Meyrowitzite, Ca(UO
2)(CO
3)
2·5H
2O, is a
carbonate mineral
Carbonate minerals are those minerals containing the carbonate ion, .
Carbonate divisions Anhydrous carbonates
*Calcite group: trigonal
** Calcite CaCO3
** Gaspéite (Ni,Mg,Fe2+)CO3
** Magnesite MgCO3
** Otavite CdCO3
**Rhodochrosite MnCO3
** ...
verified in May of 2018 by the Commission of New Minerals, Nomenclature and Classification of the
International Mineralogical Association. It is an extremely rare mineral, discovered in the Markey mine Utah, U.S.A. The mineral is a transparent yellow and has blades up to approximately 0.2 mm in length. It is soluble in water or aqueous solutions. Meyrowitzite is named in honor of Robert Meyrowitz (1916-2013), an American analytical chemist. After serving in WW II, he joined the
United States Geological Survey
The United States Geological Survey (USGS), formerly simply known as the Geological Survey, is a scientific agency of the United States government. The scientists of the USGS study the landscape of the United States, its natural resources, ...
(USGS). He was known for developing innovative new methods for analyzing small and difficult to study mineralogical samples along with his formulation of the high-index immersion liquids.
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Occurrence
Meyrowitzite was discovered underground in the Markey mine, Red Canyon, Suan Juan County, Utah, U.S.A. It has not been found in any other location. Mineralized channels of meyrowitzite are in the
Shinarump Member of the
Chinle Formation. The Shinarump member is made up of medium-to coarse-grained sandstone, conglomeratic sandstone beds, and thick
siltstone lenses. Ore minerals were deposited as replacements of wood and other organic materials and as disseminations in the enclosing sandstone. Since the closing of the Markey mine, oxidation of primary ores in the humid underground environment has produced a variety of secondary minerals. These secondary minerals are primarily
sulfate
The sulfate or sulphate ion is a polyatomic anion with the empirical formula . Salts, acid derivatives, and peroxides of sulfate are widely used in industry. Sulfates occur widely in everyday life. Sulfates are salts of sulfuric acid and many ...
s as
efflorescent crusts on the surfaces of mine walls. It is found on calcite-veined
asphaltum
Asphaltite (also known as uintahite, asphaltum, gilsonite or oil sands) is a naturally occurring soluble solid hydrocarbon, a form of asphalt (or bitumen) with a relatively high melting temperature. Its large-scale production occurs in the Uintah ...
in association with
gypsum
Gypsum is a soft sulfate mineral composed of calcium sulfate dihydrate, with the chemical formula . It is widely mined and is used as a fertilizer and as the main constituent in many forms of plaster, blackboard or sidewalk chalk, and drywal ...
,
markeyite, and
rozenite
Rozenite is a hydrous iron sulfate mineral, Fe2+SO4•4(H2O).
It occurs as a secondary mineral, formed under low humidity at less than as an alteration of copper-free melanterite, which is a post mine alteration product of pyrite or marcasite. It ...
.
Properties
Meyrowitzite has bladed crystals with a length up to about 0.2 mm. The blades are commonly irregular and radiating outward from a central point. Blades are elongate on
10 flattened on and exhibit the forms , , , , and . There was no
twinning observed. It is a transparent yellow with vitreous
luster and a very pale yellow
streak. It displays variable
fluorescence
Fluorescence is the emission of light by a substance that has absorbed light or other electromagnetic radiation. It is a form of luminescence. In most cases, the emitted light has a longer wavelength, and therefore a lower photon energy, tha ...
from weak greenish-yellow to moderate greenish blue under a 405 nm laser. It has a hardness of 2 based on
Mohs hardness scale
The Mohs scale of mineral hardness () is a qualitative ordinal scale, from 1 to 10, characterizing scratch resistance of various minerals through the ability of harder material to scratch softer material.
The scale was introduced in 1812 by th ...
. It has
brittle tenacity, irregular
fracture, and one perfect
cleavage on . The
density
Density (volumetric mass density or specific mass) is the substance's mass per unit of volume. The symbol most often used for density is ''ρ'' (the lower case Greek letter rho), although the Latin letter ''D'' can also be used. Mathematical ...
was measured at 2.70(2) g*cm^-3 by flotation in a methylene iodide and toluene mixture. It is easily soluble in room temperature water. It is
optically biaxial (+) with α = 1.520(2), β = 1.528(2), and γ = 1.561(2) measured in white light. The 2V measured using extinction data analyzed with EXCALIBRW is 53.0(6)°; the calculated 2V is 53.3°. The dispersion is weak, r > v. The optical orientation is Z = b, Y ^ a ≈ 19° in obtuse β. Crystals are weakly
pleochroic
Pleochroism (from Greek πλέων, ''pléōn'', "more" and χρῶμα, ''khrôma'', "color") is an optical phenomenon in which a substance has different colors when observed at different angles, especially with polarized light.
