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  • 1
    Publication Date: 2015-06-02
    Description: Apatite is ubiquitous in igneous, metamorphic, and sedimentary rocks and is significant to more fields of study than perhaps any other mineral. To help understand why, one needs to know apatite's structure, composition, and crystal chemistry. Apatite has a robust hexagonal atomic framework based on two distinct metal-cation sites ( M 1, M 2), a tetrahedral-cation site ( T ), and an anion column along four edges of the unit cell. These cation and anion sites can, among them, incorporate more than half of the long-lived elements in the periodic table, giving rise to the "apatite supergroup," which contains over 40 mineral species. The structure and composition impart properties that can be technologically, medically, and geologically very useful.
    Print ISSN: 1811-5209
    Electronic ISSN: 1811-5217
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  • 2
    Publication Date: 2016-08-03
    Description: The method of accommodation of solid solution along the OH-Cl binary in calcium phosphate apatites is not fully understood; because of steric constraints in mixtures of OH and Cl anions in the apatite [0,0, z ] anion column, the positions of OH and Cl anions in the pure hydroxylapatite and chlorapatite end-members cannot coexist in the binary anion column. We have undertaken high-precision single-crystal X-ray structure studies of eight synthetic samples along the OH-Cl apatite binary ( R 1 0.0159). We found that for all samples solid solution is attainable in space group P 6 3 / m , but the particular method of solid solution depends on composition. For samples with Cl 〉 OH, three column anion sites (two for Cl, one for OH) provide allowable bond distances with the Ca2 atoms and allow a sequence of column anions that provides sufficient anion-anion distances and also effects reversal of the sense of ordering of the column anions relative to the mirror planes at z = 1/4 and 3/4. In a sample with OH 〉 Cl, three sites exist in the anion column that also provide allowable bond distances to the triangle of Ca2 atoms or its disordered Ca2' equivalent, and afford a sequence of atoms that permits reversal of the anion column and maintenance of P 6 3 / m symmetry. One of those sites is occupied by OH and provides acceptable Ca2-OH distances, and another accommodates Cl with ideal Ca2-Cl distances. A third column anion site is unique among the calcium phosphate apatites. That site, termed the ClOH site, accommodates both OH and Cl. The site has an ideal bond distance for OH to the Ca2 atoms in the Ca2 triangle and also has an ideal bond distance for a Cl occupant to disordered Ca2' atoms; thus, because of the disordering of the Ca2-Ca2' atoms, a single site can accommodate either anion with ideal, but disparate, bond distances to Ca. Finally, in OH-Cl apatites with OH Cl, also crystallizing in space group P 6 3 / m , four anion positions are occupied in the anion column, including the ClOH site that allows occupancy by both OH and Cl. In addition to that site and distinct OH and Cl sites, OH is found to occupy the site within the mirror plane at (0,0,1/4), the site occupied by F in F-bearing apatite. Occupancy of that site is essential to reversing the sense of ordering of the anion column relative to the mirror planes and preserving P 6 3 / m symmetry. Thus, the methods of effecting solid solution along the OH-Cl are composition dependent and complex.
    Print ISSN: 0003-004X
    Electronic ISSN: 1945-3027
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  • 3
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    Unknown
    Mineralogical Society of America
    Publication Date: 2015-05-13
    Description: In the past 150 years, with the discovery of petroleum and the invention of the gasoline-powered internal combustion engine, the rate of extraction of minerals from the Earth has made humans a geologic agent for the first time in the history of the planet. Unprecedented changes have resulted in human society as a result of this extraordinary use of minerals, and perhaps no mineral illustrates that linkage more than the mineral apatite; even the exponential growth of the human population to seven billion Earth inhabitants has been allowed by the extraction of sufficient P from apatite ore to provide fertilizer to feed the planet’s population. Apatite is used extensively in various geological applications, including dating techniques and studies of rare earth element variation in rocks, and is also widely used in material science and medical applications. Apatite forms virtually all hard parts of the human body, and the bioengineering of anion exchange in the apatite material of human tooth enamel through fluoridation is considered one of the top 10 public health achievements of the twentieth century by the U.S. Centers for Disease Control. In addition, the carbonate content of apatite calcifications is currently being investigated as a non-invasive tool in distinguishing between benign and malignant breast tumors. In material applications, apatite is the principle raw material in the fluorescent lighting industry, and its unique crystal chemical properties make it useful in the production of lasers with controllable properties. Apatite is increasingly being employed in the environmental remediation industry through the process of phosphate-induced metal stabilization (PIMS), and its properties make it a useful material for the storage of radioactive waste as substituents in the Ca sites. Despite its remarkable utility and its fundamental role in feeding the world’s population, the details of the apatite atomic arrangement are not fully understood. The Ca phosphate apatites are an anion solid solution (F = fluorapatite; OH = hydroxylapatite; Cl = chlorapatite), and the anion positions in binary and ternary members of the solid solution are not predictable from the anion positions in the pure end-members because of steric effects of anion-anion interactions. Recent attention has focused on a more complete understanding of the apatite atomic arrangement and its properties, both in inorganic and biominerals apatites, and knowledge of the atomic arrangement is advancing. Apatite illustrates the role of minerals in the evolution of modern society, and also the importance of research in the mineral sciences in the broadest sense.
