Qeltite (IMA2021–032), ideally Ca3Ti(Fe2Si)Si2O14, was found in gehlenite–rankinite–wollastonite paralava from a pyrometamorphic rock of the Hatrurim Complex at Nabi Musa locality, Judean Desert, West Bank, Palestine. It generally occurs as light-brown flattened crystals up to 40–50 μm in length and less than 5 μm in thickness. Its aggregates reach 100–200 μm in size. Its empirical crystal chemical formula based on 14 O is: (Ca2.96Sr0.02Mn0.01)Σ2.99Ti4+(Fe3+1.59Si0.60Al0.43Ti4+0.38Cr0.01)Σ3.01(Si1.99P0.01)Σ2O14. The strongest reflections in its calculated X-ray diffraction pattern are [d, Å, (I, %), hkl]: 3.12, (100), 111; 2.85, (61), 201; 2.85, (48), 021; 2.32, (45), 211; 6.93, (31), 100; and 1.81, (30), 212. Qeltite is trigonal and crystallises in the noncentrosymmetric P321 space group, with a = 8.0077(5) Å, c = 4.9956(4) Å, V = 277.42(4) Å3 and Z = 1. Its microhardness VHN25 is 708(17) kg/mm2 and its hardness on the Mohs scale is ~6. Its calculated density is 3.48 g/cm3. It was found in fine-grained mineral aggregates within coarse-grained main minerals of rankinite–gehlenite paralava with subordinate wollastonite, Ti-bearing andradite and kalsilite. In these aggregates, the mineral is associated with khesinite, paqueite and pseudowollastonite, indicating a high-temperature genesis (~1200°C). Its crystallisation can be compared with the crystallisation of minerals containing refractory inclusions in meteorites.

Deynekoite, Ca9□Fe3+(PO4)7 (R3c, a = 10.3516(3)Å, c = 37.1599(17)Å, V = 3448.4(3)Å3 and Z = 6), a new mineral of the merrillite group was found in the contact facies of paralava of the Hatrurim Complex in the Daba-Siwaqa pyrometamorphic rock field, Jordan. The paralava, consisting of diopside, tridymite, anorthite, wollastonite and fluorapatite, is enriched in Fe-bearing phosphides and phosphates at the contact with the altered country rock. Cristobalite overgrowing tridymite has a fish-scales texture indicating that temperature of paralava could have reached 1500°C. Deynekoite with empirical formula (Ca8.90Na0.11K0.02)Σ9.03(Fe3+0.62Mg0.30Al0.05)Σ0.97P6.98V5+0.05O27.70(OH)0.30 forms transparent, light-yellow or light-brown grains up to 30–40 μm in size. Microhardness of deynekoite, VHN25 = 319(29) kg/mm2, corresponds to Mohs hardness = 4.5. Its density was calculated as 3.09 g⋅cm–3 on the basis of its empirical composition and structural data. Deynekoite is uniaxial (−), its refractive indices are ω = 1.658(3), ɛ = 1.652(3) (λ = 589 nm), and pleochroism is not observed. The formation of phosphides on the boundary of the paralava and country rock is connected with carbothermal reductive reactions and realised at temperatures above 1300°С. With decreasing temperature and increasing oxygen activity, phosphides are replaced by Fe2+-bearing phosphates. Deynekoite, which contains Fe3+ (substituting for Fe2+-phosphates) and a small amount of water, formed at temperatures of 600–800°C.

