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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]

The new mineral khurayyimite Ca7Zn4(Si2O7)2(OH)10·4H2O occurs in colorless spherulitic aggregates in small cavities of altered spurrite marbles located in the northern part of the Siwaqa pyrometamorphic rock area, Central Jordan. It is a low-temperature, hydrothermal mineral and is formed at a temperature lower than 100 °C. Synchrotron single-crystal X-ray diffraction experiments have revealed that khurayyimite crystallizes in space group P21/c, with unit cell parameters a = 11.2171(8), b = 9.0897(5), c = 14.0451(10) Å, β = 113.297(8)º, V = 1315.28(17) Å3 and Z = 2. The crystal structure of khurayyimite exhibits tetrahedral chains of periodicity 6. The sequence of SiO4 and ZnO2(OH)2-tetrahedra along the chain is Si–Si-Zn. The neighboring SiO4-tetrahedra of the corrugated chains are bridged by additional ZnO2(OH)2-tetrahedra to form 3-connected dreier rings. The chains can be addressed as loop-branched sechser single chains {lB, 11∞}[6Zn4Si4O21]. The chains are linked by clusters of five CaO6 and two CaO7 polyhedra with additional OH groups and H2O molecules in the coordination environment. Based on the connectedness and one-dimensional polymerisations of tetrahedra (TO4)n−, chains of khurayyimite belong to the same group as vlasovite Na2ZrSi4O11, since they can be described with geometrical repeat unit cTr = 2T43T4 and topological repeat unit cVr = 2V23V2. [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]

Ellinaite, a natural analog of the post-spinel phase β-CaCr2O4, was discovered at the Hatrurim Basin, Hatrurim pyrometamorphic formation (the Mottled Zone), Israel, and in an inclusion within the super-deep diamond collected at the placer of the Sorriso River, Juína kimberlite field, Brazil. Ellinaite at the Hatrurim Basin is confined to a reduced rankinite-gehlenite paralava, where it occurs as subhedral grains up to 30 pm in association with gehlenite, rankinite and pyrrhotite or forms the rims overgrowing zoned chromite-magnesiochromite. The empirical formula of the Hatrurim sample is (Ca0.960Fe0.0162+Na0.012Mg0.003)0.992 (Cr1.731v0.1833+Ti3.0683+Al0.023Ti0.0034+)2.008O4. The mineral crystallizes in the orthorhombic system, space group Pnma, unit-cell parameters refined from X-ray single-crystal data: a 8.868(9), b 2.885(3), c 10.355(11) Å, V 264.9(5) ų and Z = 4. The crystal structure of ellinaite from the Hatrurim Basin has been solved and refined to R1 = 0.0588 based on 388 independent observed reflections. Ellinaite in the Juína diamond occurs within the micron-sized polyphase inclusion in association with ferropericlase, magnesioferrite, orthorhombic MgCr2O4, unidentified iron carbide and graphite. Its empirical formula is Ca1.07(Cr1.71Fe0.063+V0.06Ti0.03Al0.03Mg0.02Mn0.02)Σ1.93O4. The unit-cell parameters obtained from HRTEM data are as follows: space group Pnma, a 9.017, b 2.874 Å, c 10.170 Å, V 263.55 ų, Z = 4. Ellinaite belongs to a group of natural tunnel-structured oxides of the general formula AB2O4, the so-called post-spinel minerals: marokite CaMn2O4, xieite FeCr2O4, harmunite CaFe2O4, wernerkrauseite CaFe23+Mn4+O6, chenmingite FeCr2O4, maohokite MgFe2O4 and tschaunerite Fe(FeTi)O4. The mineral from both occurrences seems to be crystallized under highly reduced conditions at high temperatures (> 1000 °C), but under different pressure: near-surface (Hatrurim Basin) and lower mantle (Juína diamond). [ABSTRACT FROM AUTHOR]

