Search Results (11)

Zoharite (IMA 2017-049), (Ba,K)₆ (Fe,Cu,Ni)₂₅S₂₇, and gmalimite (IMA 2019-007), ideally K₆□Fe²⁺₂₄S₂₇, are two new sulfides of the djerfisherite group. They were discovered in an unusual gehlenite–wollastonite paralava with pyrrhotite nodules located in the Hatrurim pyrometamorphic complex, Negev Desert, Israel. Zoharite and gmalimite build grained aggregates confined to the peripheric parts of pyrrhotite nodules, where they associate with pentlandite, chalcopyrite, chalcocite, digenite, covellite, millerite, heazlewoodite, pyrite and rudashevskyite. The occurrence and associated minerals indicate that zoharite and gmalimite were formed at temperatures below 800 °C, when sulfides formed on external zones of the nodules have been reacting with residual silicate melt (paralava) locally enriched in Ba and K. Macroscopically, both minerals are bronze in color and have a dark-gray streak and metallic luster. They are brittle and have a conchoidal fracture. In reflected light, both minerals are optically isotropic and exhibit gray color with an olive tinge. The reflectance values for zoharite and gmalimite, respectively, at the standard COM wavelengths are: 22.2% and 21.5% at 470 nm, 25.1% and 24.6% at 546 nm, 26.3% and 25.9% at 589 nm, as well as 27.7% and 26.3% at 650 nm. The average hardness for zoharite and for gmalimite is approximately 3.5 of the Mohs hardness. Both minerals are isostructural with owensite, (Ba,Pb)₆(Cu,Fe,Ni)₂₅S₂₇. They crystallize in cubic space group Pm$\overline{3}$m with the unit-cell parameters a = 10.3137(1) Å for zoharite and a = 10.3486(1) Å for gmalimite. The calculated densities are 4.49 g·cm⁻³ for the zoharite and 3.79 g·cm⁻³ for the gmalimite. The primary structural units of these minerals are M₈S₁₄ clusters, composed of MS₄ tetrahedra surrounding a central MS₆ octahedron. The M site is occupied by transition metals such as Fe, Cu, and Ni. These clusters are further connected via the edges of the MS₄ tetrahedra, forming a close-packed cubic framework. The channels within this framework are filled by anion-centered polyhedra: SBa₉ in zoharite and SK₉ in gmalimite, respectively. In the M₈S₁₄ clusters, the M atoms are positioned so closely that their d orbitals can overlap, allowing the formation of metal–metal bonds. As a result, the transition metals in these clusters often adopt electron configurations that reflect additional electron density from their local bonding environment, similar to what is observed in pentlandite. Due to the presence of shared electrons in these metal–metal bonds, assigning fixed oxidation states—such as Fe²⁺/Fe³⁺ or Cu⁺/Cu²⁺—becomes challenging. Moreover, modeling the distribution of mixed-valence cations (Fe²⁺/³⁺, Cu⁺/²⁺, and Ni²⁺) across the two distinct M sites—one located in the MS₆ octahedron and the other in the MS₄ tetrahedra—often results in ambiguous outcomes. Consequently, it is difficult to define an idealized end-member formula for these minerals. Full article

Laser ablation combined with inductively coupled plasma mass spectrometry for the analysis of trace elements in specially prepared glass beads is adapted to silicate rocks of unusual compositions. The modified technique is applied to standard samples and garnet-rich combustion metamorphic rocks (paralavas) from the Hatrurim Formation, Israel. Thirty-two to thirty-five minor and trace elements, including high field strength elements, rare earth elements and Y, are determined in 5–8 mg powder aliquots of samples with large ranges of major-, minor-, and trace-element contents. As the first step of the study, the composition of the NIST SRM 612, BCR-2, and AGV-2 reference materials is analyzed to assess the accuracy and precision of analytical data. The results for standard samples agree well with the compiled estimates (3.5 to 12.4% relative standard deviation) for all elements except Cu (18.1%). The following step is to analyze, with the same procedure, the glass beads of paralava, which are remarkable due to their high trace-element loading. Good agreement (70%–100%) with the compositions determined previously by aqueous nebulizer mode ICP-MS confirms that the method is a promising tool for the rapid and precise analysis of compositionally complex materials available in small amounts. Full article