Backgroun ...
in shades of pale yellow, X ≈ Y < Z. The
Gladstone–Dale compatibility, 1 – (KP/KC) is –0.039 (excellent) using the
empirical formula
In chemistry, the empirical formula of a chemical compound is the simplest whole number ratio of atoms present in a compound. A simple example of this concept is that the empirical formula of sulfur monoxide, or SO, would simply be SO, as is the ...
, and –0.035 (excellent) using the ideal formula, where k(UO
3) = 0.134.
Raman spectroscopy
Raman spectroscopy is a method of chemical analysis that is non-destructive. The analysis provides detailed information about
chemical structure
A chemical structure determination includes a chemist's specifying the molecular geometry and, when feasible and necessary, the electronic structure of the target molecule or other solid. Molecular geometry refers to the spatial arrangement of ...
, phase,
polymorphy,
crystallinity, and
molecular interactions. Meyrowitzite's Raman spectroscopy was conducted on a Horiba XploRA PLUS. The spectrum was recorded using a 785 nm diode laser because of significant
fluorescence
Fluorescence is the emission of light by a substance that has absorbed light or other electromagnetic radiation. It is a form of luminescence. In most cases, the emitted light has a longer wavelength, and therefore a lower photon energy, tha ...
when using a 532 nm
diode laser
The laser diode chip removed and placed on the eye of a needle for scale
A laser diode (LD, also injection laser diode or ILD, or diode laser) is a semiconductor device similar to a light-emitting diode in which a diode pumped directly with e ...
. Meryrowitzites spectrum is similar to that of Zellerites. However, Meyrowitzite's spectrum has a larger number of bands primarily in the UO
2+2. This is most likely due to the site-symmetry which for Meyrowitzite is
monoclinic
In crystallography, the monoclinic crystal system is one of the seven crystal systems. A crystal system is described by three vectors. In the monoclinic system, the crystal is described by vectors of unequal lengths, as in the orthorhombic s ...
and
orthorhombic for Zellerite.
Chemical analysis
Chemical Analysis
Analytical chemistry studies and uses instruments and methods to separate, identify, and quantify matter. In practice, separation, identification or quantification may constitute the entire analysis or be combined with another method. Separati ...
of Meyrowitzite was performed on a Cameca SX-50
electron microprobe
An electron microprobe (EMP), also known as an electron probe microanalyzer (EPMA) or electron micro probe analyzer (EMPA), is an analytical tool used to non-destructively determine the chemical composition of small volumes of solid materials. It ...
with four
wavelength-dispersive spectrometers and using Probe for
EPMA software at the University of Utah. The
acceleration voltage
In accelerator physics, the term acceleration voltage means the effective voltage surpassed by a charged particle along a defined straight line. If not specified further, the term is likely to refer to the ''longitudinal effective acceleration vol ...
was 15 keV, with a 10 nA beam current, and a beam diameter of 5μm. The raw X-ray intensities were corrected with a φρ(z) algorithm for the matrix effect. The concentration of the total oxygen and carbon, calculated from the ideal formula, were used in the matrix correction. Because of crystal dehydration, the surfaces suffered and it was impossible to obtain a well-polished crystal surface. The sample was not damaged because of the beam. The H
2O and (CO
2) amounts were calculated based on the structure determination (2 C and 13 O apfu) due to insufficient material instead of the more common method of direct determination. The
empirical formula
In chemistry, the empirical formula of a chemical compound is the simplest whole number ratio of atoms present in a compound. A simple example of this concept is that the empirical formula of sulfur monoxide, or SO, would simply be SO, as is the ...
is Ca
0.94(U
1.00O2)(CO
3)2·5(H
2.02O). The ideal formula is Ca(UO
2)(CO
3)
2·5H
2O, which requires CaO 10.78, UO
3 54.98, CO
2 16.92, and H
2O 17.32, totaling 100 wt%.