Schreibersite, (Fe,Ni)3P, the most abundant cosmic phosphide, is a principal carrier of phosphorus in the natural Fe-Ni-P system and a likely precursor for prebiotic organophosphorus compounds at the early stages of Earth's evolution. The crystal structure of the mineral contains three metal sites allowing for unrestricted substitution of Fe for Ni. The distribution of these elements across the structure could serve as a tracer of crystallization conditions of schreibersite and its parent celestial bodies. However, discrimination between Fe (Z = 26) and Ni (Z = 28) based on the conventional X-ray structural analysis was for a long time hampered due to the proximity of their atomic scattering factors. We herein show that this problem has been overcome with the implementation of area detectors in the practice of X-ray diffraction. We report on previously unknown site-specific substitution trends in schreibersite structure. The composition of the studied mineral encompasses a Ni content ranging between 0.03 and 1.54 Ni atoms per formula unit (apfu): the entire Fe-dominant side of the join Fe3P-Ni3P. Of 23 schreibersite crystals studied, 22 comprise magmatic and non-magmatic iron meteorites and main group pallasites. The near end-member mineral (0.03 Ni apfu) comes from the pyrometamorphic rocks of the Hatrurim Basin, Negev desert, Israel. It was found that Fe/Ni substitution in schreibersite follows the same trends in all studied meteorites. The dependencies are nonlinear and can be described by second-order polynomials. However, the substitution over the M2 and M3 sites within the most common range of compositions (0.6 < Ni <1.5 apfu) is well approximated by a linear regression: Ni(M2) = 0.84 × Ni(M3) - 0.30 apfu (standard error 0.04 Ni apfu). The analysis of the obtained results shows a strong divergence between the variation of unit-cell parameters of natural schreibersite and those of synthetic (Fe,Ni)3P. This indicates that Fe/Ni substitution trends in the mineral and its synthetic surrogates are different. A plausible explanation might be related to the differences in the system equilibration time of meteoritic schreibersite (millions of years) and synthetic (Fe,Ni)3P (~100 days). However, regardless of the reason for the observed difference, synthetic (Fe,Ni)3P cannot be considered a structural analog of natural schreibersite, and this has to be taken into account when using synthetic (Fe,Ni)3P as an imitator of schreibersite in reconstructions of natural processes. [ABSTRACT FROM AUTHOR]

Zuktamrurite, FeP2, is a new mineral, a natural iron diphosphide found in the pyrometamorphic rocks of the Hatrurim Formation, in the southern part of the Negev Desert, Israel and on the Transjordan Plateau, Jordan. The mineral occurs as irregular grains up to 50 µm in size associated with murashkoite, FeP, and barringerite, (Fe,Ni)2P. In reflected light, zuktamrurite is white with a distinct bluish tint. It is non-pleochroic but exhibits distinct anisotropy in bluish colours. Reflectance values for the IMA COM recommended wavelengths are [Rmax/Rmin, % (λ, nm)]: 50.40/47.20 (470); 49.16/46.23 (546); 48.97/46.16 (589); 49.40/46.40 (650). It is brittle. Electron microprobe analysis of the holotype specimen gave the following chemical composition (wt%, average of 5 points): Fe 40.23; Ni 7.97; P 51.70; total 99.90. The empirical formula calculated on the basis of 3 apfu is (Fe0.86Ni0.16)1.02P1.98 corresponding to FeP2. Zuktamrurite is orthorhombic, space group Pnnm, unit cell parameters refined from the single-crystal data: a 4.9276(6), b 5.6460(7), c 2.8174(4) Å, V 78.38(1) Å3, Z = 2. Dx = 5.003 g cm−3. The crystal structure was solved and refined to R1 = 0.0121 on the basis of 109 unique reflections with I > 2σ(I). The strongest lines of the powder X-ray diffraction pattern [(d, Å) (I, %) (hkl)]: 3.714 (54) (110); 2.820 (31) (020); 2.451 (100) (120, 101); 2.242 (55) (111); 1.760 (37) (211). The mineral is named for the Zuk-Tamrur cliff (Dead Sea) located nearby the type locality, the Halamish Wadi, southern Negev Desert, Israel. Zuktamrurite is the phosphide analogue of löllingite (loellingite), FeAs2. It is the most phosphorus-rich phosphide ever found in nature. [ABSTRACT FROM AUTHOR]

