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Tourmaline is a widespread borosilicate mineral that is well known for its variable chemistry. Although a major amount of octahedral Al in tourmaline is commonplace, the occurrence of significant amounts of tetrahedral Al is relatively rare. This paper focuses on tourmaline from the collection of the A.E. Fersman Mineralogical Museum (Russia) originated from Italy with up to 25% of Si replaced by Al at the tetrahedral site. The tourmaline is characterized by optical and scanning electron microscopy, Raman spectroscopy, infrared spectroscopy, Mössbauer spectroscopy, energy-dispersive and wavelength-dispersive X-ray analysis, laser ablation inductively coupled plasma optical emission spectrometry and single-crystal X-ray diffraction. The studied tourmaline occurs as transparent dark blue crystals (with equant external morphology) up to 3 mm in size and forms veinlets cutting a (Mg,Al)-rich metamorphosed mafic-ultramafic rock (Mg >> Fe) composed of spinel, pargasite, clinochlore, phlogopite, and hydroxylapatite. The studied tourmaline meets the criteria defining magnesio-lucchesiite and can be compositionally formed via Tschermak-like ([6]Me2+ + [4]Si4+ ↔ [6]Al3+ + [4]Al3+, where [6]Me2+ = Mg,Fe) or plagioclase-like ([9]Ca2+ + [4]Al3+ ↔ [9]Na+ + [4]Si4+) substitutions. Zones with a relatively high Si content (Si-rich) have pronounced indications of dissolution, while silicon-depleted zones (Si-poor) overgrow Si-rich zones, eventually creating a visible replacement zone of the crystal. We suggest that Si-poor tourmaline results from the Si-rich tourmaline losing Si during a metasomatic process. The resulting empirical crystal-chemical formula for the Si-poor zone is: X     C a   0.95     N a   0.03     ◻ 0.02         Σ 1.00     Y     M g   1.08     A l   0.98     F e   0.50   2 +     F e   0.43   3 +         Σ 3.00     Z     A l   5.91     F e   0.09   3 +         Σ 6.00     T     S i   4.57     A l   1.43         Σ 6.00     O   18           (BO3)3V(OH)3W[O0.95(OH)0.05]Σ1.00 [a = 15.9811(2), c = 7.12520(10) Å, R1 = 1.7%] and for the Si-rich zone is: X     C a   0.89     N a   0.11         Σ 1.00     Y     M g   1.55     A l   0.80     F e   0.34   2 +     F e   0.31   3 +         Σ 3.00     Z     A l   5.51     M g   0.44     F e   0.05   3 +         Σ 6.00     T     S i   5.35     A l   0.65         Σ 6.00     O   18           (BO3)3V(OH)3W[O0.93(OH)0.07]Σ1.00 [a = 15.9621(3), c = 7.14110(10) Å, R1 = 1.7%]. According to pressure-temperature (P-T) calculations of mineral assemblage stability and comparable data on synthetic [4]Al-rich tourmalines, the studied tourmaline was formed at 600–750 °C and 0.10–0.20 GPa. The formation of tetrahedral Al-rich tourmalines requires several unusual factors: (1) desilication of primary rocks and (2) high temperatures and relatively low pressures. [ABSTRACT FROM AUTHOR]

A series of novel KSrY1–xErx(BO3)2 (x = 0–1) phosphors that emit near‐infrared radiation was synthesized using solid‐state methods. Pure Y and Er crystals were grown using a KF flux via the top‐seeded solution growth technique. In situ high‐temperature single crystal X‐ray diffraction, Raman spectroscopy and DFT calculations were used for characterization. Within the series, a polymorphic phase transition from space group P21/m to R3m was discovered between 550 and 600°C. The concentration dependence of the luminescence intensity was measured for the samples. A strong emission of Er3+ electron transition 4I13/2 → 4I15/2 was detected within the 1529–1549 nm range, with the maximum observed for the KSrY0.4Er0.6(BO3)2 composition. [ABSTRACT FROM AUTHOR]

