Mottled Zone Research Articles

Detection of subsurface cavities in the structurally bounded Labe prefecture area, Republic of Guinea using two-dimensional electrical resistivity tomography (ERT)

ABSTRACT This study is conducted within the Gambia River Basin Development Organization Energy Project (OMVG) framework. The construction of a high voltage interconnection network fed by a hydropower station to supply electricity to OMVG Member States was done on stable ground. During the installation pits for the pylons in Labé Prefecture, Republic of Guinea, cavities were discovered in the geological formations during the initial planned route. Structurally, the study area is bounded by two major faults to the east and west of northeast direction. The geomorphology is made up of a central plateau, intermountain depressions, piedmont plains, talwegs, and glacis. Geological investigations were obtained by a geophysical Two-dimensional Electrical Resistivity Tomography (ERT) method. The results show that the synthetic lithological profile from top to base was sandy-clayey soil, hard cuirass, and a layer of gravel followed by a mottled zone comprising an indurated part and an imbibed part just before the source rock. The cavities were observed probably because of the dissolution of certain minerals constituting the weathering crust due to the infiltration, underground waters, and the seasonal variation in the level of the surface watercourses. Geophysical results showed a very good agreement with the visual observations.

Automated mapping of regolith units with support vector machine and artificial neural network using data from Landsat-8 OLI, ALOS PALSAR DEM, and Sentinel-1A radar images: the case of the Sissingué Gold Project, Northern Côte d’Ivoire

ABSTRACT The Sissingué Gold Project is in Northern Côte d’Ivoire and part of the southern extension, a large peneplain of the landscape in South Mali. The area has experienced extensive weathering and erosion over a long time, resulting in a widespread and complex regolith cover. This diverse and vast regolith cover poses considerable difficulties for exploration. To overcome this problem, we adopted mapping of regolith units using machine learning (ML) with support vector machine (SVM) and artificial neural network (ANN) algorithms. The main objectives were to (1) make the predictive regolith map of the study region using these algorithms with data obtained from Landsat-8 operational land imager, Advanced Land Observing Satellite Phased Array Type L-Band Synthetic Aperture Radar digital elevation model and Sentinel-1A; (2) show the method of pre-processing and processing the required data and (3) develop the regolith landform unit (RLU) map from the predictive regolith map and collected data based on the Relict – Erosional – Depositional model. Tests using the SVM and ANN algorithms showed that both ML tools could accurately map regolith landforms. An innovative method of optimizing data using parameters is presented. The results showed that ANN outperformed SVM with an overall accuracy of 87.01% and a kappa coefficient of 0.84, whereas the corresponding values for SVM were 86.69% and 0.84, respectively. However, the validation data obtained from SVM-based prediction exhibited a better score than that of validation data obtained from ANN-based prediction. The Sentinel-1A radar band combined with Landsat-8 data reduced the vegetation-masking effect and improved the classification results. The RLUs of this area are composed primarily of relicts at 24.91%, including lateritic residuum and soil, depositional material at 36.39% with exotic sediments and ferrierite and the remaining 38.7% of erosional material made of saprolite, colluvial fragments, and mottled zones on flanks.

Correlation Between Fundus Autofluorescence Pattern and Retinal Function on Microperimetry in Choroideremia.

