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Ancient Ardaxšīr Khwarrah, today known as Shahr-e Gur, situated near the modern town of Firuzabad in Fars, Iran, holds historical significance as the inaugural capital city of the Sasanian Empire. During archaeological excavations conducted in 2005 by an Iranian–German team directed by Mas'oud Azarnoush and Dietrich Huff, a mud-brick complex was uncovered, revealing a remarkably well-preserved stretch of wall painting and a polychrome painted floor. The discovery prompted the hypothesis of a potential funerary context dating back to the Sasanian period. Both the wall painting and painted floor have suffered extensive deterioration attributed to the environmental conditions of the archaeological site, which was inscribed on the UNESCO World Heritage List in 2020. To address the urgent need for preservation and further understanding of the site's artistic and structural elements, an emergency diagnostic project was initiated. Non-invasive investigations were carried out on the wall and floor by optical digital microscopy and portable energy-dispersive X-ray fluorescence. Additionally, representative minute samples underwent analysis through various techniques, including micro-X-ray fluorescence, polarised light microscopy, scanning electron microscopy with energy-dispersive X-ray spectroscopy, micro-Raman spectroscopy, micro-Fourier Transform Infrared Spectroscopy, gas chromatography-mass spectrometry and pyrolysis coupled with gas chromatography-mass spectrometry. The palette of the floor and mural paintings were identified to contain red and yellow ochres, lead-based pigments, carbon black and bone white. The unexpected presence of Egyptian blue mixed with green earth was recognised in the green hues of the wall painting. The detection of protein material in both the wall painting and polychrome floor indicates the use of "a secco" technique, thereby shedding light on the artistic practices employed in Ardaxšīr Khwarrah. [ABSTRACT FROM AUTHOR]

The characterization of phosphorite features within specific North African sedimentary series remains incomplete. Hence, the primary aim of this research is to determine the composition of powder patterns and phosphatic allochem fragments within the Jebel Dhyr syncline, situated in northeastern Algeria. By focusing on this region, the study endeavors to investigate the mineralogical properties and geochemical aspects of Paleocene-Eocene phosphorites in the broader context of North Africa. The methodology employed encompasses geological, petrographic, geochemical, and mineralogical analyses of the rocks. To achieve this objective, we have employed various techniques including thin section analysis, atomic absorption spectrometry, and X-ray diffraction (XRD). The geological section across the Jebel Dhyr area has revealed a succession of horizontally layered rocks. These rocks consist of eight prominent phosphorite layers interspersed with carbonate formations. Additionally, occasional thin layers of flint can be observed within these carbonate layers. XRD analysis of the whole rock established the presence of apatite group minerals such as hydroxylapatite, fluroapatite, francolite, and dahllite. Other minerals identified include carbonates, quartz, zeolites, feldspar, clays, sulphides, and gypsum. XRD recordings on the phosphatic allochem grains (pellets, coprolites, intraclasts, and shark teeth) identified different mineral phases, with coprolites and pellets showing hydroxylapatite and fluorapatite, sometimes associated with dahllite, while granules of different forms revealed hydroxylapatite associated with fluorapatite or francolite. Teeth from the Jebel Dhyr phosphate beam showed the systematic presence of fluorapatite. This study provides valuable information for the comprehensive utilization of phosphorus resources in the Algeria-Tunisia border.