Crystalline calcium carbonates (CCCs) are among the most widespread minerals on the Earth's surface and play a crucial role in the global carbon cycle, heavy metal sorption and incorporation. Among the numerous factors that influence the precipitation of CCCs from solution, the most determinant are the presence of additives in the mineral-forming medium, temperature, and crystallization time (aging time). The current work fills the gaps in the study of calcium carbonate crystallization from heavy metal (Me2+ = Co, Ni, Cu Fe)-containing solutions (Me2+/Ca 0.005–1.600) at different temperatures (3 and 23 °C) and aging times (21–158 days). The resulting precipitates were studied using optical and scanning electron microscopy, powder X-ray diffraction and energy-dispersive X-ray spectroscopy. Three crystalline calcium carbonates (synthetic analogues of calcite, aragonite and monohydrocalcite), as well as amorphous carbonate (AC), were found in the resulting precipitates. Temperature and aging time have a considerable effect on the phase composition, morphology and heavy metal content in CCCs. Low temperature (3 °C) and short aging times are generally favorable for the formation of monohydrocalcite and amorphous carbonate, while calcite tends to form at a higher temperature (23 °C) and in long-term experiments. Heavy metals can be incorporated into the calcite/monohydrocalcite crystal lattice in sufficient amounts, while aragonite can host a very small amount of Me2+ (or none). Calcite can concentrate Co (up to ~0.25 atoms per formula unit (apfu)) and Ni/Cu (up to ~0.05 apfu), while its Fe content is very close to the detection limits. Calcite precipitated at a higher Me2+/Ca ratio and temperature (23 °C) contains less Me2+ compared to calcite precipitated at a lower Me2+/Ca ratio and temperature (3 °C). Monohydrocalcite can host up to ~0.1 apfu of Co/Ni/Cu with no detectable preference for Me2+. The amount of Me2+ in monohydrocalcite decreases as aging time or temperature increases. It is worth noting that AC is the main carrier of heavy metals in the system being investigated and it should be considered the main host phase in heavy metal adsorption from aqueous solutions. The results obtained can be used to solve environmental issues and in mineral resource management. [ABSTRACT FROM AUTHOR]

Yakubovichite, CaNi2Fe3+(PO4)3, a new mineral containing up to 20 wt% NiO, represents a novel type of terrestrial phosphate mineralization featuring an extreme enrichment in Ni. The mineral was discovered in the Hatrurim Formation (Mottled Zone)—pyrometamorphic complex whose outcrops are exposed in Israel and Jordan in the area coincident with the Dead Sea Transform fault system. Nickel-rich minerals in these assemblages also include Ni phosphides: halamishite Ni5P4, negevite NiP2, transjordanite and orishchinite—two polymorphs of Ni2P, nazarovite Ni12P5, polekhovskyite MoNiP2; Ni-spinel trevorite NiFe2O4, bunsenite NiO, and nickeliferous members of the hematite-eskolaite series, Fe2O3-Cr2O3 containing up to 2 wt% NiO. Yakubovichite forms polycrystalline segregations up to 0.2 mm in size composed of equant crystal grains, in association with crocobelonite, hematite, other phosphates, and phosphides. It has a deep yellow to lemon-yellow color, is transparent to translucent with vitreous luster, and has no cleavage. Mohs hardness = 4. Yakubovichite is orthorhombic, Imma, unit-cell parameters of the holotype material: a = 10.3878(10), b = 13.0884(10), c = 6.4794(6) Å, V = 880.94(2) Å3, Z = 4. Chemical composition of holotype material (electron microprobe, wt%): Na2O 1.82, K2O 1.76, CaO 6.37, SrO 0.49, BaO 1.37, MgO 2.13, NiO 21.39, CuO 0.16, Fe2O3 18.80, Al2O3 1.06, V2O3 0.44, Cr2O3 0.15, P2O5 44.15, total 100.09. The empirical formula calculated on the basis of 12 O atoms per formula unit is (Ca0.55Na0.29K0.18Ba0.04Sr0.02)1.08(Ni1.39Mg0.26Fe30.24+ V30.03+ Cu0.01Cr0.01)Σ1.94 (Fe30.90+ Al0.10)Σ1P3.02O12. Dcalc = 3.657 g cm–3. The strongest lines of powder XRD pattern [d(Å)(I)(hkl)]: 5.82(44)(011), 5.51(73)(101), 5.21(32)(200), 4.214(34)(121), 2.772(97)(240), 2.748(100)(202), 2.599(38)(400). Yakubovichite is the first mineral that crystallizes in the α-CrPO4 structure type. It has a direct synthetic analog, CaNi2Fe3+(PO4)3. Since yakubovichite is the first natural Ni-phosphate of non-meteoritic origin, the possible sources of Ni in the reported mineral assemblages are discussed. Pyrometamorphic rocks of the Hatrurim Formation were formed at the expense of the sediments belonging to a Cretaceous-Paleogene (Cretaceous-Tertiary) boundary (~66 Ma age). This geological frame marks the event of mass extinction of biological species on Earth that was likely caused by the Chicxulub impact event. The anomalous enrichment of pyrometamorphic assemblages in Ni may be related to metamorphic assimilation of Ni-rich minerals accumulated in the Cretaceous-Paleogene layer, which was formed due to a Chicxulub collision. [ABSTRACT FROM AUTHOR]

Crocobelonite, CaFe23+(PO4)2O, is a new natural oxyphosphate discovered in the pyrometamorphic complexes of the Hatrurim Formation in Israel and Jordan. Crocobelonite-bearing assemblages contain a series of anhydrous Fe-Ni phosphates, hematite, diopside, anorthite, and phosphides—barringerite Fe2P, transjordanite Ni2P, murashkoite FeP, halamishite Ni5P4, and negevite NiP2. Crocobelonite forms submillimeter-sized aggregates of prismatic to acicular crystals of saffron-red to pinkish-red color. There are two polymorphic modifications of the mineral whose structures are interrelated by the unit-cell twinning. Crocobelonite-2O is orthorhombic, Pnma, a = 14.2757(1), b = 6.3832(1), c = 7.3169(1) Å, V 666.76(1) Å3, Z = 4. This polymorphic modification is isotypic with synthetic oxy-phosphates A V 2 3 + P O 4 2 O where A = Ca, Sr, Cd. The crystal structure has been refined to RB = 0.71% based on powder XRD data, using the Rietveld method and the input structural model obtained from the single-crystal study. Chemical composition (electron microprobe, wt%) is: CaO 16.03, MgO 0.56, Fe2O3 43.37, Al2O3 0.33, SiO2 0.32, P2O5 39.45, Total 100.06. The empirical formula based on O = 9 apfu is C a 1.02 F e 1.94 3 + M g 0.05 A l 0.02 2.01 P 1.98 S i 0.02 2.00 O 9.00 The strongest lines of powder XRD pattern [d(Å)(I)(hkl)] are: 6.54(16)(200), 5.12(26)(201), 3.549(100)(102), 3.200(50) (401), 2.912(19)(220), 2.869(40)(411), 2.662(21)(501). Crocobelonite- 1M is monoclinic, P21/m, a = 7.2447(2), b = 6.3832(1), c = 7.3993(2) Å, β = 106.401(2)°, V = 328.252(14) Å3, Z = 2. This polymorphic modification does not have direct structural analogs. Its crystal structure has been solved and refined based on the single-crystal data to R1 = 1.81%. Chemical composition is: CaO 15.56, MgO 0.16, NiO 0.78, Fe2O3 41.28, Al2O3 0.45, V2O3 0.42, Cr2O3 0.23, TiO2 0.79, P2O5 39.94, Total 99.61, corresponding to the empirical formula (O = 9 a p f u) C a 0.99 F e 1.85 3 + N i 0.04 T i 0.04 A l 0.03 V 0.02 3 + C r 0.01 M g 0.01 2.00 P 2.01 O 9.00 with Dcalc = 3.604 g/cm3. The strongest lines of powder XRD pattern [d(Å)(I)(hkl)] are 6.98(17)(100), 4.40(22)(101), 3.547(100)(201), 3.485(21)(200), 3.195(50)(020), 2.855(38)(102), 2.389(33)(122). Crocobelonite represents a novel type of phosphate mineral formed by oxidation of phosphide minerals at temperatures higher than 1000 °C and near-atmospheric pressure (pyrolytic oxidation). [ABSTRACT FROM AUTHOR]