In patients with choroideremia, it is not known how smooth and mottled patterns on short-wavelength fundus autofluorescence (AF) imaging relate to retinal function. A retrospective case-note review was undertaken on 190 patients with choroideremia at two specialist centers for retinal genetics. Twenty patients with both smooth and mottled zones on short-wavelength AF imaging and concurrent mesopic microperimetry assessments were included. Mean retinal sensitivities within the smooth and mottled zones were compared between choroideremia patients, and identical points on mesopic microperimetry collected from 12 age-matched controls. Longitudinal analyses were undertaken at 2 and 5years in a subset of patients. In patients with choroideremia, mean retinal sensitivities at baseline were significantly greater in the smooth zone (26.1 ± 2.0 dB) versus the mottled zone (20.5 ± 4.2 dB) (P < 0.0001). Mean retinal sensitivities at baseline were similar in the smooth zone between choroideremia patients and controls (P = 0.054) but significantly impaired in the mottled zone in choroideremia compared to controls (P < 0.0001). The rate of decline in total sensitivity over 5 years was not significant in either the smooth or mottled zone in a small subset of choroideremia patients (n = 7; P = 0.344). In choroideremia, retinal sensitivity as determined by microperimetry correlates with patterns on AF imaging: retinal function in the smooth zone, where the retinal pigment epithelium is anatomically preserved, is similar to controls, but retinal sensitivity in the mottled zone is impaired. Patterns on AF imaging may represent a novel, objective outcome measure for clinical trials in choroideremia as a surrogate for retinal function.

Rock Magnetic and Mineralogical Properties of Lateritic Soil Profiles Developed on Two Different Parent Rocks in Northern Kerala, South-Western India

The rock magnetic and mineralogical properties of two lateritic soil profiles developed on two different parent rocks (khondalite and granite) in northern Kerala, south-western India were investigated to better understand pedogenic processes under tropical climate. Field investigations reveal the presence of various horizons in the lateritic profiles, such as saprolite, mottled zone, pebble horizon and top soil. The particle size, rock magnetic, Vibrating Sample Magnetometer (VSM), Scanning Electron Microscopy (SEM)-Energy-Dispersive X-ray Spectrometer (EDS) and X-Ray Diffraction (XRD) analyses were performed on samples collected from different horizons of the two profiles. Magnetic susceptibility (χlf) values of the lateritic profiles vary from 9.97 to 1717.04 x 10-8 m3 kg-1, with the granitic profile exhibiting overall higher values. The percentage frequency-dependent susceptibility (χ %) ranges between 0 % and 13.9 %. The XRD data reveal the presence of kaolinite, gibbsite (except for top soil layer) and quartz along with magnetic minerals like magnetite, hematite and goethite. The upper horizons (top-soil and pebble horizon) exhibit high values for concentration dependent magnetic parameters like χlf and χfd%, whereas, the lower horizons (saprock, saprolite, pallid zone horizons) exhibit low values. The tropical soils in the region have undergone a higher degree of pedogenesis with increased magnetic mineral concentration compared to temperate soils. The magnetic enhancement in the topsoil may be due to the neoformation of ultra fine-grained SP magnetite/maghemite (with minor anti-ferro magnetic component), aided by sufficient Fe supply, alternate wetting and drying cycles, dehydration, oxidation and redox conditions. Keywords: Lateritic Soils; Soil Magnetism; XRD; SEM; Magnetic Enhancement; Pedogenesis; Southern India

Unique Minerals from the Varicolored Marble (Mottled Zone) of Central Jordan

Aspects in Mining & Mineral Science Unique Minerals from the Varicolored Marble (Mottled Zone) of Central Jordan Hani N Khoury* Department of Geology, The University of Jordan, Amman Jordan 11940, Jordan *Corresponding author:Hani N Khoury, Department of Geology, The University of Jordan, Amman Jordan 11940, Jordan Submission: March 23, 2023; Published: April 11, 2023 DOI: 10.31031/AMMS.2023.11.000758 ISSN 2578-0255Volume11 Issue2