The new mineral mazorite, ideally Ba3(PO4)2, a P-analogue of gurimite Ba3(VO4)2, was discovered in rankinite paralava hosted by the massive gehlenite-bearing pyrometamorphic rocks of the Hatrurim Complex in Israel. It has also recently been discovered in xenolith samples from the Bellerberg volcano in Germany. Holotype mazorite usually forms colourless plate-like crystals up to 70–100 μm in length but also occurs in small aggregates in association with other rare Ba-bearing minerals such as zadovite, celsian, hexacelsian, bennesherite, sanbornite, walstromite, fresnoite, gurimite, alforsite and barioferrite. The mineral is transparent, exhibits vitreous lustre and has a good cleavage on (001). Optically, mazorite is uniaxial (+), with ω = 1.760(3) and ɛ = 1.766(3) (λ = 589 nm). The empirical formula of the holotype mazorite calculated on 8O is (Ba2.69K0.22Na0.04Ca0.02Sr0.01)Σ2.98(P1.16V0.57S0.24Al0.04Si0.03)Σ2.04O8. Mazorite crystallises in space group R$\bar{3}$m, with unit-cell parameters a = 5.6617(5) Å, c = 21.1696(17) Å, V = 587.68(9) Å3 and Z = 3. Its crystal structure consists of BaO12, BaO10, and PO4 polyhedra, ordered along the c-axis in PO4–BaO10–BaO12–BaO10–PO4 columnar arrangement characteristic for palmierite-supergroup minerals. A tetrahedrally coordinated site is generally occupied by P5+ but can be partially substituted by V5+ and S6+. This substitution is shown in the Raman spectrum of mazorite, which reveals bands that can be assigned to the stretching and bending vibrations of (PO4)3–, (VO4)3– and (SO4)2– groups. The Raman spectra of mazorite from two localities (Hatrurim and Bellerberg) and spectra of minerals belonging to the mazorite Ba3(PO4)2 to gurimite Ba3(VO4)2 solid-solution series are presented. The gradual shift of the Raman bands, caused by cation substitutions, is well observed. The high V5+ → P5+ substitution is also observed for gurimite, for which the first X-ray structural data are also presented. Mazorite and other Ba-bearing minerals crystallised from a small portion of residual melt enriched in incompatible elements, such as Ba, V, P, U, S, Ti and Nb, at a temperature of ~1000°C.

Fluoralforsite, ideally Ba5(PO4)3F, (space group P63/m (#176), Z = 2, a = 10.0031(2) Å, c= 7.5382(2) Å and V = 653.23(3) Å3), is a new mineral species of the apatite group – a Ba-analogue of fluorapatite and a F-analogue of alforsite. It was discovered in rankinite paralava filling cracks in pyrometamorphic gehlenite hornfels near the tributary of wadi Zohar and Gurim Anticline, Hatrurim Basin, Negev Desert, Israel. Fluoralforsite occurs in small intergranular spaces between large gehlenite and garnet crystals and in enclaves inside large rankinite crystals with other Ba minerals such as walstromite, zadovite, bennesherite, gurimite, mazorite, barioferrite and baryte. It forms tiny transparent, colourless crystals up to 50 μm with a white streak and a vitreous lustre. The cleavage was not observed. It exhibits a brittle tenacity and a conchoidal fracture. The estimated Mohs hardness is 4–4½, and its calculated density is 4.57 g/cm–3. Fluoralforsite is uniaxial (–) with refractive indices (589 nm) nω = 1.689(3) and nɛ = 1.687(3). The empirical crystal-chemical formula for the holotype calculated on the basis of 8 cations is: (Ba3.81Ca0.97Na0.07K0.05Sr0.05Fe0.05)Σ5(P5+2.32V5+0.29S6+0.22Si0.17)Σ3O12(F0.85Cl0.13)Σ0.98. The crystal structure was refined from single-crystal X-ray diffraction data with R1 = 0.0192. The structural investigation indicated an ordered arrangement of Ba/Ca at the M1 site within individual columns running along the c-axis, but a disordered distribution among adjacent columns throughout the structure, which enables the maintenance of the P63/m space group. Fluoralforsite was formed at the final stage of crystallisation as a result of a reaction between the primary mineral assemblages and residual melt.