Fluorpyromorphite, ideally Pb5(PO4)3F, a new apatite-group member, an F-dominant analog of pyromorphite and hydroxylpyromorphite. It is a supergene mineral found at two localities: Sukhovyaz Mountain, Ufaley District, Southern Urals (holotype) and Mountain 1004, Tolbachik volcano, Kamchatka (co-type), both in Russia. At Sukhovyaz, fluorpyromorphite forms anhedral grains up to 0.2 mm across (usually much smaller), filling cavities in quartz and sometimes partially replacing fluorapatite. Associated supergene minerals include pyromorphite, hydroxylpyromorphite, fluorphosphohedyphane, mimetite, and nickeltsumcorite. At Tolbachik, fluorpyromorphite occurs in the oxidation zone of paleo-fumarolic deposits in close association with pyromorphite, fluorphosphohedyphane, wulfenite, cerussite, munakataite, vanadinite, chrysocolla, and opal. It forms crude long-prismatic to acicular crystals up to 0.1 mm long and up to 5 μm thick combined in bunches and spherulites up to 0.2 mm. Fluorpyromorphite is colorless (Sukhovyaz) or yellow (Tolbachik), translucent to transparent and has a vitreous luster. It is brittle, with an uneven fracture and poor cleavage on (001). The calculated density values are 7.382 (holotype) and 6.831 (cotype) g/cm³. Fluorpyromorphite is optically uniaxial (-). In reflected light, it is light-grey, weakly anisotropic. The reflectance values (Rmin/Rmax, %) are: 15.8/16.6 (470 nm), 16.2/17.2 (546 nm), 15.9/16.9 (589 nm), 15.4/16.2 (650 nm). The chemical composition is (electron microprobe, wt. %; holotype/co-type): CaO 0.10/3.16, SrO 0.17/0.00, PbO 83.51/77.39, P2O5 16.13/16.35, CrO3 0.00/0.49, SeO3 0.00/0.98, F 1.00/1.35, Cl 0.29/0.40, H2Ocalc 0.13/0.00, -O=(F,Cl) -0.49/-0.66, total 100.84/99.46. The empirical formulae based on 13 anions (O + F + Cl + OH) pfu are Pb4.95Ca0.02Sr0.02P3.00O12F0.70(OH)0.19Cl0.11 (holotype) and Pb4.26Ca0.69P2.83Se6+ 0.09Cr6+0.06 O11.99F0.87Cl0.14 (co-type). Fluorpyromorphite is hexagonal, space group P63m, unit-cell parameters (from powder X-ray diffraction data; holotype / co-type) are: a = 9.779(5) / 9.732(1), c = 7.241(9) / 7.242(1) Å, V = 599.6(7) / 594.0(2) Å3, and Z = 2. The crystal structure was refined using the Rietveld method to Rp= 0.1764 (holotype). Fluorpyromorphite is isostructural with other members of the apatite group, a subdivision of the apatite supergroup. [ABSTRACT FROM AUTHOR]

The new apatite-group mineral pliniusite, ideally Ca5(VO4)3F, was found in fumarole deposits at the Tolbachik volcano, Kamchatka, Russia, and in a pyrometamorphic rock of the Hatrurim Complex, Israel. Pliniusite, together with fluorapatite and svabite, forms a novel and almost continuous ternary solid-solution system characterized by wide variations of T5+ = P, As, and V. In paleo-fumarolic deposits at Mountain 1004 (Tolbachik), members of this system, including the holotype pliniusite, are associated with hematite, tenorite, diopside, andradite, kainotropite, baryte and supergene volborthite, brochantite, gypsum and opal. In sublimates of the active Arsenatnaya fumarole (Tolbachik), pliniusite–svabite–fluorapatite minerals coexist with anhydrite, diopside, hematite, berzeliite, schäferite, calciojohillerite, forsterite, enstatite, magnesioferrite, ludwigite, rhabdoborite-group fluoroborates, powellite, baryte, udinaite, arsenudinaite, paraberzeliite, and spinel. At Nahal Morag, Negev Desert, Israel, the pliniusite cotype and V-bearing fluorapatite occur in schorlomite-gehlenite paralava with rankinite, walstromite, zadovite-aradite series minerals, magnesioferrite, hematite, khesinite, barioferrite, perovskite, gurimite, baryte, tenorite, delafossite, wollastonite, and cuspidine. Pliniusite forms hexagonal prismatic crystals up to 0.3 × 0.1 mm and open-work aggregates up to 2 mm across (Mountain 1004) or grains up to 0.02 mm (Nahal Morag and Arsenatnaya fumarole). Pliniusite is transparent to semitransparent, colorless or whitish, with a vitreous luster. The calculated density is 3.402 g/cm−3. Pliniusite is optically uniaxial (–), ω = 1.763(5), ε = 1.738(5). The empirical formulas of pliniusite type specimens calculated based on 13 anions (O+F+Cl) per formula unit are (Ca4.87Na0.06Sr0.03Fe0.02)Σ4.98(V1.69As0.66P0.45S0.12Si0.09)Σ3.01 O11.97F1.03 (Mountain 1004) and (Ca4.81Sr0.12Ba0.08Na0.05)Σ5.06(V2.64P0.27S0.07Si0.03)Σ3.01O12.15F0.51Cl0.34 (Nahal Morag). Pliniusite has a hexagonal structure with space group P63/m, a = b = 9.5777(7), c = 6.9659(5) Å, V = 553.39(7) Å3, and Z = 2. The structure was solved using single-crystal (holotype) X‑ray difraction, R = 0.0254. The mineral was named in honor of the famous Roman naturalist Pliny the Elder, born Gaius Plinius Secundus (AD 23–79). It is suggested that the combination of high temperature, low pressure, and high oxygen fugacity favors the incorporation of V5+ into calcium apatite-type compounds, leading to the formation of fluorovanadates. [ABSTRACT FROM AUTHOR]