Nickolayite, FeMoP, a new natural molybdenum phosphide

AbstractNickolayite, FeMoP, is a new terrestrial phosphide structurally related to allabogdanite (high-pressure modification of (Fe,Ni)2P), and the meteoritic phosphides florenskyite, FeTiP and andreyivanovite, FeCrP. From the point of view of chemical composition, nickolayite is an Fe-analogue of monipite, MoNiP. The mineral was discovered in the Daba-Siwaqa complex, Central Jordan, a part of the pyrometamorphic Hatrurim Formation (the Mottled Zone), whose outcrops encompass a 150 × 200 km area around the Dead Sea in the Middle East. Nickolayite appears as an accessory phase in the fused clinopyroxene–plagioclase rocks texturally resembling gabbro–dolerite. The irregularly shaped grains of the mineral, up to 80 μm in size are associated with baryte, tridymite, chromite, hematite, pyrrhotite, fluorapatite, titanite and powellite. Macroscopically, nickolayite grains possess light-grey to greyish-white colour and metallic lustre. The mineral is ductile. The mean VHN hardness (50 g load) is 538 kg mm–2. The calculated density based on the empirical formula and the unit-cell parameters is 7.819 g cm–1. In reflected light, nickolayite has a white colour, with no bireflectance or pleochroism. The COM approved reflectance values [Rmax/Rmin(%), λ(nm)] are: 48.5/46.5 (470), 50.5/48.5 (546), 51.8/49.9 (589) and 53.9/52.0 (650). The chemical composition of the holotype crystal is (electron microprobe, average of 4 analyses, wt.%): Fe 32.21, Mo 47.06, Ni 3.69, Co 0.13, P 17.45, total 100.54, that corresponds to the empirical formula Fe1.00(Mo0.87Ni0.11Fe0.02)Σ1.00P1.00and an ideal formula of FeMoP. Nickolayite is orthorhombic, space groupPnma, unit-cell parameters of holotype material are:a= 5.9519(5),b= 3.7070(3),c= 6.8465(6) Å,V= 151.06(2) Å3andZ= 4. The crystal structure of holotype material was solved and refined toR1= 0.0174 based on 251 unique observed reflections. The origin of the mineral is probably connected to the processes of co-reduction of molybdenum- and phosphorus-bearing minerals during high-temperature pyrometamorphic processes.

Expanding the speciation of terrestrial molybdenum: Discovery of polekhovskyite, MoNiP2, and insights into the sources of Mo-phosphides in the Dead Sea Transform area

Abstract 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.

Ellinaite, CaCr&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;O&amp;lt;sub&amp;gt;4&amp;lt;/sub&amp;gt;, a new natural post-spinel oxide from Hatrurim Basin, Israel, and Juína kimberlite field, Brazil

Abstract. 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 µm 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+Ti0.0683+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) Å3 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 Å3, 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 (&gt;1000 ∘C), but under different pressure: near-surface (Hatrurim Basin) and lower mantle (Juína diamond).

Nazarovite, Ni12P5, a new terrestrial and meteoritic mineral structurally related to nickelphosphide, Ni3P

Abstract 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 &amp;lt;0.2/4.10; Co &amp;lt;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.

Keplerite, Ca9(Ca0.5☐0.5)Mg(PO4)7, a new meteoritic and terrestrial phosphate isomorphous with merrillite, Ca9NaMg(PO4)7

