Yevgeny Vapnik

Chromatite and its Cr3+- and Cr6+-bearing precursor minerals from the Nabi Musa Mottled Zone complex, Judean Desert

Abstract Chromatite (CaCrO4, tetragonal) is mainly known from Cr6+-contaminated soils associated with chromium ore processing residue. This extremely rare mineral was found at the Nabi Musa locality (Judean Desert, Israel), in a peculiar rock complex of the Mottled Zone. We have explored the possible mechanisms responsible for leaching Cr6+ from natural rocks, by means of field observations, batch experiments, thermodynamic modeling, and mineralogical analyses of the Nabi Musa rocks (XRPD, EMPA, SEM, FTIR, and optical microscopy). A remarkable feature of the Mottled Zone rocks is a broad occurrence of high- and ultrahigh-temperature combustion metamorphic rocks, with Cr3+ accumulated mainly in opaque minerals such as Fe-spinel, brownmillerite, and perovskite. Another feature of the Mottled Zone sequence is abundant Cr3+ (bentorite and volkonskoite) and Cr6+ mineralization (Cr6+-bearing ettringite and baryte-hashemite solid solution) in low-temperature hydrothermal veins. Field, mineralogical, and thermodynamic modeling data suggest that Cr was leached from Cr3+-bearing opaque minerals during late hydrothermal alteration of combustion metamorphic rocks by unusual hyperalkaline waters (pH up to 12). The Cr3+ was then oxidized to Cr6+, and subsequently partially immobilized in Cr6+-bearing ettringite. As a consequence of the highway construction across Nabi Musa hill in 2006, the buried veins filled by Cr6+-substituted ettringite were exhumed and exposed to supergene alteration. The ensuing decomposition of Cr6+-bearing ettringite was followed by Cr6+ release into pore waters in rainy seasons, and then by precipitation of chromatite on the evaporation barrier under the hard desert insolation in dry seasons. The chromatite formation has been due to both unique rock and water chemistry of the Mottled Zone sequence and to the arid climate of the Judean Desert.

Shulamitite Ca3TiFe3+AlO8 – a new perovskite-related mineral from Hatrurim Basin, Israel

Shulamitite, ideally Ca 3 TiFe 3+ AlO 8 , is a mineral intermediate between perovskite CaTiO 3 and brownmillerite Ca 2 (Fe,Al) 2 O 5 . It was discovered as a major mineral in a high-temperature larnite-mayenite rock from the Hatrurim Basin, Israel. Shulamitite is associated with larnite, F-rich mayenite, Cr-containing spinel, ye9elimite, fluorapatite, and magnesioferrite, and retrograde phases (portlandite, hematite, hillebrandite, afwillite, foshagite and katoite). The mineral forms reddish brown subhedral grains or prismatic platelets up to 200 μm and intergrowths up to 500 μm. The empirical formula of the holotype shulamitite (mean of 73 analyses) is (Ca 2.992 Sr 0.007 LREE 0.007 )(Ti 0.981 Zr 0.014 Nb 0.001 )(Fe 3+ 0.947 Mg 0.022 Cr 0.012 Fe 2+ 0.012 Mn 0.001 )(Al 0.658 Fe 3+ 0.288 Si 0.054 )O 8 . The X-ray diffraction powder-pattern (Mo Kα -radiation) shows the strongest lines {d [A]( I obs )} at: 2.677(100), 2.755(40), 1.940(40), 11.12(19), 1.585(17), 1.842(16), 1.559(16), 3.89 (13), 1.527(13). The unit-cell parameters and space group are: a = 5.4200(6), b = 11.064(1), c = 5.5383(7) A, V= 332.12(1) A 3 , Pmma, Z = 2. The calculated density is 3.84 g/cm 3 . The crystal structure of shulamitite has been refined from X-ray single-crystal data to R 1 = 0.029 %. No partitioning among octahedral sites was found for Ti and Fe 3+ in the structure of shulamitite, these cations are randomly distributed among all octahedra indicating an example of “valency-imposed double site occupancy”. The strong bands in the Raman spectrum of shulamitite are at: 238,250, 388,561, and 742 cm −1 . Shulamitite from the Hatrurim Basin crystallized under combustion metamorphism conditions characterized by very high temperatures (1150−1170 °C) and low pressures (high- T -region of the spurrite-merwinite facies). Chemical data for shulamitite and its Fe-analog from other metacarbonate occurrences (natural and anthropogenic) are given here.