Cave environment allows long-term processes of rock weathering and chemical deposition that cannot occur on Earth surface directly exposed to meteoric and external biochemical agents. Apart from the common carbonate speleothems, chemical precipitation from infiltration water can also produce phosphate-rich formations usually occurring as parietal dark crusts or spheroidal nodules. Despite the potential purposes of these kind of deposits as paleoenvironmental proxies, they have been still poorly investigated by cave scientists. Monte Corchia cave (NW Tuscany, Central Italy) is one of the most studied caves in the world, particularly for paleoclimate reconstructions from calcite speleothems. Several samples of parietal formations were collected in relict phreatic and epiphreatic passages at different altitudinal levels that reflect different evolutionary stages of this large cave system. Samples were analyzed by diffractometry and SEM-EDS possibly revealing the occurrence of hydroxyapatite or fluorapatite mixed with Fe/Mn incrustations and allogenic clastic particles. Crusts often cover the entire section of relict phreatic or epiphreatic passages and can be related to precipitation during waterfilled phases. Phosphate nodules are almost entirely composed by hydroxyapatite or fluoroapatite and could be the result of long-term chemical (or bio-chemical) precipitation in air-filled environments.

The structural stability of vanadinite, Pb5[VO4]3Cl, is reported by high-pressure experiments using synchrotron radiation X-ray diffraction (XRD) and Raman spectroscopy. XRD experiments were performed up to 44.6 GPa and 700 K using an externally-heated diamond anvil cell (EHDAC), and Raman spectroscopy measurements were performed up to 26.8 GPa at room temperature. XRD experiments revealed a reversible phase transition of vanadinite at 23 GPa and 600 K, which is accompanied by a discontinuous volume reduction and color change of the mineral from transparent to reddish during compression. The high-pressure Raman spectra of vanadinite show apparent changes between 18.0 and 22.8 GPa and finally become amorphous at 26.8 GPa, suggesting structural transitions of this mineral upon compression. The structural changes can be distinguished by the emergence of a new vibrational mode that can be attributed to the distortion of [VO4] and the larger distortion of the V–O bonds, respectively. The [VO4] internal modes in vanadinite give isothermal mode Grüneisen parameters varying from 0.149 to 0.286, yielding an average VO4 internal mode Grüneisen parameters of 0.202.

Based on the results of more than 600 electron microprobe analyses of 25 minerals the distribution pattern of the Cr impurity in vanadates, phosphates, and arsenates collected in oxidation zones of six ore deposits of the Urals was studied. Among them are Pb minerals of the brackebuschite, apatite, adelite, and tsumcorite groups and alunite supergroup, as well as carminite, cornwallite, and bayidonite. Vanadates and arsenates with brackebuschite-type structures show a high affinity to Cr. The maximum content of the Cr impurity is characteristic of minerals with specified Fe trivalent cations (ferribushmakinite, arsenbrackebuschite, and gartrellite) or Al (plumbogummite and bushmakinite). The prevailing scheme of isomorphous substitution, according to which chromium enters into the compositions of these minerals, is heterovalent: Cr + M → Т + M (where Т = V, As, P; M = Fe, Al; M = Сu, Zn), whereas the role of isovalent substitutions Cr → S and Cr → Mo in oxosalts that formed in mineral occurrences of the Urals is insignificant. [ABSTRACT FROM AUTHOR]

The preparation and properties of hexagonal strontium-yttrate-silicate apatite (SrY 4 [SiO 4 ] 3 O, space group P6 3 /m) as the main product of sinter-crystallization process, in which the non-equilibrium melt was formed in the temperature interval from 1300 to 1550 °C in the SrO-Y 2 O 3 -SiO 2 system is described in this work. The formation of non-equilibrium melt is facilitated by borate fluxes, alkaline fluxes and talc. The apparent activation energy and the frequency factor of the sinter-crystallization process were determined to be 1525 kJ·mol −1 and 1.04·10 45 s −1 , respectively. The material shows low value of linear thermal expansion coefficient of (1.1±0.1)·10 −6 °C −1 in the temperature range from 25 to 850 °C. The important feature of this compound is the formation of colored center after the exposition to X-ray radiation hence prepared material is an important candidate for optical applications, sensors and dosimeters. [ABSTRACT FROM AUTHOR]

