New electron-microprobe analyses of mayenite from the Ettringer Bellerberg volcano near Mayen in the Eifel district, Germany have high Cl contents and Raman spectroscopy indicates the presence of OH groups. Neither of these components is included in the generally accepted chemical formula, Ca12Al14O33. A refinement of the crystal structure by single-crystal X-ray methods reveals a previously unrecognized partial substitution. The O2 site which forms one of the apices of an AlO4 tetrahedron (with 3 × O1 sites) is replaced by 3 × O2a sites, which change the coordination of the central Al atom from tetrahedral to octahedral. This substitution is related to partial hydration of Ca12Al14O32Cl2 according to the isomorphic scheme (O2– + Cl–) ↔ 3(OH)–. The revised composition of Eifel mayenite is best described by the formula Ca12Al14O32–xCl2–x(OH)3x (x ∼0.75); the original formula, Ca12Al14O33, is inadequate. The analysed mineral can be considered to consist of endmember Ca12Al14O32Cl2 (62.5 mol.%) and endmember Ca12Al14O30(OH)6 (37.5 mol.%).

Dellaite crystals of close to end-member composition, Ca6(Si2O7)(SiO4)(OH)2, and with ∼1.5 wt.% Cl. yielding Ca6(Si2O7)(SiO4)(OH)1.75Cl0.25 have been found in skarns within the gabbroid rocks of the Birkhin complex (Eastern Siberia, Russia). The greatest Cl content analysed in a dellaite domain in this skarn is 5.2 wt.% Cl corresponding to 0.8 Cl p.f.u. Dellaite occurs in altered merwmite-larnite-bredigite-gehlenite skarns and also in calcio-olivine skarns with residual larnite. The crystal structures of Cl-free and Cl-bearing (∼1.5 wt.% Cl) dellaite have been refined, including hydrogen positions, from single-crystal X-ray data to R1 = 3.7 and 3.8%, respectively. In addition, both dellaite varieties were studied by Raman spectroscopy indicating stronger hydrogen bonds for the Cl-bearing sample, which agrees with the structural data. Cl is strongly selective and enriches at one (O6) of the two OH positions allowing for the formation of a stronger hydrogen bond O8—H8…C16 compared to O8—H8…O6. Raman spectra of the domain with ∼0.8 Cl p.f.u. confirm the general enhancement of a low-frequency band in the OH range suggesting the dominance of the O—H…Cl hydrogen bond systems.

Dellaite and killalaite, Ca3.2(H0.6Si2O7)(OH), have related modular structures, differentiated only by the Si2O7 units in killalaite and alternating Si2O7 and SiO4 units in dellaite. The similarity in cell dimensions and chemical composition suggests that trabzonite, Ca4Si3Oi0-2H2O, with Si3Oi0 trimers also belongs to the same family of structures.

The crystal structure of kyzylkumite, ideally Ti2V3+O5 (OH), from the Sludyanka complex in South Baikal, Russia was solved and refined (including the hydrogen atom position) to an agreement index, R1, of 2.34% using X-ray diffraction data collected on a twinned crystal. Kyzylkumite crystallizes in space group P21/c, with a = 8.4787(1), b = 4.5624(1), c = 10.0330(1) Å , β = 93.174(1)º, V = 387.51(1) Å3 and Z = 4. Tivanite, TiV3+O3OH, and kyzylkumite have modular structures based on hexagonal close packing of oxygen, which are made up of rutile [TiO2] and montroseite [V3+O(OH)] slices. In tivanite the rutile:montroseite ratio is 1:1, in kyzylkumite the ratio is 2:1. The montroseite module may be replaced by the isotypic paramontroseite V4+O2 module, which produces a phase with the formula Ti2V4+O6. In the metamorphic rocks of the Sludyanka complex, vanadium can be present as V4+ and V3+ within the same mineral (e.g.in batisivite, schreyerite and berdesinskiite). Kyzylkumite has a flexible composition with respect to the M4+/M3+ ratio. The relationship between kyzylkumite and a closely related Be-bearing kyzylkumite-like mineral with an orthorhombic norbergite-type structure from Byrud mine, Norway is discussed. Both minerals have similar X-ray powder diffraction patterns.