Abstract Keplerite is a new mineral, the Ca-dominant counterpart of the most abundant meteoritic phosphate, which is merrillite. The isomorphous series merrillite-keplerite, Ca9NaMg(PO4)7-Ca9(Ca0.5☐0.5) Mg(PO4)7, represents the main reservoir of phosphate phosphorus in the solar system. Both minerals are related by the heterovalent substitution at the B-site of the crystal structure: 2Na+ (merrillite) → Ca2+ + ☐ (keplerite). The near-end-member keplerite of meteoritic origin occurs in the main-group pallasites and angrites. The detailed description of the mineral is made based on the Na-free type material from the Marjalahti meteorite (the main group pallasite). Terrestrial keplerite was discovered in the pyrometamorphic rocks of the Hatrurim Basin in the northern part of Negev desert, Israel. Keplerite grains in Marjalahti have an ovoidal to cloudy shape and reach 50 μm in size. The mineral is colorless, transparent with a vitreous luster. Cleavage was not observed. In transmitted light, keplerite is colorless and non-pleochroic. Uniaxial (−), ω = 1.622(1), ε = 1.619(1). Chemical composition (electron microprobe, wt%): CaO 48.84; MgO 3.90; FeO 1.33; P2O5 46.34, total 100.34. The empirical formula (O = 28 apfu) is Ca9.00(Ca0.33Fe0.202+☐0.47)1.00Mg1.04P6.97O28. The ideal formula is Ca9(Ca0.5☐0.5)Mg(PO4)7. Keplerite is trigonal, space group R3c, unit-cell parameters refined from single-crystal data are: a = 10.3330(4), c = 37.0668(24) Å, V = 3427.4(3) Å3, Z = 6. The calculated density is 3.122 g/cm−3. The crystal structure has been solved and refined to R1 = 0.039 based on 1577 unique observed reflections [I&amp;gt;2σ(I)]. A characteristic structural feature of keplerite is a partial (half-vacant) occupancy of the sixfold-coordinated B-site (denoted as CaIIA in the earlier works). The disorder caused by this cation vacancy is the most likely reason for the visually resolved splitting of the ν1 (symmetric stretching) (PO4) vibration mode in the Raman spectrum of keplerite. The mineral is an indicator of high-temperature environments characterized by extreme depletion of Na. The association of keplerite with “REE-merrillite” and stanfieldite provides evidence for the similarity of temperature conditions that occurred in the Mottled Zone to those expected during the formation of pallasite meteorites and lunar rocks. Because of the cosmochemical significance of the merrillite-keplerite series and by analogy to plagioclases, the Na-number measure, 100×Na/(Na+Ca) (apfu), is herein proposed for the characterization of solid solutions between merrillite and keplerite. The merrillite end-member, Ca9NaMg(PO4)7, has the Na-number = 10, whereas keplerite, Ca9(Ca0.5☐0.5)Mg(PO4)7, has Na-number = 0. Keplerite (IMA 2019-108) is named in honor of Johannes Kepler (1571–1630), a prominent German naturalist, for his contributions to astronomy and crystallography.

Natural cubic perovskite, Ca(Ti,Si,Cr)O3–δ, a versatile potential host for rock-forming and less-common elements up to Earth’s mantle pressure

Abstract 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 Pm3m) 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.

Experimental investigation of Te addition on chilled cast iron tappet manufacturing process

ABSTRACT The chilled cast iron tappet comprises three gradient microstructures, including chill, mottle, and gray iron. In this work, the effect of Tellurium (Te) on the chilled iron tappet’s microstructure and properties is studied. The addition of Te to gray cast alloy enhances its mechanical and thermal properties, which can be used in new designing of materials for heavy automotive applications. The gray cast iron alloy with 0.01 to 0.05 wt.% of Te was prepared in order to examine the effect of Te wt.% on the chill depth, microstructure, wear, and hardness. The scanning electron micrographs are used to distinguish and analyze the chill zone, mottle, and gray zone in the tappet, and the hardness was studied by Vickers hardness test, and wear behavior by a pin on disc method was measured. The present study showed that the addition of Te strongly influenced the formation of chill and efficiently enhanced the tappet’s mechanical properties along with the favorable effect to eliminate the mottled zone and separate the chill zone and gray zone with a clear boundary.

Mapping the near-surface geoelectrical structure of the Mottled Zone using the very low frequency–electromagnetic method