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  • 4
    Publication Date: 2014-02-15
    Description: Apatite sensu lato, Ca 10 (PO 4 ) 6 (F,OH,Cl) 2 , is the tenth most abundant mineral on Earth, and is fundamentally important in geological processes, biological processes, medicine, dentistry, agriculture, environmental remediation, and material science. The steric interactions among anions in the [0,0, z ] anion column in apatite make it impossible to predict the column anion arrangements in solid solutions among the three end-members. In this work we report the measured atomic arrangements of synthetic apatite in the F-Cl apatite binary with nominal composition Ca 10 (PO 4 ) 6 (F 1 Cl 1 ), synthesized in vacuum at high temperature to minimize both hydroxyl- and oxy-component of the apatite. Four crystals from the high-temperature synthesis batch were prepared to assess the homogeneity of the batch and the precision of the location of small portions of an atom in the apatite anion column by single-crystal X-ray diffraction techniques. Crystals were ground to spheres of 80 μm diameter, and full-spheres of Mo K α diffraction data were collected to = 33º, with average redundancies 〉16. Final R 1 values ranged from 0.0145 to 0.0158; the lattice parameters ranged from a = 9.5084(2)–9.5104(3), c = 6.8289(3)–6.8311(2) Å. Based on this study, solid solution in P 6 3 / m apatites along the F-Cl join is attained by creation of an off-mirror fluorine site at (0,0,0.167), a position wherein the fluorine atom relaxes away from its normal position within the {00 l } mirror plane in P 6 3 / m apatites; that relaxation is coupled with relaxation of a chlorine atom at the adjacent mirror plane away from the off-mirror fluorine, allowing acceptable F-Cl distances in the anion column. There are a total of four partially occupied anion positions in the anion column, including two for fluorine [(0,0,1/4) and (0,0,0.167)] and two for chlorine [(0,0,0.086) and (0,0,0)]; the chlorine site at the origin was previously postulated but not observed in calcium apatite solid solutions.
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  • 5
    Publication Date: 2014-10-02
    Description: As metamorphic petrologists attempt to understand the pressure-temperature-time-deformational history of metamorphic rocks, numerous thermobarometers have been developed that help recreate that history. As these thermobarometers are developed, they invariably mature as they are tested on various metamorphic assemblages. In the work "Ti resetting in quartz during dynamic recrystallization: Mechanisms and significance," by Ashley et al. in this issue, the authors demonstrate that the metamorphic process of dynamic recrystallization of quartz lowers the [Ti] in quartz as recrystallizing quartz crystals re-equilibrate in equilibrium with the composition of the intergranular medium, which is typically undersaturated in Ti. The authors conclude that analyses using the TitaniQ thermobarometer in rocks that contain dynamically recrystallized quartz cannot be meaningfully interpreted until methods are developed that can account quantitatively for the reduction of [Ti] resulting from crystal plastic flow. The paper is essential reading for all who use thermobarometers that use quartz as one of the reacting phases.