Zuktamrurite, FeP2, is a new mineral, a natural iron diphosphide found in the pyrometamorphic rocks of the Hatrurim Formation, in the southern part of the Negev Desert, Israel and on the Transjordan Plateau, Jordan. The mineral occurs as irregular grains up to 50 µm in size associated with murashkoite, FeP, and barringerite, (Fe,Ni)2P. In reflected light, zuktamrurite is white with a distinct bluish tint. It is non-pleochroic but exhibits distinct anisotropy in bluish colours. Reflectance values for the IMA COM recommended wavelengths are [Rmax/Rmin, % (λ, nm)]: 50.40/47.20 (470); 49.16/46.23 (546); 48.97/46.16 (589); 49.40/46.40 (650). It is brittle. Electron microprobe analysis of the holotype specimen gave the following chemical composition (wt%, average of 5 points): Fe 40.23; Ni 7.97; P 51.70; total 99.90. The empirical formula calculated on the basis of 3 apfu is (Fe0.86Ni0.16)1.02P1.98 corresponding to FeP2. Zuktamrurite is orthorhombic, space group Pnnm, unit cell parameters refined from the single-crystal data: a 4.9276(6), b 5.6460(7), c 2.8174(4) Å, V 78.38(1) Å3, Z = 2. Dx = 5.003 g cm−3. The crystal structure was solved and refined to R1 = 0.0121 on the basis of 109 unique reflections with I > 2σ(I). The strongest lines of the powder X-ray diffraction pattern [(d, Å) (I, %) (hkl)]: 3.714 (54) (110); 2.820 (31) (020); 2.451 (100) (120, 101); 2.242 (55) (111); 1.760 (37) (211). The mineral is named for the Zuk-Tamrur cliff (Dead Sea) located nearby the type locality, the Halamish Wadi, southern Negev Desert, Israel. Zuktamrurite is the phosphide analogue of löllingite (loellingite), FeAs2. It is the most phosphorus-rich phosphide ever found in nature. [ABSTRACT FROM AUTHOR]

Cr3+-rich ettringite with Cr3+→Al substitution and Cr/(Cr + Al) ratios up to 0.40-0.50 was found in mineral assemblages of the Ma’aleh Adumim area of Mottled Zone (Judean Desert). The Cr3+-rich compositions were the latest in the thaumasite → ettringite-thaumasite solid solution → ettringite → ettringite-bentorite solid solution series. The mineral-forming solution was enriched in Cr3+ and had a pH buffered by afwillite at ~11-12. Chromium was inherited from larnite rocks produced by high-temperature combustion metamorphic alteration of bioproductive calcareous sediments. The Cr/(Cr + Al) ratios are within 0.10-0.15 in most of the analysed crystals. This degree of substitution imparts pink colouration to the crystals, but does not affect their habit (a combination of monohedra and a prism). The habit changes to pyramid faces in coarse and later Cr3+-bearing crystals as Cr/(Cr + Al) ratios increase abruptly to 0.40-0.50. Single-crystal XRD analysis of one Cr-free and two Cr3+-rich samples and their structure determination and refinement indicate that the Cr-rich crystals (with Cr/(Cr + Al) to 0.3) preserve the symmetry and metrics of ettringite. The Ca-O bonding network undergoes differentiation with increase of Cr3+ concentration at octahedral M sites. The compression of Ca2 and expansion of Ca1 polyhedra sub-networks correlates with the degree of Cr3+→Al substitution. [ABSTRACT FROM AUTHOR]

Crystal structures of two uranyl selenite minerals derriksite, Cu4[(UO2)(SeO3)2](OH)6, and demesmaekerite, Pb2Cu5[(UO2)2(SeO3)6(OH)6](H2O)2, which structures are based on uranyl selenite 1D structural units, were studied employing single-crystal X-ray diffraction analysis at various temperatures. The refinement of their crystal structures reveals the detailed dynamics of the interatomic interactions during the heating process, which allows describing the thermal behavior. Uranyl selenite chains and their mutual arrangement mainly provide the rigidity of the crystal structure. Thus the lowest expansion in the structure of derriksite is observed along the direction of uranyl selenite chains, while the largest expansion occurs in the direction normal to chains, with the space occupied by lone electron pairs of Se4+ atoms and low covalent bond distribution density. The maximal expansion in the crystal structure of demesmaekerite is manifested approximately along the [100], which matches the direction of chains of less strongly bonded Cu-centered octahedra, and gaps between Cu chains occupied by the Pb cations. The crystal structure of demesmaekerite undergoes contraction in the direction of the space between the U-bearing chains with the deficiency of strong covalent bonds. Contraction of the structure can also be attributed to the orthogonalization of the oblique triclinic angles of the unit cell. It is demonstrated that the assignment of U-bearing units during structure description is reasonably justified since, regardless of their dimensionality, these substructural units are one of the most stable and rigid blocks in the structural architecture, and they govern the thermal behavior of the entire structure. [ABSTRACT FROM AUTHOR]