Silicocarnotite, Ca₅[(PO₄)(SiO₄)](PO₄), was first described from slag over 140 years ago. In 2013, it was officially recognised as a mineral after being discovered in the larnite–gehlenite hornfels of the pyrometamorphic Hatrurim Complex. This paper describes the composition and structure of V-bearing silicocarnotite, crystals of which were found in a thin paralava vein cutting through the gehlenite hornfels. A network of thin paralava veins a few centimetres thick is widespread in the gehlenite hornfels of the Hatrurim Basin, Negev Desert, Israel. These veins, typically coarse crystalline rock and traditionally referred to as paralava, have a symmetrical structure and do not contain glass. Silicocarnotite in the paralava, whose primary rock-forming minerals are gehlenite, flamite, Ti-bearing andradite, rankinite and pseudowollastonite, was a relatively late-stage high-temperature mineral, crystallising at temperatures above 1100 °C. It formed from the reaction of a Si-rich residual melt with pre-existing fluorapatite. A single-crystal structural study of silicocarnotite (Pnma, a = 6.72970(12) Å, b = 15.5109(3) Å, c = 10.1147(2) Å) suggests that the phenomenon of Ca1 position splitting observed in this mineral is most likely related to the partial ordering of Si and P in the T2O₄ tetrahedrons. Raman studies of silicocarnotite with varying vanadium content have shown that phases with V₂O₅ content of 3–5 wt.% exhibit additional bands at approximately 864 cm⁻¹, corresponding to vibrations of ν₁(VO₄)³⁻. Full article

Crystals of karwowskiite, Ca₉Mg(Fe²⁺_0.5□_0.5)(PO₄)₇, a new mineral of the merrillite group, were found on an amygdule wall in the central part of an anorthite–tridymite–diopside paralava of the Hatrurim Complex, Daba-Siwaqa, Jordan. The amygdule was filled with a sulfide melt, which after crystallization gave a differentiated nodule, consisting of troilite and pentlandite parts and containing tetrataenite and nickelphosphide inclusions. Karwowskiite crystals are colorless, although sometimes a greenish tint is observed. The mineral has a vitreous luster. The microhardness VHN₂₅ is 365 (12), corresponding to 4 on the Mohs hardness scale. Cleavage is not observed, and fracture is conchoidal. The calculated density is 3.085 g/cm³. Karwowskiite is uniaxial (−): ω = 1.638 (3), ε = 1.622 (3) (λ = 589 nm), and pleochroism is not observed. The composition of karwowskiite is described by the empirical formula: Ca_9.00(□_0.54Fe²⁺_0.23Mg_0.12Na_0.04 Sr_0.03 Ni_0.03K_0.01) _Σ1.00Mg_1.00(PO₄)_7.02. Karwowskiite is distinct from the known minerals of the merrillite subgroup with the general formula A₉XM[TO₃(Ø)]₇, where A = Ca, Na, Sr, and Y; X = Na, Ca, and □; M = Mg, Fe²⁺, Fe³⁺, and Mn; T = P; and Ø = O, in that the X site in it is occupied by Fe²⁺_0.5□_0.5. Karwowskiite is trigonal, space group R-3c with a = 10.3375 (2) Å, c = 37.1443 (9) Å, and V = 3437.60 (17) ų. Karwowskiite crystallizes at temperatures lower than 1100 °C in a thin layer of secondary melt forming on the walls of amygdules and gaseous channels in paralava as a result of contact with heated gases which are by-products of the combustion process. Full article