Gismondine-Sr, recently discovered in the Hatrurim Complex in Israel, has been recognised in a xenolith sample from the Bellerberg volcano in Germany. The empirical crystal-chemical formula indicates elevated K content: (Sr1.74Ca1.05Ba0.09K1.56Na0.49)Σ4.93[Al7.98Si8.06O32]⋅9.62H2O. Additionally, Ba-rich gismondine and amicite have been found in the low-temperature mineral association of the pyrometamorphic rock from the Hatrurim Complex. The Raman spectra of the studied zeolites and the crystal structure of gismondine-Sr from the second occurrence are presented. A review of zeolites with GIS framework-type structure leads to the following conclusions: (1) garronite-Na and gobbinsite are equivalent and constitute a solid solution with garronite-Ca; (2) gismondine-Ca, -Sr, and amicite belong to one mineral series; (3) two zeolites series with different R-factors (defined as Si/(Si+Al+Fe)) can be distinguished within GIS topology: the garronite series (R > 0.6) including garronite-Ca and gobbinsite, with general formula (MyD0.5(x–y))[AlxSi(16–x)O32]⋅nH2O, where M and D refer to monovalent and divalent cations, respectively; and the gismondine series, including amicite, gismondine-Sr and gismondine-Ca, with R ≈ 0.5, and the general formula (MyD0.5(8–y))[Al8Si8O32]⋅nH2O. The Raman band between 475 cm–1 and 485 cm–1 is distinctive for the garronite series, whereas the band around 460 cm–1 is characteristic of the gismondine series. On the basis of these findings, a revision of GIS zeolites nomenclature is suggested.

Corundum with inclusions of enigmatic super-reduced minerals was found in mineral separates received as a result of alluvial sediment exploration near Mt Carmel, Israel by the Shefa Yamim Company. This corundum, registered as ‘Carmel sapphireTM’, has been an object of numerous publications by W. Griffin's scientific team, in which they propose a questionable hypothesis of sapphire formation at the crust–mantle boundary with the participation of CH4+H2 fluids. Typically the Carmel sapphire is in small fragments of breccia with white cement, which in the opinion of Griffin et al. is a carbonate-cemented volcanic ash. Our investigation of the ‘white breccia’ showed that it consists of unsorted angular fragments of Carmel sapphire from ~1 μm to 7 mm in size cemented by aluminium hydroxides (bauxite) and is a waste product of the fused alumina process, i.e. it has an anthropogenic origin. Phases typical for slags of fused alumina production and metallurgical slags were identified in the ‘white breccia’. Carmel sapphire has numerous microscopic spherical inclusions of Si–Fe alloy indicating that the removal of Si and Fe from the corundum melt occurred at a temperature >2000°С. Osbornite, TiN, from Carmel sapphire has a chemical zonation characteristic of osbornite from fused alumina with enrichment of central zones in carbon. Comparison of the growth heterogeneity of Carmel sapphire and ‘electrocorundum’ indicates that the crystallisation of the corundum melt proceeded in a similar way. Unfortunately, in the case of Carmel sapphire from the Carmel locality, the contamination of geological samples with anthropogenic material has led to popularisation of biased views.

Calciolangbeinite, ideally K2Ca2(SO4)3, exists in two modifications, cubic and, first described in the present paper, orthorhombic. They are topologically-similar polymorphs which can be designated as calciolangbeinite-C and calciolangbeinite-O. Calciolangbeinite-O is the first natural orthorhombic langbeinite-like sulfate. It clearly differs from calciolangbeinite-C in the powder X-ray diffraction pattern, optical data and Raman spectrum. Calciolangbeinite-O is found in sublimates of the active Arsenatnaya fumarole at the Tolbachik volcano, Kamchatka, Far Eastern Region, Russia and in pyrometamorphic rocks of the Hatrurim Complex at Jabel Harmun, Judean Desert, Palestinian Autonomy and Har Parsa, Negev Desert, both in Israel. Calciolangbeinite-C is known only in fumarole sublimates at Tolbachik. Calciolangbeinite forms a continuous solid-solution system with langbeinite K2Mg2(SO4)3. The majority of the system is represented by cubic phases, and only members with compositions K2(Ca2.0–1.9Mg0.0–0.1)(SO4)3 have orthorhombic symmetry under room-temperature conditions. The crystal structure of calciolangbeinite-O was studied on a single crystal, chemically very close to K2Ca2(SO4)3, from Tolbachik (R1 = 2.75%). The unit-cell parameters are: a = 10.3330(2), b = 10.5027(2), c = 10.1763(2) Å, V = 1104.37(4) Å3 and Z = 4; space group is P212121. Calciolangbeinite-O is a low-temperature modification of K2Ca2(SO4)3 belonging to the K2Cd2(SO4)3 structure type whereas calciolangbeinite-C (space group P213), a high-temperature modification, has the langbeinite-type structure. The significant Mg admixture in calciolangbeinite-C from Tolbachik probably stabilises its cubic structure at room temperature. In both high-temperature fumaroles and pyrometamorphic rocks calciolangbeinite crystallises in the cubic modification, and during cooling its chemical variety close to the end-member K2Ca2(SO4)3 undergoes phase transition to calciolangbeinite-O, whereas the Mg-enriched varieties of the mineral remain calciolangbeinite-C.