Mottled Zones (MZ) in south Levant regions show discrete, varied-dimensional rock complex exposures and many unexplored areas in the vicinity of the Dead Sea Transform Fault (DSF). The research area, located south of the Daba–Siwaqa Mottled Zone complex in Jordan, was surveyed using the very low-frequency electromagnetic method (VLF-EM) for the purpose of resolving the geoelectrical setting of MZ rocks, the associated structural features, and the underlying sedimentary layers. The VLF-EM tipper data acquired along five profiles was analyzed using Fraser, Karous-Hjelt, and apparent resistivity linear filters. The quantitative interpretation was conducted using a 2D inversion of the VLF-EM tipper data, and a proposed synthetic model was tested and analyzed at MZ exposure. The majority of MZ rocks are likely to be located in a region of negative Fraser values (≥ −10.0%) and negative Karous-Hjelt values (≥ −8.0%). The apparent resistivity map exhibits MZ rocks at high values (1000–2500 Ω·m).The derived resistivity models recovered from the 2D inversion of the VLF-EM data showed a relatively resistive MZ rock body immersed in relatively less resistive (conductive) sedimentary layers composed of clayey marl and marl. The known and inferred locations of MZ rocks derived from the 2D resistivity section are compatible with the locations proposed by the filtering techniques. Furthermore, the 2D resistivity sections showed a stressed underlying sequence of sedimentary rocks demonstrating sub-vertical contacts and possible displacement along fault planes. A synthetic 2D resistivity model revealed a wedge-shaped formation of 38.0 m thick MZ rocks that can be resolved from the underlying sedimentary layers.

Discovery of terrestrial allabogdanite (Fe,Ni)2P, and the effect of Ni and Mo substitution on the barringerite-allabogdanite high-pressure transition

Abstract Minerals formed at high pressures are sensitive indicators of extreme pressure-temperature conditions that occur in nature. The discovery of the high-pressure polymorph of (Fe,Ni)2P, allabogdanite in the surficial pyrometamorphic rocks of the Hatrurim Formation (the Mottled Zone) surrounding the Dead Sea basin in Israel is the first terrestrial occurrence of a mineral previously only found in iron meteorites. Stepwise annealing experiments demonstrate that allabogdanite is metastable at ambient pressure and that it irreversibly transforms into its low-pressure polymorph, barringerite, upon heating to 850 ± 50 °C. High-pressure, high-temperature diamond-anvil cell (DAC) experiments confirm the results of annealing experiments. The DAC data indicate that Hatrurim allabogdanite is metastable below 7.4 GPa, and the low-to high-pressure phase transition (barringerite → allabogdanite) occurs at 25 ± 3 GPa and 1400 ± 100 °C. The observed transition pressure of Hatrurim allabogdanite is significantly higher than that of pure synthetic Fe2P (8 GPa) due to partial substitution of Fe for Ni (4 wt%) and Mo (2.5 wt%). Because the influence of substituting impurities on the conditions of phase transitions can be unexpectedly strong, our findings confirm that caution should be exercised when extrapolating data from experiments on synthetic compounds to natural systems. Based on the discovery of terrestrial allabogdanite (Fe,Ni)2P coupled with experiments probing the phase transitions in this natural composition, we contend that terrestrial allabogdanite formed via transformation from barringerite and posit potential scenarios of its formation.

Negevite, the pyrite-type NiP2, a new terrestrial phosphide

Abstract Negevite, ideally NiP2, is a new phosphide mineral from pyrometamorphic complex of the Hatrurim Formation (the Mottled Zone), Southern Levant. It is found in phosphide assemblages of the Hatrurim Basin, south Negev Desert, Israel, and Daba-Siwaqa complex, Jordan. The mineral occurs as tiny isometric grains reaching 15 μm in size and forms intimate intergrowths with other phosphides related to the Fe-Ni-P system. In reflected light, negevite is white with yellowish tint and isotropic. Reflectance values for COM recommended wavelengths [R (%), λ (nm)] are as follows: 54.6 (470), 55.0 (546), 55.3 (589), 55.6 (650). Chemical composition of the holotype specimen (electron micro-probe, wt%): Ni 42.57, Co 3.40, Fe 2.87, P 42.93, S 8.33, total 100.10, corresponding to the empirical formula (Ni0.88Co0.07Fe0.06)Σ1.01(P1.68S0.31)Σ1.99. The crystal structure of negevite was solved and refined to R1 = 1.73% based on 52 independent observed [I &amp;gt;2σ(I)] reflections. The mineral is cubic, space group Pa3, a = 5.4816(5) Å, V = 164.71(3) Å3, and Z = 4. Dx = 4.881(1) g/cm3 calculated on the basis of the empirical formula. Negevite is a first natural phosphide belonging to the pyrite structure type. It is a chemical and structural analog of vaesite, NiS2, krutovite, NiAs2, and penroseite, NiSe2. The well-explored catalytic and photocatalytic properties of a synthetic counterpart of negevite could provide new insights into the possible role of higher phosphides as a source of low-valent phosphorus in prebiotic phosphorylation processes.