For the first time, chromium disulphides, known from meteorites, such as caswellsilverite, NaCrS₂; grokhovskyite, CuCrS₂; and a potentially new mineral, AgCrS₂, as well as the products of their alteration, such as schöllhornite, Na_0.3CrS₂∙H₂O, and a potentially new mineral with the formula {Fe_0.3(Ba,Ca)_0.2} CrS₂·0.5H₂O, have been found in terrestrial rock. Layered chromium disulphides were found in unusual phosphide-bearing breccia of the pyrometamorphic Hatrurim Complex in the Negev Desert, Israel. The chromium disulphides belong to the central fragment of porous gehlenite paralava cementing altered host rock clasts. The empirical formula of caswellsilverite is (Na_0.77Sr_0.03Ca_0.01)_Σ0.81(Cr³⁺_0.79Cr⁴⁺_0.18V³⁺_0.01 Fe³⁺_0.01)_Σ0.99S₂·0.1H₂O, and the end-member content of NaCrS₂ is 76%. It forms single crystals in altered pyrrhotite aggregates. Grokhovskyite has the empirical formula {Cu⁺_0.84Fe³⁺_0.10Ca_0.06 Na_0.01 Sr_0.01Ba_0.01}_Σ1.03(Cr³⁺_0.94 Fe³⁺_0.05 V³⁺_0.05)_Σ1.00S₂·0.35H₂O, and the CuCrS₂ end-member content is 75–80%. A potentially new Ag-bearing chromium disulphide is characterised by the composition (Ag_0.89Cu_0.07)_Σ0.96(Cr_0.98 Fe_0.03V_0.01Ni_0.01)_Σ1.04S₂. Caswellsilverite, grokhovskyite and AgCrS₂ form in gehlenite paralava at high temperatures (near 1000 °C) and low pressure under reducing conditions. The structure of the layered chromium disulphides, MCrS₂, is characterised by the presence of hexagonal octahedral layers (CrS₂)¹⁻, between which M-sites of the monovalent cations Ag, Cu and Na set. A low-temperature alteration of the layered chromium disulphides, when schöllhornite and {Fe_0.3(Ba,Ca)_0.2}CrS₂·0.5H₂O form, is reflected in the composition and structural modification of the layer with monovalent cations, whereas the octahedral layer (CrS₂)¹⁻ remains unchanged. Full article

The Hatrurim Basin, Israel, is located on the western border of the Dead Sea Transform. This is one of the localities of a unique pyrometamorphic complex whose genesis remains problematic. This paper deals with zeolite-bearing rock that is known in the Hatrurim Basin only. The strata subjected to zeolitization is called the “olive unit” and consists of anorthite–pyroxene (diopside–esseneite) hornfels. Zeolitization occurred in an alkaline environment provided by the interaction of meteoric water with Portland-cement-like rocks of the Hatrurim Complex. The resulting zeolite-bearing rocks contain 20–30% zeolitic material. The main zeolitic minerals are calcic: thomsonite-Ca ± Sr, phillipsite-Ca, gismondine-Ca, and clinoptilolite-Ca. The remainder is calcite, diopsidic pyroxene, garnets (either Ti-andradite and/or hydrogrossular), and less frequently, fluorapatite, opal, and others. Their major mineralogical and chemical compositions resemble carbonated zeolite-blended Portland mortar. Rocks show different values of porosity. Their mechanical characteristics are much better for samples with porosity values below 24%. The related parameters are like those of blended concretes. The minimal age of zeolitization is 5 Ka. The natural zeolite-bearing rocks are resistant to weathering in the Levant desert climate. Full article