In addition to spurrite, Ca5(SiO4)2(CO3), and tilleyite, Ca5(Si2O7)(CO3)2, galuskinite, C is the third mineral in the CaO—SiO2—CO2 ternary system. Galuskinite, monoclinic, space group P21/c (a = 18.79, b = 6.72, c = 10.47 Å, β = 90.79°, V = 1322 Å3, Z = 4), occurs in thin veins which cut calcio-olivine, γ-Ca2SiO4, skarn with larnite, β-Ca2SiO4, relics. Pavlovskyite, Ca8(SiO4)2(Si3O10), and dellaite, Ca6(Si2O7)(SiO4)(OH)2, form a margin between the veins and the calcio-olivine skarn. The sanidinite facies high-temperature skarn formed ∼500 Ma ago when gabbroid rocks of the Birkhin complex (Baikal area, Eastern Siberia, Russia) intruded and contact-metamorphosed limestone xenoliths. Galuskinite is a retrograde product of skarn alteration and has neither been described from cement clinker production processes nor from studies of the CaO—SiO2—CO2 system. The crystal structure of galuskinite, refined from single crystal X-ray data to Ri = 3.1%, has a modular character. One may define a polysomatic series with spurrite and larnite as endmembers and galuskinite as a 1:1 polysome built from regular alternating spurrite and larnite modules. Differences between the X-ray powder patterns of galuskinite and spurrite are most obvious in the low 8 region. Galuskinite is named after the Russian mineralogists Irina O. Galuskina and Evgeny V. Galuskin, Faculty of Earth Sciences. University of Silesia, Poland, for their outstanding contributions to skarn mineralogy.

Several silicate-minerals, such as ardennite – Mn2+4MgAl5[Si5(As5+,V5+)O22](OH)6, Z = 2, tiragalloite – Mn2+4[Si3As5+O12(OH)], Z = 4 and medaite – Mn2+6[Si5(V5+,As5+)O18(OH)], Z = 4 possess (V5+,As5+,P5+)O4 tetrahedra. Using electron-microprobe analysis (EMPA) and single-crystal X-ray diffraction methods, the crystal chemistry of ardennite from Salam-Château, Belgium and the Vernetto mine, Italy, tiragalloite from the Gambatesa mine, Italy, and medaite from the Molinello mine, Italy and the Fianel mine, Switzerland, were studied. Structure refinements converged to R1 values of 2.10–5.67%. According to chemical analysis, the Σ(As+V+P) content increases with decreasing Si content. Thus, Si replaces pentavalent cations in tetrahedral coordination. The (As5+,V5+,P5+,Si4+)O4 tetrahedra are categorized by their connections to SiO4 tetrahedra. The (As5+,V5+,P5+,Si4+)O4 tetrahedron of ardennite is isolated, and those of tiragalloite and medaite terminate a tetrahedral chain. The <T–O> of the isolated (As5+,V5+,P5+,Si4+)O4 tetrahedron shows a positive correlation with the mean ionic radius. For (As5+,V5+,P5+,Si4+)O4 tetrahedra with one T–O–T link, <T–O> and mean ionic radius are also correlated. In addition, the longest bridging T–O bond occurs between (As,V,P,Si)O4 and the adjacent SiO4 tetrahedron. The bridging O atom is over-bonded to satisfy the charge requirement of Σ(As+V+Si).

Eringaite, Ca3Sc2(SiO4)3, a new mineral of the garnet group, is an accessory mineral in metasomatic rodingite-like rocks from the Wiluy River, Sakha-Yakutia Republic, Russia. Eringaite forms regular growth zones and irregular spots in complex garnet crystals containing a kimzeyite core. An electron back-scatter diffraction pattern with an excellent match to a garnet model with a = 12.19 Å was obtained for a grain with the largest Sc2O3 content having the crystal chemical formula (Ca2.98Y0.01Mg0.01)Σ3(Sc0.82Ti4+0.44Fe3+0.30Zr0.21Mg0.10Al0.09Cr3+0.08Fe2+0.05V3+0.01)Σ2.01(Si2.48Al0.30Fe3+0.22)Σ3O12. Eringaite is light brown to yellow with a creamy white streak. The crystals are transparent with a vitreous lustre. The calculated density of eringaite is 3.654 g cm–3. The following main modes of the Raman spectrum are characteristic of eringaite: 335, 511, 735, 880 and 937 cm–1. The strongest lines of the calculated powder diffraction data are as follows [(hkl) dhkl (I)] (400) 3.064 (69), (420) 2.740 (100), (422) 2.502 (68), (640) 1.670 (30), (642) 1.638 (82), (840) 1.370 (20), (842) 1.137 (19), (10.4.2) 1.119 (29).

The exact nature of tripuhyite remains controversial more than 100 years after the first description of the mineral. Different stoichiometries and crystal structures (rutile or tri-rutile types) have been suggested for this Fe-Sb-oxide. To address these uncertainties, we studied tripuhyite from Tripuhy, Minas Gerais, Brazil (type material) and Falotta, Grisons, Switzerland using single-crystal and powder X-ray diffraction (XRD), optical microscopy and electron microprobe analysis.