Ryabchikovite, ideally CuMg(Si2O6), a new pyroxene-group mineral (IMA No. 2021-011) was discovered in exhalations of the active Arsenatnaya fumarole, Tolbachik volcano, Kamchatka, Russia. The associated minerals are diopside, hematite, cuprospinel, fluorophlogopite, anhydrite, johillerite, tilasite, and aphthitalite-group sulfates. Ryabchikovite forms thin (up to 25 μm), light brown to reddish-brown epitactic crusts on short-prismatic brownish-gray crystals of diopside (up to 0.5 mm). The new mineral is optically biaxial (+), α = 1.685(5), β = 1.690(5), γ = 1.703(4), and 2V (meas) = 60(15)°. The average chemical composition (wt%, electron microprobe data) is: MgO 18.05, CaO 0.77, CuO 26.46, ZnO 2.23, Al2O3 0.93, Fe2O3 1.89, SiO2 50.10, total 100.43. The empirical formula calculated based on 6 O atoms per formulas unit is M g 1.05 C u 0.78 Z n 0.06 F e 0.06 3 + C a 0.03 S i 1.96 A l 0.04 O 6 Electron backscattered diffraction and powder X-ray difraction show that ryabchikovite is a Cu,Mg-ordered analog of clinoenstatite. Ryabchikovite adopts the space group P21/с and has the following unit-cell parameters: a = 9.731(9), b = 8.929(8), c = 5.221(4) Å, β = 110.00(6)°, V = 426.3(7) Å3, and Z = 4. Ryabchikovite is named in honor of the outstanding Russian geochemist and petrologist Igor Dmitrievich Ryabchikov (1937–2017). Our studies reveal that copper analogs of rock-forming minerals could be found in fumarolic systems. Their crystallization does not require high temperatures or/and pressures (below 500 °C/Pa). [ABSTRACT FROM AUTHOR]

Polekhovskyite, MoNiP2, is the first terrestrial Mo phosphide, a phosphorus-rich homolog of meteoritic monipite, MoNiP. The mineral represents a novel phosphide type of terrestrial Mo speciation. It was discovered among phosphide assemblages in pyrometamorphic rocks of the Hatrurim Formation (the Mottled Zone) in Israel, the area confined to the Dead Sea Transform fault system. Polekhovskyite occurs in the altered diopside microbreccia, as micrometer-sized euhedral crystals intimately intergrown with murashkoite, FeP and transjordanite, Ni2P, in association with Si-rich fluorapatite, hematite, and magnetite. In reflected light, the mineral has a bluish-gray color with no observable bireflectance and anisotropy. Chemical composition (electron microprobe, wt%): Mo 44.10, Ni 22.73, Fe 4.60, P 29.02, total 100.45, which corresponds to the empirical formula Mo0.99(Ni0.83Fe0.18)1.01P2.01 and leads to the calculated density of 6.626 g/cm. Polekhovskyite is hexagonal, space group P63/mmc, a = 3.330(1), c = 11.227(4) Å, V = 107.82(8) Å3, and Z = 2. The crystal structure has been solved and refined to R1 = 0.0431 based on 50 unique observed reflections. The occurrence of Mo-bearing phosphides at the Dead Sea Transform area is a regional-scale phenomenon, with the localities tracked across both Israel and Jordan sides of the Dead Sea. The possible sources of Mo required for the formation of Mo-bearing phosphides are herein reviewed; they are likely related to the processes of formation of the Dead Sea Transform fault system. The problem of anthropogenic contamination of geological samples with Mo and Ni is also discussed in the paper in the context of the general aspects of discrimination between natural and technogenic ultra-reduced phases. [ABSTRACT FROM AUTHOR]