In the last 15 years, zeolite-like mayenite, Ca₁₂Al₁₄O₃₃, has attracted significant attention in material science for its variety of potential applications and for its simple composition. Hydrogen plays a key role in processes of electride material synthesis from pristine mayenite: {Ca₁₂Al₁₄O₃₂}²⁺(O²) → {Ca₁₂Al₁₄O₃₂}²⁺(e⁻)₂. A presence of molecular hydrogen in synthetic mayenite was not confirmed by the direct methods. Spectroscopy investigations of mayenite group mineral fluorkyuygenite, with empirical formula (Ca_12.09Na_0.03)_∑12.12(Al_13.67Si_0.12Fe³⁺_0.07Ti⁴⁺_0.01)_∑12.87O_31.96 [F_2.02Cl_0.02(H₂O)_3.22(H₂S)_0.15□_0.59]_∑6.00, show the presence of an unusual band at 4038 cm⁻¹, registered for the first time and related to molecular hydrogen, apart from usual bands responding to vibrations of mayenite framework. The band at 4038 cm⁻¹ corresponding to stretching vibrations of H₂ is at lower frequencies in comparison with positions of analogous bands of gaseous H₂ (4156 cm⁻¹) and H₂ adsorbed at active cation sites of zeolites (4050–4100 cm⁻¹). This points out relatively strong linking of molecular hydrogen with the fluorkyuygenite framework. An appearance of H₂ in the fluorkyuyginite with ideal formula Ca₁₂Al₁₄O₃₂[(H₂O)₄F₂], which formed after fluormayenite, Ca₁₂Al₁₄O₃₂[□₄F₂], is connected with its genesis. Fluorkyuygenite was detected in gehlenite fragments within brecciaed pyrometamorphic rock (Hatrurim Basin, Negev Desert, Israel), which contains reduced mineral assemblage of the Fe-P-C system (native iron, schreibersite, barringerite, murashkoite, and cohenite). The origin of phosphide-bearing associations is connected with the effect of highly reduced gases on earlier formed pyrometamorphic rocks. Full article

Walstromite, BaCa₂Si₃O₉, known only from metamorphic rocks of North America, was found in small veins of unusual rankinite paralava within gehlenite hornfelses of the Hatrurim Complex, Israel. It was detected at two localities—Gurim Anticline and Zuk Tamrur, Hatrurim Basin, Negev Desert. The structure of Israeli walstromite [with P $\overline{1}$ space group and cell parameters a = 6.74874(10) Å, b = 9.62922(11) Å, c = 6.69994(12) Å, α = 69.6585(13)°, β = 102.3446(14)°, γ = 96.8782(11)°, Z = 2, V = 398.314(11) ų] is analogous to the structure of walstromite from type locality—Rush Creek, eastern Fresno County, California, USA. The Raman spectra of all tree minerals exhibit bands related to stretching symmetric vibrations of Si-O-Si at 650–660 cm⁻¹ and Si-O at 960–990 cm⁻¹ in three-membered rings (Si₃O₉)⁶⁻. This new genetic pyrometamorphic type of walstromite forms out of the differentiated melt portions enriched in Ba, V, S, P, U, K, Na, Ti and F, a residuum after crystallization of rock-forming minerals of the paralava (rankinite, gehlenite-åkermanite-alumoåkermanite, schorlomite-andradite series and wollastonite). Walstromite associates with other Ba-minerals, also products of the residual melt crystallization as zadovite, BaCa₆[(SiO₄)(PO₄)](PO₄)₂F and gurimite, Ba₃(VO₄)₂. The genesis of unusual barium mineralization in rankinite paralava is discussed. Walstromite is isostructural with minerals—margarosanite, BaCa₂Si₃O₉ and breyite, CaCa₂(Si₃O₉), discovered in 2018. Full article

The crystal structure of bentorite, ideally Ca₆Cr₂(SO₄)₃(OH)₁₂·26H₂O, a Cr³⁺ analogue of ettringite, is for the first time investigated using X-ray single crystal diffraction. Bentorite crystals of suitable quality were found in the Arad Stone Quarry within the pyrometamorphic rock of the Hatrurim Complex (Mottled Zone). The preliminary semi-quantitative data on the bentorite composition obtained by SEM-EDS show that the average Cr/(Cr + Al) ratio of this sample is >0.8. Bentorite crystallizes in space group P31c, with a = b = 11.1927(5) Å, c =21.7121(10) Å, V = 2355.60(18) ų, and Z = 2. The crystal structure is refined, including the hydrogen atom positions, to an agreement index R₁ = 3.88%. The bentorite crystal chemical formula is Ca₆(Cr_1.613Al_0.387)_Σ2[(SO₄)_2.750(CO₃)_0.499]_Σ3.249(OH)_11.502·~25.75H₂O. The Raman spectra of bentorite from two different localities exhibit the presence of the main stretching and bending vibrations related to the sulfate group at 983 cm⁻¹ (ν₁), 1109 cm⁻¹ (ν₃), 442 cm⁻¹ (ν₂), and 601 cm⁻¹ (ν₄). Moreover, the presence of bands assigned to the symmetric Cr(OH)₆³⁻ stretching mode and hydroxyl deformation vibrations of Cr–OH units at ~540 cm⁻¹ and ~757 cm⁻¹, respectively, may be used to distinguish between ettringite and bentorite. In situ high temperature single crystal XRD experiments show that the decomposition of bentorite starts at ca. 45 °C and that a dehydroxylation product similar to metaettringite is formed. Full article