Electron microprobe analyses showed the Fe/Sb ratios to be close to one in tripuhyite from both localities. Single crystal XRD studies revealed that tripuhyite from the type locality and from Falotta have the rutile structure (P42mnm, a = 4.625(4) c = 3.059(5) and a = 4.6433(10) c= 3.0815(9) Å, respectively). Despite careful examination, no evidence for a tripled c parameter, characteristic of the tri-rutile structure, was found and hence the structure was refined with the rutile model and complete Fe-Sb disorder over the cationic sites in both cases (type material: R1 = 3.61%; Falotta material: R1 = 3.96%). The specular reflectance values of type material tripuhyite and lewisite were measured and the following refractive indices calculated (after Koenigsberger): tripuhyite nmin = 2.14, nmax = 2.27; lewisite (cubic) n = 2.04.

These results, together with those of 57Fe and 121Sb Mössbauer spectroscopy on natural and synthetic tripuhyites reported in the literature, indicate that the chemical formula of tripuhyite is Fe3+Sb5+O4 (FeSbO4). Thus, tripuhyite can no longer be attributed to the tapiolite group of minerals of general type AB2O6. A comparison of the results presented with the mineralogical data of squawcreekite suggests that tripuhyite and squawcreekite are identical. In consequence, tripuhyite was redefined as Fe3+Sb5+O4 with a rutile-type structure. Both the proposed new formula and unit cell (rutile-type) of tripuhyite as well as the discreditation of squawcreekite have been approved by the Commission on New Mineral and Mineral Names (CNMMN) of the International Mineralogical Association (IMA).

Schäferite, NaCa2Mg2(V5+O4)3; palenzonaite, NaCa2Mn22+(V5+O4)3; berzeliite, NaCa2Mg2(As5+O4)3; and manganberzeliite, NaCa2Mn2+2(As5+O4)3, are cubic minerals with garnet structures (space group Iad) in which tetrahedrally coordinated V5+ and/or As5+ at the Z site are charge balanced by disordered Na+ and Ca2+ at the X site, and divalent Mg2+ and Mn2+ cations at the octahedrally coordinated Y site. The crystal chemistry of palenzonaite (from the Molinello and Gambatesa mines, Italy, and the Fianel mine, Switzerland), berzeliite (from Långban, Sweden, and Montaldo, Italy), and manganberzeliite (from Varenche, Italy, and the Gozaisho mine, Japan) were studied by electron microprobe analysis and single-crystal X-ray diffraction methods. Structure refinements converged to R1 values of 1.36–2.42%. The tetrahedral site in these garnet structures is mainly occupied by pentavalent As5+ or V5+ (only up to about 20% randomly distributed Si4+ is present). Charge balance is maintained by variations in the Ca/Na ratio at the X site. Heterovalent substitution (Na+ ↔ Ca2+) at the distorted square antiprism X site in vanadate- and arsenate-bearing garnets allows full occupancy of the octahedral Y site by divalent cations (primarily Mg2+ and Mn2+). There is a positive correlation between the <Z–O> and <Y–O> bond lengths and the mean ionic radii of the substituent elements, but there is no correlation between the <X–O> bond length and the variable Na/Ca site occupancy. The ionic radii of octahedrally coordinated Mg2+ and Mn2+ are such that the shared octahedral–dodecahedral edges are similar in length to the unshared octahedral edges, which is a measure of lattice distortion in garnet structures.

The new mineral species vapnikite, Ca3UO6, was found in larnite pyrometamorphic rocks of the Hatrurim Formation at Jabel Harmun in the Judean desert, Palestinian Autonomy, Israel. Vapnikite is an analogue of the synthetic ordered double-perovskite β-Ca3UO6 and is isostructural with the natural fluorperovskite – cryolite Na3AlF6. Vapnikite Ca3UO6 (P21/n, Z = 2, a = 5.739(1), b = 5.951(1), c = 8.312(1) Å, β = 90.4(1)°, V = 283.9(1) Å3) forms yellow-brown xenomorphic grains with a strong vitreous lustre. Small grains up to 20−30 µm in size are wedged between larnite, brownmillerite and ye’elimite. Vapnikite has irregular fracture, cleavage and parting were not observed. The calculated density is 5.322 g cm−3, the microhardness is VHN25 = 534 kg mm−2 (mean of seven measurements) corresponding to the hardness of ∼5 on the Mohs scale. The crystal structure of vapnikite Ca3UO6 differs from that of its synthetic analogue β-Ca3UO6 by having a larger degree of Ca, U disorder. Vapnikite formed at the high-temperature retrograde stage of pyrometamorphism when larnite rocks were altered by fluids/melts of high alkalinity.