Raman Spectroscopy and Single-Crystal High-Temperature Investigations of Bentorite, Ca6Cr2(SO4)3(OH)12·26H2O

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 &gt;0.8. Bentorite crystallizes in space group P31c, with a = b = 11.1927(5) Å, c =21.7121(10) Å, V = 2355.60(18) Å3, 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(Cr1.613Al0.387)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.

A distinct retinal pigment epithelial cell autofluorescence pattern in choroideremia predicts early involvement of overlying photoreceptors.

Choroideremia is an X-linked retinal disease characterized by early retinal pigment epithelium (RPE) loss and subsequent retinal degeneration. The RPE adopts either a smooth or mottled appearance on fundus autofluorescence (FAF). It is not known how RPE changes predict the health of the overlying ellipsoid zone (EZ). A retrospective review of FAF and optical coherence tomography (OCT) images from 20 patients with choroideremia was performed. The percentage of intact EZ in each smooth and mottled FAF region was determined using one horizontal trans-foveal OCT section. Fourteen out of 20 patients had distinct smooth and mottled areas in both eyes and were included in the sub-analysis. On average, 62.5±10.1% of the EZ in each smooth region of the right eyes was intact compared to 10.0±4.3% in the mottled areas. The same trend was observed in left eyes: 76.5±7.2% of the EZ was intact in the smooth regions versus 9.8±3.9% in the mottled areas (two-way anova, p<0.0001). Thus, the mottled FAF regions were associated with EZ disruption more so than the smooth areas. Retinal pigment epithelium (RPE) changes correlate with the health of the overlying EZ in choroideremia. The smooth FAF region likely represents early stages of the disease, with most of the area containing preserved EZ, whereas the mottled zone indicates more advanced stages and has mostly disrupted EZ. Because of the clear relationship between FAF findings and EZ integrity, FAF imaging can be used to monitor disease progression and identify areas of preserved EZ that could be rescued by gene therapy.

Optical image and microchemical analysis of gold grains from a weathered profile of the Minvoul greenstone belt, northern Gabon

AbstractMorphological characterization and quantification of gold particles by optical image analysis (OIA) and by compositional analysis of microprobes using scanning electron microscope and electron microprobe analysis techniques were carried out on gold grains from the Minvoul area (Archean greenstone belt in Gabon). Large grains of almost pure gold were found throughout a weathering profile, which consisted of saprolite, mottled clay zone, iron duricrust, pisolitic gravels and yellow latosol. In the deeper horizons, gold was dissolved as shown by corrosion features on the surface of particles with average sizes of 2.6Φ and 2.35Φ in the saprolite and mottled clay zones, respectively. The occurrence of secondary gold in the duricrust was indicated by the larger size of the nuggets (average, 1.8Φ), the high fineness (&gt; 995 in average) and the close textural relationship between gold and neoformed iron oxyhydroxides. The uppermost horizons composed of yellow latosol and pisolitic gravels were interpreted as transported materials based on their size distribution (average 0.85Φ and 1.34Φ), sorting and shape parameters. The best morphological parameter to describe the whole weathering profile was found to be the perimeter/area ratio. The highest ratios were recorded in the saprolite (average 0.192 μm−1), and decreased towards the surface (average 0.057 μm−1). The combination of the OIA technique and the microchemical analysis of gold grains allowed us to define specific morphological and compositional characteristics of the gold particles for each horizon. Both methods proved to be of great utility to understand gold concentration, dissolution and dispersion processes in supergene environments.

