2.76/47/116, 1.789/73/220, 3.29/60/113, 2.78/36/024, 2.12/25/125, 2.21/21/208. Raman spectra of gazeeviteare compared with spectra of other minerals. The formation of gazeevite and minerals of the nabimusaite–dargaite series is connected with high-temperature alteration of an early assemblage of clinker minerals affected by later fluids generated by volcanic activity or combustion processes.

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Two intermediate compounds of the system Ca2SiO4–Ca3(PO4)2–CaNaPO4 were synthesized by reaction sintering at 1600°C and analyzed structurally, chemically, and optically. The structure of Ca7(PO4)2(SiO4)2 nagelschmidtite (space group P61, a = 10.7754(1) Å, c = 21.4166(3) Å) was determined by single crystal X‐ray analysis. Its unit cell can be interpreted as a supercell (≈ 2 × a, 3 × c) of the high‐temperature polymorph α‐Ca2SiO4. Evidence for pseudo‐hexagonal symmetry is shown. Using electron microprobe, the solid solution Ca7−xNax(PO4)2+x(SiO4)2−x, (x ≤ 2), of nagelschmidtite was confirmed. Volume thermal expansion coefficients of Ca6.8Na0.2(PO4)2.2(SiO4)1.8 and Ca5.4Na1.5(PO4)3.7(SiO4)0.3 were determined using high‐temperature X‐ray powder diffraction, yielding mean αV = 3.95 and 5.21 [×10−5/°C], respectively. Ca15(PO4)2(SiO4)6 is a distinct phase in the binary section Ca2SiO4–Ca3(PO4)2 and was found to extend into the ternary space according to Ca15−xNax(PO4)2+x(SiO4)6−x, (x ≤ 0.1). Quenching experiments of the latter allowed for structural analysis of a strongly disordered, defective high‐temperature polymorph of the α‐Ca2SiO4–α‐Ca3(PO4)2 solid solution. Structural relations between nagelschmidtite, Ca15(PO4)2(SiO4)6 and the end‐member compounds of the system are discussed.