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  • 1
    Publication Date: 2011-01-01
    Description: Through the complementary use of single-crystal X-ray diffraction and X-ray absorption spectroscopy, we present in this paper the first direct results on the site occupancy of thorium in the fluorapatite structure and the structural distortion created by its substitution. Structure refinements based on single-crystal X-ray diffraction data from synthetic Th-doped fluorapatite indicates that Th substitutes almost exclusively in the M2 site. A single-crystal X-ray study of natural fluorapatite from Mineville, New York, also indicated that substituting heavy scatterers (including Th) are concentrated in the apatite M2 site, but definitive site assignments of specific elements were not possible. Extended X-ray absorption fine-structure spectroscopy (EXAFS) was used to probe the local structure of Th in the synthetic fluorapatite (single-crystal form) with a Th concentration of roughly 20000 ppm, as well as Th in the natural Mineville fluorapatite (powder form) with a Th concentration of ~2000 ppm. The EXAFS fitting results also indicate that Th partitions into the M2 site and yield a ~0.05-0.08 A decrease of average M2-O bond distances associated with local structure distortions that are not obtainable from single-crystal X-ray diffraction studies.
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    Electronic ISSN: 1945-3027
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  • 2
    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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  • 3
    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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  • 4
    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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  • 5
    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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  • 6
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    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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  • 7
    Publication Date: 2010-12-22
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  • 8
  • 9
  • 10
    Publication Date: 2014-01-01
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