Rare-earth element and stable isotope signatures of kaolin from a Pliocene lateritic weathering profile at mid-latitude region (Andalusia, Spain): Implications for paleoweathering and paleoclimatic reconstructions

This study reports the impact of weathering on behavior of rare earth elements (REE) in a coastal lateritic profile developed on Pliocene sediments at mid-latitude location (~37° N), in the Guadalquivir Basin (Spain). It also explores the stable isotope signature of kaolinite providing constraints on paleotemperature and isotopic composition of the ancient meteoric water. The paleoweathering profile (~20 m thick) comprises a white sandy clayey saprolite overlain by a red-mottled clay zone, which in turn is capped by a pisolitic ferricrete. The kaolinitic regolith was practically reduced to a mixture of kaolinite and quartz by intense chemical weathering under warm and seasonally humid climate.The kaolinized material is markedly depleted in total REE (mean value of 77.30 mg kg−1 in the white saprolite and 72.70 mg kg−1 in the mottled zone) relative to the parent rock (168.96 mg kg−1). Development of acidic and oxidizing conditions promoted a suitable soil environment for REE release and leaching with percolating rainwater, leading to an apparent loss of REE from the profile (up to 87%). The parent rock-normalized REE patterns display concave-upward shapes tracing a remarkable depletion in middle REE (MREE), with no significant anomalies. The REE concentrations normalized against the North American Shale Composite (NASC) showed consistently similar fractionation patterns. The MREE-depleted signature (NASC-normalized ratios of La/Sm up to 3.32 and Gd/Lu as low as 0.45) probably arises from reductive dissolution of iron oxyhydroxide phases due to seasonal water saturation, as indicated from redoximorphic features.The <2 μm kaolinite separates showed δ18O values ranging from 17.3‰ to 20.0‰, and δD values between −71‰ and −60‰. The δ18O and δD mean values indicated a crystallization temperature of about 24 °C, which is higher than the local present-day annual mean air temperature (~18 °C). For the calculated temperature, the oxygen isotope fractionation factor between kaolinite and water (αk-w = 1.0248) implies that kaolinite formed in equilibrium with meteoric waters (δ18O = −5.4‰ and δD = −33‰) that closely reflect the regional meteoric precipitation.The lateritic weathering profiles evolved during the mid-Pliocene warm period in the southwestern Iberian margin could be useful for predicting potential future environmental effects of increased atmospheric CO2 on the Earth's critical zone.

Reappraising columnar joints in different rock types and settings

Columnar joints comprise a network of opening-mode fractures that divide material into prismatic columns. They are known in several materials and rock types, including basalt, mud, sandstone, and starch. In all types, the resultant prismatic columns have a similar geometry, facilitating a comparison of columnar joints in different materials and processes such as cooling and drying. In this study, we provide a unique example of columnar joints in low-grade meta-chalks that are the product of spontaneous combustion metamorphism of organic-rich chalks in the “Mottled Zone Complex”, Israel. Although the geometry of the prismatic columns observed in these rocks resembles those seen in basalts, our approximate calculations, based on thermal expansion and temperature difference, show that contraction due to cooling is two orders of magnitude less than the measured contraction. Moreover, the cooling effect should be much more significant in high-grade (ca. 550–900 °C) rather than in low-grade (ca. 200 °C) rocks, but only the latter contain prismatic columns. The prismatic columns are restricted to a discrete stratigraphic level between 1 and 10 meters above a chert and phosphorite unit. We suggest that burning of organic matter in the protolith results in mass and volume losses, and is the principal process that leads to contraction. Changes in texture and pore-structure (recrystallization) accompany the contraction resulting in the rearrangement of the protolith into columnar meta-chalk. This intriguing example of columnar joints in meta-chalk indicates that the geometric similarity of prismatic columns should not serve as the sole argument for their formation during cooling.