The structure of hibonite from Myanmar (space group P63/mmc, Z = 2, at room temperature a = 5.5909(1), c = 21.9893(4) Å), with simplified formula CaAl12O19 and composition (Ca0.99Na0.01)Σ1.00 was investigated between temperatures of 100 K and 923 K by single-crystal X-ray diffraction methods. Structure refinements have been performed at 100, 296, 473 and 923 K. In hibonite from Myanmar, Ti substitutes for Al mainly at the octahedral Al4 site and, to a lesser degree, at the trigonal bipyramidal site, Al2. The Al4 octahedra build face-sharing dimers. If Ti4+ substitutes at Al4, adjacent cations repulse each other for electrostatic reasons, leading to off-centre cation displacement associated with significant bond-length distortion compared to synthetic (Ti-free) CaAl12O19. Most Mg and smaller proportions of Zn and Si are assigned to the tetrahedral Al3 site. 12-coordinated Ca in hibonite replaces oxygen in a closest-packed layer. However, Ca is actually too small for this site and engages in a ‘rattling-type’ motion with increasing temperature. For this reason, Ca does not significantly increase thermal expansion coefficients of hibonite. The expansion of natural Ti,Mg-rich hibonite between 296 and 923 K along the x and the z axes is αa = 7.64×10–6 K–1 and αc = 11.19×10–6 K–1, respectively, and is thus very similar to isotypic, synthetic CaAl12O19 and LaMgAl11O19 (LMA).

The crystal structure of the rare skarn mineral trabzonite, Ca4[Si3O9(OH)]OH, from the type locality near Ikizdere, Turkey and from the Upper Chegem caldera, Northern Caucasus, Kabardino-Balkaria, Russia has been solved and refined using single-crystal X-ray data. This shows that the chemical formula should be modified from Ca4(Si3O10)˙2H2O, reported in the original trabzonite description, to an OH-bearing composition. The crystal structure, which contains Si3O10 trimers embedded in a framework of CaO6–8 polyhedra, has orthorhombic symmetry, space group Ama2, a = 20.6, b = 9.1, c = 10.3 Å. The orthorhombic A-centred cell is easily obtained by transformation from the original monoclinic cell of P21/m symmetry. The revised formula means that trabzonite and foshagite are polymorphs; foshagite has wollastonite-like silicate chains and in contrast to trabzonite it does not contain silanol groups. The structure and composition of killalaite from both localities was also studied. Single-crystal X-ray structure refinement of killalaite from the Northern Caucasus confirmed it to be non-stoichiometric with a composition between Ca6[Si2O6(OH)]2(OH)2 and Ca7[Si2O7]2(OH)2(Z = 2). Trabzonite, killalaite and dellaite form a series of modular structures which differ mainly in the degree of condensation of the SiO4 units.

The new minerals manganvesuviante and tweddillite, both formed by hydrothermal alteration of primary manganese ores, are described from the Kalahari manganese fields (Republic of South Africa). In addition, single-crystal X-ray structure refinements of both new minerals are presented.

Manganvesuvianite is a tetragonal vesuvianite mineral with the simplified formula Ca19Mn3+(Al,Mn3+,Fe3+)10(Mg,Mn2+)2Si18O69(OH)9, characterized by Mn3+ occupying the five-coordinated position (square pyramid). The crystals simple prismatic forms: {100}, {110} terminated by {101} and exhibit deep maroon red colour. With polarized light the crystals are strongly pleochroic, yellowish parallel to E and dark red to lilac parallel to O.

Tweddillite is an epidote-group mineral (space group P21/m, a = 8.932(5), b = 5.698(4), c = 10.310(5) Å, β = 114.56(4), V = 477.3(8) Å3) with the simplified formula CaSr(Mn3+,Fe3+)2Al[Si3O12](OH), closely related to strontiopiemontite. The difference between strontiopiemontite and tweddillite is the concentration of octahedral Mn3+. Strontiopiemontite has Mn3+ mainly on the M3 site whereas tweddillite has Mn3+ with minor Fe3+ on M3 and M1. Tweddillite forms aggregates of very thin dark red {001} blades characterized by striking pleochroism. The crystals appear dark red parallel to b and orange-yellow parallel to a. Perpendicular to (001) the blades appear magenta to red.

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.

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.

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.

Extended abstract of a paper presented at Microscopy and Microanalysis 2010 in Portland, Oregon, USA, August 1 – August 5, 2010.

Extended abstract of a paper presented at Microscopy and Microanalysis 2009 in Richmond, Virginia, USA, July 26 – July 30, 2009

Few electron optical inventions have revolutionized the TEM/ STEM as profoundly as the spherical aberration (Cs) corrector has. Characterization of technologically important materials increasingly needs to be done at the atomic or even sub-atomic level. This characterization includes determination of atomic structure as well as structural chemistry. With Cs correctors, the sub-Angstrom imaging barrier has been passed, and fast atomic scale spectroscopy is possible. In addition to improvements in resolution, Cs correctors offer a number of other significant improvements and benefits.

Extended abstract of a paper presented at Microscopy and Microanalysis 2007 in Ft. Lauderdale, Florida, USA, August 5 – August 9, 2007