Nazarovite, Ni12P5, is a new natural phosphide discovered on Earth and in meteorites. Terrestrial nazarovite originates from phosphide assemblages confined to pyrometamorphic suite of the Hatrurim Formation (the Mottled Zone), the Dead Sea basin, Negev desert, Israel. Meteoritic nazarovite was identified among Ni-rich phosphide precipitates extracted from the Marjalahti meteorite (main group pallasite). Terrestrial mineral occurs as micrometer-sized lamella intergrown with transjordanite (Ni2P). Meteoritic nazarovite forms chisel-like crystals up to 8 μm long. The mineral is tetragonal, space group I4/m. The unit-cell parameters of terrestrial and meteoritic material, respectively: a 8.640(1) and 8.6543(3), c 5.071(3), and 5.0665(2) Å, V 378.5(2), and 379.47(3) Å3, Z = 2. The crystal structure of terrestrial nazarovite was solved and refined on the basis of X‑ray single-crystal data (R1 = 0.0516), whereas the structure of meteoritic mineral was refined by the Rietveld method using an X‑ray powder diffraction profile (RB = 0.22%). The mineral is structurally similar to phosphides of schreibersite–nickelphosphide join, Fe3P-Ni3P. Chemical composition of nazarovite (terrestrial/meteoritic, electron microprobe, wt%): Ni 81.87/78.59, Fe <0.2/4.10; Co <0.2/0.07, P 18.16/17.91, total 100.03/100.67, leading to the empirical formula Ni11.97P5.03 and (Ni11.43Fe0.63Co0.01)12.07P4.94, based on 17 atoms per formula unit. Nazarovite formation in nature, both on Earth and in meteorites, is related to the processes of Fe/Ni fractionation in solid state, at temperatures below 1100 °C. [ABSTRACT FROM AUTHOR]

Perovskite, CaTiO3, originally described as a cubic mineral, is known to have a distorted (orthorhombic) crystal structure. We herein report on the discovery of natural cubic perovskite. This was identified in gehlenite-bearing rocks occurring in a pyrometamorphic complex of the Hatrurim Formation (the Mottled Zone), in the vicinity of the Dead Sea, Negev Desert, Israel. The mineral is associated with native α-(Fe,Ni) metal, schreibersite (Fe3P), and Si-rich fluorapatite. The crystals of this perovskite reach 50 μm in size and contain many micrometer-sized inclusions of melilitic glass. The mineral contains significant amounts of Si substituting for Ti (up to 9.6 wt% SiO2), corresponding to 21 mol% of the davemaoite component (cubic perovskite-type CaSiO3), in addition to up to 6.6 wt% Cr2O3. Incorporation of trivalent elements results in the occurrence of oxygen vacancies in the crystal structure; this is the first example of natural oxygen-vacant ABO3 perovskite with the chemical formula Ca(Ti,Si,Cr)O3–δ (δ ~0.1). Stabilization of cubic symmetry (space group Pm3̅m) is achieved via the mechanism not reported so far for CaTiO3, namely displacement of an O atom from its ideal structural position (site splitting). The mineral is stable at atmospheric pressure to 1250 ± 50 °C; above this temperature, its crystals fuse with the embedded melilitic glass, yielding a mixture of titanite and anorthite upon melt solidification. The mineral is stable upon compression to at least 50 GPa. The a lattice parameter exhibits continuous contraction from 3.808(1) Å at atmospheric pressure to 3.551(6) Å at 50 GPa. The second-order truncation of the Birch-Murnaghan equation of state gives the initial volume V0 equal to 55.5(2) Å3 and room temperature isothermal bulk modulus K0 of 153(11) GPa. The discovery of oxygen-deficient single perovskite suggests previously unaccounted ways for incorporation of almost any element into the perovskite framework up to pressures corresponding to those of the Earth's mantle. [ABSTRACT FROM AUTHOR]