A common attribute of two rare natural chromium-bearing oxides: mcconnellite, CuCrO2, discovered more than 40 years ago in Guyana, and a new mineral ellinaite, CaCr2O4, described from two localities (Brazil and Israel) recently, is that these minerals are poorly studied due to their rarity and small size. Mcconnellite and ellinaite in the present study were found in varicoloured marbles of the pyrometamorphic Hatrurim Complex in the Tulul Al Hammam area, Daba-Siwaqa, Jordan. Structural data obtained for ellinaite (Pnma, a = 9.0875(2), b = 2.9698(1), c = 10.6270(3) Å and V = 286.80(2) Å3), with an empirical formula (Сa1.00Sr0.01)Σ1.01(Cr3+1.79Al0.07Ca0.04Fe3+0.04 Ti4+0.03Mg0.03)Σ2.00O4, is similar to the structural data of synthetic analogue β-CaCr2O4 but differs significantly from the data obtained for ellinaite from Brazil and Israel despite the fact that all the natural phases have a similar composition. Single-crystal X-ray diffraction data for mcconnellite from Jordan (R$\bar{3}$m, a = b = 2.9756(1) and c = 17.124(1) Å) with composition (Cu0.98Ca0.03Sr0.01)Σ1.02(Cr3+0.90Al0.05 Fe3+0.03)Σ0.98O2, is the first determination of a natural Cu-delafossite-type structure. This paper also presents the results of a single-crystal Raman study for mcconnellite and ellinaite, which indicates that the spectral features of these minerals is dependent on crystal orientation.

Levantite, with the end-member formula KCa3(Al2Si3)O11(PO4), is the phosphate analogue of latiumite, KCa3(Al3Si2)O11(SO4, CO3) found in gehlenite–wollastonite hornfels on Har Parsa, Negev Desert, Israel. Levantite forms later zones on long-prismatic crystals of latiumite. Rarer homogeneous colourless levantite crystals up to 0.2 mm long and with mean composition (K0.94Ba0.01Na0.01□0.04)Σ1.00(Ca2.96Mg0.03)Σ2.99{(Si2.69Al2.06Fe3+0.16P0.06)Σ4.97O11}[(PO4)0.65(SO4)0.35]Σ1.00 were noted. Minerals of the levantite–latiumite series are associated with gehlenite, wollastonite, clinopyroxene of the esseneite–diopside series, anorthite and Ti-bearing andradite. Levantite crystalises in space group P21 with unit-cell parameters a = 12.1006(9) Å, b = 5.1103(4) Å, c = 10.8252(9) Å, β = 107.237(8)°, V = 639.34(9) Å3 and Z = 2. The structure of levantite is analogous to latiumite. It is formed by tetrahedral hybrid zweier double layers [(Si,Al)10O22] connected by Ca atoms. Three Ca atoms linked to different double layers are bridged over by (PO4) and minor (SO4) groups. K atoms reside in the cavities between two superimposed zweier double layers. The measured micro-indentation hardness of levantite gave VHN50 = 580(19) (mean of 14), range 550–611 kg/mm2, which correlates with 5 on the Mohs scale. Cleavage is good on (100). Twinning on (100) is polysynthetic or simple. The calculated density is 2.957 g cm–3. Levantite is optically negative with α = 1.608(2), β = 1.618(2), γ = 1.622(2) (λ = 589 nm), 2Vmeas. = 70(5)° and 2Vcalc. = 64.3°. Dispersion of the optical axes r > v is weak; the optical orientation is: Z = b, X ^ c = 22–27°; and it is non-pleochroic. Minerals of the levantite–latiumite series from Israel show characteristic Raman spectra with the main bands at 994 cm–1 [ν1(SO4)2–] and 945 cm–1 [ν1(PO4)3–]. The band intensity ν1(PO4)3–/ν1(SO4) ratio is well correlated with P and S contents in the investigated minerals. The strongest lines in the powder diffraction pattern [dobs, Å (I, %) (hkl)] are: 3.0762(100)(310), 2.8551(96)($\bar 2$13), 2.9704(92)($\bar 3$12), 2.8573(83)(013), 2.5552(66)(020), 2.8228(48)(212), 2.8893(40)(400), and 3.0634(30)(103).