A natural barioferrite, BaFe³⁺₁₂O₁₉, from a larnite–schorlomite–gehlenite vein of paralava within gehlenite hornfels of the Hatrurim Complex at Har Parsa, Negev Desert, Israel, was investigated by Raman spectroscopy, electron probe microanalysis, and single-crystal X-ray analyses acquired over the temperature range of 100–400 K. The crystals are up to 0.3 mm × 0.1 mm in size and form intergrowths with hematite, magnesioferrite, khesinite, and harmunite. The empirical formula of the barioferrite investigated is as follows: (Ba_0.85Ca_0.12Sr_0.03)_∑1(Fe³⁺_10.72Al_0.46Ti⁴⁺_0.41Mg_0.15Cu²⁺_0.09Ca_0.08Zn_0.04Mn²⁺_0.03Si_0.01)_∑11.99O₁₉. The strongest bands in the Raman spectrum are as follows: 712, 682, 617, 515, 406, and 328 cm⁻¹. The structure of natural barioferrite (P6₃/mmc, a = 5.8901(2) Å, c = 23.1235(6) Å, V = 694.75(4) ų, Z = 2) is identical with the structure of synthetic barium ferrite and can be described as an interstratification of two fundamental blocks: spinel-like S-modules with a cubic stacking sequence and R-modules that have hexagonal stacking. The displacement ellipsoids of the trigonal bipyramidal site show elongation along the [001] direction during heating. As a function of temperature, the mean apical Fe–O bond lengths increase, whereas the equatorial bond lengths decrease, which indicates dynamic disorder at the Fe2 site. Full article

Ariegilatite, BaCa₁₂(SiO₄)₄(PO₄)₂F₂O (R $\overline{3}$ m, a = 7.1551(6) Å, c = 41.303(3) Å, V = 1831.2(3) ų, Z = 3), is a new member of the nabimusaite group exhibiting a modular intercalated antiperovskite structure derived from hatrurite. It was found in a few outcrops of pyrometamorphic rocks of the Hatrurim Complex located in the territories of Israel, Palestine and Jordan. The holotype specimen is an altered spurrite marble from the Negev Desert near Arad city, Israel. Ariegilatite is associated with spurrite, calcite, brownmillerite, shulamitite, CO₃-bearing fluorapatite, fluormayenite-fluorkyuygenite and a potentially new mineral, Ba₂Ca₁₈(SiO₄)₆(PO₄)₃(CO₃)F₃O. Ariegilatite is overgrown and partially replaced by stracherite, BaCa₆(SiO₄)₂[(PO₄)(CO₃)]F. The mineral forms flat disc-shaped crystals up to 0.5 mm in size. It is colorless, transparent, with white steaks and vitreous luster. Optically, ariegilatite is uniaxial, negative: ω = 1.650(2), ε = 1.647(2) (λ = 589 nm). The mean composition of the holotype ariegilatite, (Ba_0.98K_0.01Na_0.01)_Σ1(Ca_11.77Na_0.08Fe²⁺_0.06Mn²⁺_0.05Mg_0.04)_Σ12(Si_3.95Al_0.03Ti_0.02)_Σ4(P_1.70C_0.16Si_0.10S⁶⁺_0.03V_0.01)_Σ2F_2.04O_0.96, is close to the end-member formula. The structure of ariegilatite is described as a stacking of the two modules {F₂OCa₁₂(SiO₄)₄}⁴⁺ and {Ba(PO₄)₂}⁴⁻ along (001). Ariegilatite, as well as associated stracherite, are high-temperature alteration products of minerals of an early clinker-like association. These alterations took place under the influence of pyrometamorphism by-products, such as gases and fluids generated by closely-spaced combustion foci. Full article