Harmunite CaFe2O4: A new mineral from the Jabel Harmun, West Bank, Palestinian Autonomy, Israel

Abstract Harmunite, naturally occurring calcium ferrite CaFe2O4, was discovered in the Hatrurim Complex of pyrometamorphic larnite rocks close to the Jabel Harmun, the Judean Desert, West Bank, Palestinian Autonomy, Israel. The new mineral occurs in larnite pebbles of the pseudo-conglomerate, the cement of which consists of intensely altered larnite-bearing rocks. Srebrodolskite, magnesioferrite, and harmunite are intergrown forming black porous aggregates to the central part of the pebbles. Larnite, fluorellestadite, ye’elimite, fluormayenite, gehlenite, ternesite, and calciolangbeinite are the main associated minerals. Empirical crystal chemical formula of harmunite from type specimen is as follows Ca1.013(Fe3+ 1.957Al0.015Cr3+ 0.011Ti4+0.004 Mg0.003)S1.993O4. Calculated density is 4.404 g/cm3, microhardness VHN50 is 655 kg/mm2. The Raman spectrum of harmunite is similar to that of the synthetic analog. Harmunite in hand specimen is black and under reflected plane-polarized light is light gray with red internal reflections. Reflectance data for the COM wavelengths vary from ~22% (400 nm) to ~18% (700 nm). The crystal structure of harmunite [Pnma; a = 9.2183(3), b = 3.0175(1), c = 10.6934(4) Å; Z = 4, V = 297.45(2) Å3], analogous to the synthetic counterpart, was refined from X-ray single-crystal data to R1 = 0.0262. The structure of CaFe2O4 consist of two symmetrically independent FeO6 octahedra connected over common edges, forming double rutile-type ∞1[Fe2O6] chains. Four such double chains are further linked by common oxygen corners creating a tunnel-structure with large trigonal prismatic cavities occupied by Ca along [001]. The strongest diffraction lines are as follows [dhkl, (I)]: 2.6632 (100), 2.5244 (60), 2.6697 (52), 1.8335 (40), 2.5225 (35), 2.2318 (34), 1.8307 (27), 1.5098 (19). Crystallization of harmunite takes place in the presence of sulfate melt. ̃

Earth's Phosphides in Levant and insights into the source of Archean prebiotic phosphorus

Natural phosphides - the minerals containing phosphorus in a redox state lower than zero – are common constituents of meteorites but virtually unknown on the Earth. Herein we present the first rich occurrence of iron-nickel phosphides of terrestrial origin. Phosphide-bearing rocks are exposed in three localities in the surroundings of the Dead Sea, Levant: in the northern Negev Desert, Israel and Transjordan Plateau, south of Amman, Jordan. Seven minerals from the ternary Fe-Ni-P system have been identified with five of them, NiP2, Ni5P4, Ni2P, FeP and FeP2, previously unknown in nature. The results of the present study could provide a new insight on the terrestrial origin of natural phosphides – the most likely source of reactive prebiotic phosphorus at the times of the early Earth.

Natural analogs of belite sulfoaluminate cement clinkers from Negev Desert, Israel

Abstract Ye’elimite-larnite rocks in the Hatrurim formation of the Negev Desert, Israel, are natural analogs of belite sulfoaluminate (BSA) cement clinkers. They have been produced by ultrahigh-temperature combustion metamorphism at ambient pressure of a calcareous sedimentary precursor. Their mineralogy consists of 35-50 vol% β-Ca2SiO4, 15-20 vol% ye’elimite, 7-15 vol% ferrites, and 15-20 vol% fluorapatite and/or fluorellestadite. A few grains of hatrurite (Ca3SiO5) and α′-Ca2SiO4 have been observed as well. The composition of α′- and β-Ca2SiO4 polymorphs by EPMA are near Ca1.96-1.98Na0.01-0.02 Si0.96P0.03Al0.01O4, whereas ye’elimite has an approximate composition by EPMA of Ca3.99Mg0.02Ba0.01 Na0.02K0.02Al5.73Fe3+0.16Si0.10S0.97P0.02O16. The Al content of brownmillerite Ca2(Fe1-xAlx)2O5 ranges from x = 0.20-0.27. Fe-analog of shulamitite (Ca3Fe2TiO8) contains up to 15.1 wt% TiO2. Ye’elimite-larnite rocks were derived from chalky sediments by burning of combustible gas with a Tmax at 1200-1350 °C. The mineral content, microstructure, and texture/fabric of the ye’elimite-larnite rocks imply that chalky and/or marly sediments with randomly distributed clay, phosphorite, and gypsum may be utilized as cheap naturally homogenized and pulverized mixtures for industrial production of BSA cement clinker, as an environment-friendly alternative to ordinary Portland cement (OPC).