Dargaite, ideally BaCa12(SiO4)4(SO4)2O3, is an additional member of the arctite group belonging to minerals with a modular intercalated antiperovskite structure derived from hatrurite. The holotype specimen was found at a small outcrop of larnite pseudoconglomerates in the Judean Mts, West Bank, Palestinian Autonomy. Larnite, fluorellestadite–fluorapatite, brownmillerite, fluormayenite–fluorkyuygenite and ye'elimite are the main minerals of the holotype specimen; ternesite, shulamitite and periclase are noted rarely. Dargaite, nabimusaite and gazeevite occur in linear zones with higher porosity within larnite rocks. Pores are filled with ettringite and Ca-hydrosilicates, less commonly with gibbsite, brucite, baryte, katoite and calciolangbeinite. Dargaite is colourless, transparent with a white streak and has a vitreous lustre. It exhibits pronounced parting and imperfect cleavage along (001). Mohs’ hardness is ~4.5–5.5. The empirical formula is (Ba0.72K0.24Na0.04)Σ1(Ca11.95Mg0.04Na0.01)Σ12([SiO4]0.91 [PO4]0.05[AlO4]0.03[Ti4+O4]0.01)Σ4([SO4]0.84[PO4]0.14[CO3]0.02)Σ2(O2.54F0.46)Σ3. Dargaite is trigonal R$\overline 3 $m, the unit-cell parameters are: a = 7.1874(4) Å, c = 41.292(3) Å, V = 1847.32(19) Å3 and Z = 3. The crystal structure of dargaite was refined from X-ray single-crystal data to R1 = 3.79%. The calculated density is 3.235 g cm–3. The following main Raman bands are distinguished on the holotype dargaite (cm–1): 122, 263, 323, 464, 523, 563, 641 and 644, 829 and 869, 947, 991 and 1116. The formation conditions of dargaite are linked to the local occurrence of pyrometamorphic by-products (gases, fluids and melts) transforming earlier mineral associations at ~900°C.

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.

Dzierżanowskite, , a thiocuprate, was found in larnite pseudoconglomerate rocks of the Hatrurim Complex at Jabel Harmun, Palestinian Autonomy, Israel. Dzierżanowskite occurs in larnite pebbles, which are embedded in a low-temperature mineral matrix. Associated minerals are larnite, brownmillerite, fluorellestadite, ye'elimite, gehlenite, periclase, ternesite, nabimusaite, vorlanite, vapnikite, fluormayenite, fluorkyuygenite, oldhamite, jasmundite, covellite, chalcocite and pyrrhotite. Electron microprobe analyses yield an average composition of Cu 55.25, Fe 0.13, S 27.46 and Ca 16.99, total 99.83 wt.%. The empirical formula of dzierżanowskite, based on 5 atoms, is Ca0.98Cu2.02Fe0.01S1.99. Dzierżanowskite forms grains up to 15 μm in size or rims on oldhamite and laminar intergrowths with chalcocite and covellite. Dzierżanowskite is dark orange, has a cream streak and a submetallic lustre. In reflected light it is grey, with a cream tint and characteristic yellow-orange internal reflections. The calculated density of dzierżanowskite is 4.391 g cm -3. Three bands at 300, 103 and 86 cm -1 are observed in the Raman spectrum. The strongest lines of the calculated powder diffraction pattern are [d, Å (I) hkl]: 2.358(100) 102, 1.970(93)110, 3.023(78) 011, 6.523(36) 001, 3.412 (28) 100, 1.834(28) 103. Dzierżanowskite was also found in unusual jasmundite rocks, forming small ‘paleofumaroles’ within areas of low-temperature hydrothermal rocks bearing larnite pseudoconglomerates at Jabel Harmun. Dzierżanowskite is a superimposed phase of the high-temperature alteration of pyrometamorphic rocks subjected to by-products (melts/fluids and gases) of pyrometamorphism originating in the deeper levels of combustion.

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.