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  • 6
    Publication Date: 2014-05-16
    Description: Ophirite, Ca 2 Mg 4 [Zn 2 Mn 2 3+ (H 2 O) 2 (Fe 3+ W 9 O 34 ) 2 ]·46H 2 O, is a new mineral species from the Ophir Hill Consolidated mine, Ophir district, Oquirrh Mountains, Tooele County, Utah, U.S.A. Crystals of ophirite are orange-brown tablets on {001} with irregular {100} and {110} bounding forms; individual crystals are up to about 1 mm in maximum dimension and possess a pale orange streak. The mineral is transparent, with a vitreous luster; it does not fluoresce in short- or long-wave ultraviolet radiation. Ophirite has a Mohs hardness of approximately 2 and brittle tenacity. No cleavage or parting was observed in the mineral. The fracture is irregular. The density calculated from the empirical formula using the single-crystal cell data is 4.060 g/cm 3 . Ophirite is biaxial (+) with a 2 V angle of 43(2)°. Indices of refraction for ophirite are α = 1.730(3), β = 1.735(3), = 1.770(3)°. The optic orientation (incompletely determined) is Y b 9° and one optic axis is approximately perpendicular to {001}. Dispersion r 〉 v , strong; pleochroism is X = light orange brown, Y = light orange brown, Z = orange brown; X 〈 Y 〈〈 Z . Chemical analyses of ophirite were obtained by electron probe microanalysis; optimization of that analysis using the results of the crystal-structure analysis yielded the formula \[ \begin{array}{l}{({\hbox{ Ca }}_{1.46}{\hbox{ Mg }}_{0.50}{\hbox{ Zn }}_{0.04})}_{\mathrm{\Sigma }2.00}{({\hbox{ Mg }}_{3.96}{\hbox{ Mn }}_{0.04}^{3+})}_{\mathrm{\Sigma }4.00}[{({\hbox{ Zn }}_{1.16}{\hbox{ Fe }}_{0.68}^{3+}{\hbox{ Ca }}_{0.14}{\hbox{ Sb }}_{0.02}^{5+})}_{\mathrm{\Sigma }2.00}{({\hbox{ Mn }}_{1.42}^{3+}{\hbox{ Sb }}_{0.32}^{5+}{\hbox{ Fe }}_{0.24}^{3+}{\hbox{ W }}_{0.02})}_{\mathrm{\Sigma }2.00}\\\relax \{{({\hbox{ H }}_{2}\hbox{ O })}_{2}{[{({\hbox{ Fe }}_{0.80}^{3+}{\hbox{ Sb }}_{0.11}^{5+}{\hbox{ Ca }}_{0.07}{\hbox{ Mg }}_{0.02})}_{\mathrm{\Sigma }1.00}{({\hbox{ W }}_{8.71}{\hbox{ Mn }}_{0.29}^{3+})}_{\mathrm{\Sigma }1.00}]}_{2}\}]\cdot 46{\hbox{ H }}_{2}\hbox{ O };\end{array} \] the simplified formula of ophirite is Ca 2 Mg 4 [Zn 2 Mn 2 3+ (H 2 O) 2 (Fe 3+ W 9 O 34 ) 2 ]·46H 2 O. Ophirite is triclinic, P 1macr;, with a = 11.9860(2), b = 13.2073(2), c = 17.689(1) Å, α = 69.690(5), β = 85.364(6), = 64.875(5)°, V = 2370.35(18) Å 3 , and Z = 1. The strongest four lines in the diffraction pattern are [ d in Å ( I )( hkl )]: 10.169(100)(100,110), 11.33(91)(011,010), 2.992(75)(334,341, 5), and 2.760(55)(412,006, 3 5). The atomic arrangement of ophirite was solved and refined to R 1 = 0.0298 for 9230 independent reflections. The structural unit, ideally { [6] Zn 2 [6] Mn 2 3+ (H 2 O) 2 ( [4] Fe 3+[6] W 9 6+ O 34 ) 2 } 12– , consists of a [Zn 2 Mn 2 3+ (H 2 O) 2 ] octahedral layer sandwiched between opposing heteropolytungstate tri-lacunary ( [4] Fe 3+[6] W 9 6+ O 34 ) Keggin anions. Similar structures with an octahedral layer between two tri-lacunary Keggin anions are known in synthetic phases. Charge balance in the ophirite structure is maintained by the {[Mg(H 2 O) 6 ] 4 [Ca (H 2 O) 6 ] 2 ·10H 2 O} 12+ interstitial unit. The interstitial unit in the structure of ophirite is formed of two distinct Mg(H 2 O) 6 octahedra and a Ca(H 2 O) 6 O 1 polyhedron, as well as five isolated water molecules. The linkage between the structural unit and the interstitial unit results principally from hydrogen bonding between oxygen atoms of the structural unit with hydrogen atoms of the interstitial unit. Ophirite is the first known mineral to contain a lacunary defect derivative of the Keggin anion, a heteropolyanion that is well known in synthetic phases. The new mineral is named ophirite to recognize its discovery at the Ophir Hill Consolidated mine, Ophir District, Oquirrh Mountains, Tooele County, Utah, U.S.A.