Mineral and fluid inclusion study of emeralds from the Lake Manyara and Sumbawanga deposits, Tanzania

Abstract Mineral and fluid inclusions were investigated in Tanzanian emeralds sampled in the Lake Manyara and Sumbawanga deposits. Microthermometry and Raman microprobe analyses were applied for this study. Primary and pseudosecondary H 2 O-CO 2 inclusions, with numerous daughter solid phases, are common in the emeralds from the Lake Manyara deposit. Magnesite, Mg-calcite, aragonite, dolomite, calcite, nahcolite, quartz and chrysoberyl were identified as trapped solids in fluid inclusions. Similar mineral inclusions were also found in the emeralds themselves. The composition of the trapped fluid present at emerald growth is estimated to be a carbonic-rich solution with chloride content of about 6 wt% NaCl equiv. The P-T conditions of emerald growth are as follows: T = 370–470°C and P =3.0–7.0 kbar. Mineral inclusions of phenakite, euclase, bertrandite and helvite are common in the emeralds of the Sumbawanga deposit. CO 2 -rich inclusions with an aqueous phase (usually below the detection limit), and CaCl 2 -rich inclusions with salinity of up to 17 wt% NaCl equiv. are related to emerald growth. The trapping of fluid inclusions postdates the growth of mineral inclusions. The P-T conditions of emerald growth are as follows: T = 220–300°C and P = 0.7–3.0 kbar.

New minerals with a modular structure derived from hatrurite from the pyrometamorphic Hatrurim Complex. Part I. Nabimusaite, KCa12(SiO4)4(SO4)2O2F, from larnite rocks of Jabel Harmun, Palestinian Autonomy, Israel

Abstract The new mineral nabimusaite, KCa12(SiO4)4(SO4)2O2F (R3̅m, 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 awhite 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), ɛ = 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.

New minerals with a modular structure derived from hatrurite from the pyrometamorphic Hatrurim Complex. Part II. Zadovite, BaCa6[(SiO4)(PO4)](PO4)2F and aradite, BaCa6[(SiO4)(VO4)](VO4)2F, from paralavas of the Hatrurim Basin, Negev Desert, Israel

Abstract Zadovite, BaCa6[(SiO4)(PO4)](PO4)2F (R3̅m, a = 7.0966(1) Å, c = 25.7284(3), V= 1122.13(3) Å3, Z= 3) and aradite, BaCa6[(SiO4)(VO4)] (VO4)2F(R3̅m,a = 7.1300(1),c = 26.2033(9) Å, V= 1153.63(6) A3,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)42- modules.

Geophysical evidence of deep hydrocarbon flow in Mottled Zone areas, Dead Sea Transform zone

The origin of unusual magnetic initially sedimentary rocks of the Mottled Zone (MZ) in Israel and Jordan remained enigmatic for several decades until integrated characterization of the MZ area was achieved by ground magnetic measurements and geologic observations along representative profiles in parallel with reprocessing and reinterpretation of available aeromagnetic and gravity data. Micromagnetic profiling was combined with gamma-radioactivity measurements, and representative samples were selected to determine rock physical properties. Results of field measurements, reduction and transformation of geophysical fields, anomaly inversion, and forward modeling accompanied by geologic analysis suggest that two types of magnetic anomalies and local gravity minima in the MZ areas are related to the same event, i.e., deep hydrocarbon flow associated with fossil mud volcanism. Physicochemical interaction of deep hydrocarbon flow and surrounding sedimentary rocks caused widespread weak magnetization and correspo...

New minerals with a modular structure derived from hatrurite from the pyrometamorphic rocks. Part III. Gazeevite, BaCa6(SiO4)2(SO4)2O, from Israel and the Palestine Autonomy, South Levant, and from South Ossetia, Greater Caucasus

Abstract The new mineral gazeevite, BaCa6(SiO4)2(SO4)2O (R3̅m, a = 7.1540(1), c = 25.1242(5) Å, V = 1113.58(3) Å3, Z = 3), was found in an altered xenolith in rhyodacites of the 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-brownmillerite andmayenite-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 structurally related 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 are intercalated 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 streak and 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 calculated density 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 gazeevite are 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.