A suite of samples with eudialyte and eudialyte decomposition minerals from the kakortokite and associated pegmatites of the Ilimaussaq complex in South Greenland has been investigated by electron microprobe analysis. Extensive decomposition of eudialyte has resulted in the formation of catapleiite as host for a number of rare and hitherto unknown REE minerals besides known minerals such as monazite and kainosite. Mineral A1 is present in very small amounts in nearly all eudialyte decomposition aggregates and comprises two varieties: Ca-rich A1 with composition HCa3REE6(SiO4)6(F...) and presumed apatite structure, and Ca-poor A1 with composition (Fe,Mn,Ca)1.5REE6Si6FO22 and unknown structure. Mineral A2 with composition (Ca,Fe)1.2REE4Si6O19-y(OH)2y⋅nH2O is indistinguishable from A1 in EMP-backscattered light and has only been found at a limited number of localities. Mineral A2 also occurs as a primary mineral at one locality. Additional rare and new REE-minerals are mineral A3 with composition Na0.2Ca0.6Fe0.2Mn0.5Al0.5REE2.8Si6F0.5O)18-y(OH)2y⋅nH2O; mineral Uk2 with composition REE2.00F1.50O2.25-y(OH)2y⋅nH2O; mineral Uk3 with composition CaREE4O7-yOH)2y⋅nH2O; and mineral Y1 with composition Na2Ca4Y2.7REE1.3F18(OH)4. The Ce:(Y+La+Pr+Nd+Sm+Gd) molar ratio for A1, A2, A3, Uk2, Uk3 and monazite is close to 1:1. Characteristic for A1, A2 and monazite are substantial solid solutions between La and (Pr+Nd+Sm+Gd) with slowly increasing content of Ce as the content of La increases. A similar pattern does not exist for the REE in fresh eudialyte. Kainosite, identified in one decomposition aggregate, has not previously been found in the Il maussaq complex. [ABSTRACT FROM AUTHOR]

The structural stability of vanadinite, Pb5[VO4]3Cl, is reported by high-pressure experiments using synchrotron radiation X-ray diffraction (XRD) and Raman spectroscopy. XRD experiments were performed up to 44.6 GPa and 700 K using an externally-heated diamond anvil cell (EHDAC), and Raman spectroscopy measurements were performed up to 26.8 GPa at room temperature. XRD experiments revealed a reversible phase transition of vanadinite at 23 GPa and 600 K, which is accompanied by a discontinuous volume reduction and color change of the mineral from transparent to reddish during compression. The high-pressure Raman spectra of vanadinite show apparent changes between 18.0 and 22.8 GPa and finally become amorphous at 26.8 GPa, suggesting structural transitions of this mineral upon compression. The structural changes can be distinguished by the emergence of a new vibrational mode that can be attributed to the distortion of [VO4] and the larger distortion of the V–O bonds, respectively. The [VO4] internal modes in vanadinite give isothermal mode Grüneisen parameters varying from 0.149 to 0.286, yielding an average VO4 internal mode Grüneisen parameters of 0.202. [ABSTRACT FROM AUTHOR]

Phosphohedyphane, Ca2Pb3 (PO4)3Cl, space group P63/m, a = 9.857(1), c = 7.130(2) Å, V = 599.9(2) ų, Z = 2, is a new mineral from the Capitana mine, Copiapó, Atacama Province, Chile and has been identified from numerous other deposits world-wide. At the Capitana mine, it occurs as transparent, colorless, tapering hexagonal prisms, as individuals up to about 0.5 mm in length and 0.1 mm in diameter, which are commonly doubly terminated. Crystals often occur in subparallel intergrowths and irregular clusters. Phosphohedyphane forms as a secondary mineral in the oxidized zone of the Capitana mine, a Cu-Pb-Ag deposit, where it closely associated with quartz, duftite, and bayldonite. Crystals exhibit core-to-rim chemical zonation and electron analyses of cores/rims yielded CaO 9.24/7.76, PbO 67.60/69.35, P2O5 18.40/17.00, As2O5 2.73/3.68, Cl 3.32/3.22, -O = Cl -0.75/-0.73, total 100.54/100.28 wt%. The name phosphohedyphane is for the relationship of the mineral to hedyphane. The mineral has an apatite structure with ordering of Ca and Pb in the two non-equivalent large cation sites, as in hedyphane. The structure refinement indicates that the Ca2(6h) site is completely occupied by Pb and the Ca1(4f) site is occupied by 92% Ca and 8% Pb. The tetrahedral site refines to 91% P and 9% As. The refinement indicates the 0,0,0 position to be fully occupied by Cl. The ordering of Ca and Pb in phosphohedyphane has important implications with respect to the chlorapatite-pyromorphite solid solution series. An analysis of compositions of natural members of the pyromorphite-mimetite-turneaureite-chlorapatite system suggests the existence of complete solid solution among pyromorphite, mimetite, hedyphane, and phosphohedyphane. No stable solid solutions appear to exist between the joins phosphohedyphane-hedyphane and chlorapatite-turneaureite in natural systems. [ABSTRACT FROM AUTHOR]