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  • 7
    Publication Date: 2012-08-01
    Description: Fe 2+ - and Mn 2+ -rich tourmalines were used to test whether Fe 2+ and Mn 2+ substitute on the Z site of tourmaline to a detectable degree. Fe-rich tourmaline from a pegmatite from Lower Austria was characterized by crystal-structure refinement, chemical analyses, and Mössbauer and optical spectroscopy. The sample has large amounts of Fe 2+ (~2.3 apfu), and substantial amounts of Fe 3+ (~1.0 apfu). On basis of the collected data, the structural refinement and the spectroscopic data, an initial formula was determined by assigning the entire amount of Fe 3+ (no delocalized electrons) and Ti 4+ to the Z site and the amount of Fe 2+ and Fe 3+ from delocalized electrons to the Y-Z ED doublet (delocalized electrons between Y-Z and Y-Y ): X (Na 0.9 Ca 0.1 ) Y (Fe 2+ 2.0 Al 0.4 Mn 2+ 0.3 Fe 3+ 0.2 ) Z (Al 4.8 Fe 3+ 0.8 Fe 2+ 0.2 Ti 4+ 0.1 ) T (Si 5.9 Al 0.1 )O 18 (BO 3 ) 3 V (OH) 3 W [O 0.5 F 0.3 (OH) 0.2 ] with a = 16.039(1) and c = 7.254(1) Å. This formula is consistent with lack of Fe 2+ at the Z site, apart from that occupancy connected with delocalization of a hopping electron. The formula was further modified by considering two ED doublets to yield: X (Na 0.9 Ca 0.1 ) Y (Fe 2+ 1.8 Al 0.5 Mn 2+ 0.3 Fe 3+ 0.3 ) Z (Al 4.8 Fe 3+ 0.7 Fe 2+ 0.4 Ti 4+ 0.1 ) T (Si 5.9 Al 0.1 )O 18 (BO 3 ) 3 V (OH) 3 W [O 0.5 F 0.3 (OH) 0.2 ]. This formula requires some Fe 2+ (~0.3 apfu) at the Z site, apart from that connected with delocalization of a hopping electron. Optical spectra were recorded from this sample as well as from two other Fe 2+ -rich tourmalines to determine if there is any evidence for Fe 2+ at Y and Z sites. If Fe 2+ were to occupy two different 6-coordinated sites in significant amounts and if these polyhedra have different geometries or metal-oxygen distances, bands from each site should be observed. However, even in high-quality spectra we see no evidence for such a doubling of the bands. We conclude that there is no ultimate proof for Fe 2+ at the Z site, apart from that occupancy connected with delocalization of hopping electrons involving Fe cations at the Y and Z sites. A very Mn-rich tourmaline from a pegmatite on Elba Island, Italy, was characterized by crystal-structure determination, chemical analyses, and optical spectroscopy. The optimized structural formula is X (Na 0.6 0.4 ) Y (Mn 2+ 1.3 Al 1.2 Li 0.5 ) Z Al 6 T Si 6 O 18 (BO 3 ) 3 V (OH) 3 W [F 0.5 O 0.5 ], with a = 15.951(2) and c = 7.138(1) Å. Within a 3 error there is no evidence for Mn occupancy at the Z site by refinement of Al Mn, and, thus, no final proof for Mn 2+ at the Z site, either. Oxidation of these tourmalines at 700–750 °C and 1 bar for 10–72 h converted Fe 2+ to Fe 3+ and Mn 2+ to Mn 3+ with concomitant exchange with Al of the Z site. The refined Z Fe content in the Fe-rich tourmaline increased by ~40% relative to its initial occupancy. The refined Y Fe content was smaller and the 〈 Y -O〉 distance was significantly reduced relative to the unoxidized sample. A similar effect was observed for the oxidized Mn 2+ -rich tourmaline. Simultaneously, H and F were expelled from both samples as indicated by structural refinements, and H expulsion was indicated by infrared spectroscopy. The final species after oxidizing the Fe 2+ -rich tourmaline is buergerite. Its color had changed from blackish to brown-red. After oxidizing the Mn 2+ -rich tourmaline, the previously dark yellow sample was very dark brown-red, as expected for the oxidation of Mn 2+ to Mn 3+ . The unit-cell parameter a decreased during oxidation whereas the c parameter showed a slight increase.
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  • 8
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    Unknown
    Mineralogical Society of America
    Publication Date: 2014-01-03
    Description: The exact nature of the mineral component of bone is not yet totally defined, even though it is recognized as a type of carbonated hydroxylapatite. It is remarkable that such fundamental natural material, which forms all hard parts of the human body except for small portions of the inner ear, is not well understood. Authors Jill Pasteris, Claude H. Yoder, and Brigitte Wopenka have undertaken detailed and truly painstaking experiments to characterize bone material and shed light on its relationship to hydroxylapatite. The authors very effectively demonstrate, through Raman spectroscopic and thermogravimetric analysis of 56 synthetic samples of carbonated apatite containing from 1 to 17 wt% CO 3 , that bone material is not simply carbonated hydroxylapatite, but instead a definable mineralogical entity, a combined hydrated-hydroxylated calcium phosphate phase of the form Ca 10–x [(PO 4 ) 6–x (CO 3 ) x ] (OH) 2–x · n H 2 O, where n ~ 1.5. They hypothesize that water molecules keep the apatite channels stable even when 80% of the hydroxyl sites are vacant (typical in bone apatite, in contrast to hydroxylapatite), and hinder carbonate ions from substituting for hydroxyl ions in the channels, thus regulating chemical access to the channels. The results of this study are extremely important in many fields and will be of particular interest to those in medicine who study diseases of the bone.
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  • 9
    Publication Date: 2017-02-02
    Description: Kegginite, Pb 3 Ca 3 [AsV 12 O 40 (VO)]·20H 2 O, is a new mineral species from the Packrat mine, near Gateway, Mesa County, Colorado, U.S.A. It is a secondary mineral found on asphaltum in a montroseite-and corvusite-bearing sandstone. Other secondary minerals found in close association with kegginite are ansermetite, gypsum, mesaite, and sherwoodite. Crystals of kegginite are orange-red simple hexagonal tablets. The streak is pinkish-orange, the luster is vitreous, the Mohs hardness is about 2, the tenacity is brittle, fracture is irregular, cleavage is good on {001}, and the calculated density is 2.69 g/cm 3 . Kegginite is optically uniaxial (–) with pleochroism: O orange-red and E red-orange; E 〈 O . Electron microprobe analyses yielded the empirical formula Pb 2.98 Ca 2.39 Mg 0.56 V 13.05 As 0.95 O 61 H 40.15 . Kegginite is trigonal, $$P\overline{3}$$ , with a = 14.936(5), c = 15.846(5) Å, V = 3061(2) Å 3 , and Z = 2. The crystal structure of kegginite ( R 1 = 0.064 for 1356 F o 〉 4 F reflections) contains a $${[{\mathrm{As}}^{5+}{\mathrm{V}}_{12}^{5+}{\mathrm{O}}_{40}(\mathrm{VO})]}^{12-}$$ polyoxometalate cluster, which is a mono-capped Keggin -isomer.
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  • 10
    Publication Date: 2017-04-04
    Description: The substitution of F, OH, and Cl in apatite has recently gained increased attention due to the complex nature of incorporation of these three constituents and the implications of apatite column anion chemistry, such as apatite’s contribution to the water budget of the Moon and Mars and the use of apatite anion chemistry as an indicator of halogen and water activities. The solid solutions among F, OH, and Cl are complex because the end-member atomic arrangements cannot fully explain the ternary and binary substitutions of these constituents due to differing atomic radii and the resulting steric constraints in the structure. Three structural variations have recently been reported for the OH-Cl binary solid solution in synthetic samples. This study elucidates column anion arrangements in a chemically zoned ternary apatite from Kurokura, Japan. The structures of the compositionally different core and rim were solved (R1 = 0.0158 and R1 = 0.0143, respectively) in space group P 6 3 /m using single-crystal X-ray diffraction data. The chemistry of these apatites was analyzed using electron microprobe analysis and crystal structure refinement. The core of the Kurokura crystal is a naturally occurring example of the OH Cl apatite structural variation in a ternary chlorapatite, with four column anion sites (one for F, two for Cl and one for both OH and Cl). The rim exhibits a previously unseen apatite structural variation in a ternary OH-rich fluorapatite (with only a trace Cl component) with three column anion sites (one each for F, OH, and Cl). Both structural variations show a splitting of the Ca2 site that enables reasonable column anion bond distances with Ca2 atoms. A sequence of anions that provides reasonable anion-anion distances while simultaneously enabling reversal of the anion sites relative to the mirror planes at z = 1/4 and z = 3/4 exists for both structure variations. This study demonstrates the structural complexity of natural ternary apatites, and that a structural variety of OH-Cl apatite occurs over a wider range of chemistry than initially anticipated. The results have implications regarding the poorly understood (and potentially complex) crystallization history of apatite from Kurokura, Japan.
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