X-Ray crystallography
X-ray crystallography is the experimental science determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions. By measuring the angles ...
and structure determination
Powder
A powder is a dry, bulk solid composed of many very fine particles that may flow freely when shaken or tilted. Powders are a special sub-class of granular materials, although the terms ''powder'' and '' granular'' are sometimes used to distin ...
and
single-crystal X-ray studies were performed using a Rigaku R-Axis Rapid II curved imaging plate microdiffractometer with monochromatized MoKα radiation. A Gandolfi-like motion was used during the powder study on the φ and ω axes. This was done to randomize the sample which was several crystals thick. Using the JADE 2010 software, d values and intensities were derived by profile fitting.
Unit-cell parameters from the powder data using JADE 2010 are a = 12.417(17) Å, b = 16.127(17) Å, c = 20.123(17) Å, β = 107.53(4)°, and V = 3842(7) Å3. Meyrowitzite crystals are relatively poor-quality for single-crystal study. The crystal fragment, measuring 80 × 80 × 30 μm, exhibited substantial
mosaicity, some spot streaking, and some extra spots indicative of one or more satellite crystals. This crystal provided usable data to a resolution of .88Å. Structural data were determined with Rigaku CrystalCleal software. This included Lorentz and polarization corrections, and the application of an empirical absorption correction using the multi-scan method with ABSCOR. Rigaku XPlain program determined the
space group
In mathematics, physics and chemistry, a space group is the symmetry group of an object in space, usually in three dimensions. The elements of a space group (its symmetry operations) are the rigid transformations of an object that leave it uncha ...
P21/n, which led to a structural solution using SIR2011. Because of the imperfect crystal fragment, numerous reflections violated the extinction conditions for
space group
In mathematics, physics and chemistry, a space group is the symmetry group of an object in space, usually in three dimensions. The elements of a space group (its symmetry operations) are the rigid transformations of an object that leave it uncha ...
P21/n
(n glide) and the commission of five poorly fitting reflections that did not violate the extinction conditions. SHELXL-2013 was used for the refining of the structure. The limited data set allowed refinement with
anisotropic displacement parameters for all fully occupied sites, but not for four approximately half-occupied H
2O sites (OW14, OW15, OW16, and OW17). It also did not allow the location of H sites in difference Fourier maps.
Structure
Meyrowitzite has a crystal structure based on a unique corrugated uranyl carbonate heteropolyhedral sheet. Meyrowitzite is
dimorphous with Zellerite but Zellerites structure is not known. The PXRD patterns for Meyrowitzite and Zellerite are quite different. Although the strongest peaks in the Zellerite pattern are represented in the Meyrowitzite pattern, the four strongest lines in the Meyrowitzite pattern are not in the Zellerite pattern.
There are three U sites in Meyrowitzite's structure. Two (U1 and U2) are surrounded by eight O atoms. This forms a squat UO
8 hexagonal bipyramid
A hexagonal bipyramid is a polyhedron formed from two hexagonal pyramids joined at their bases. The resulting solid has 12 triangular faces, 8 vertices and 18 edges. The 12 faces are identical isosceles triangles.
Although it is face-transitiv ...
. (U3) is surrounded by seven O atoms forming a squat UO
7 pentagonal bipyramid
In geometry, the pentagonal bipyramid (or dipyramid) is third of the infinite set of face-transitive bipyramids, and the 13th Johnson solid (). Each bipyramid is the dual of a uniform prism.
Although it is face-transitive, it is not a Plat ...
. The two short apical bonds of all three bipyramids constitute the UO
2 2+
uranyl group. Of the six CO
3 2– groups in the structure, three centered by C1, C2, and C3 share alternating equatorial edges of the U1
hexagonal bipyramid
A hexagonal bipyramid is a polyhedron formed from two hexagonal pyramids joined at their bases. The resulting solid has 12 triangular faces, 8 vertices and 18 edges. The 12 faces are identical isosceles triangles.
Although it is face-transitiv ...
, thereby forming the well-known uranyl tricarbonate (UTC) unit. The other three, centered by C4, C5, and C6, share alternating equatorial edges of the U2 hexagonal bipyramid, forming a second UTC unit. The five equatorial corners of the U3
pentagonal bipyramid
In geometry, the pentagonal bipyramid (or dipyramid) is third of the infinite set of face-transitive bipyramids, and the 13th Johnson solid (). Each bipyramid is the dual of a uniform prism.
Although it is face-transitive, it is not a Plat ...
are shared with O atoms of the C1, C2, C3, C4, and C6 carbonate groups. These linkages create a unique corrugated uranyl carbonate heteropolyhedral sheet parallel to . The U2 UTCs are oriented perpendicular to the plane of the sheet with the unshared corner of the C5 carbonate group pointing away from the sheet. Three Ca atoms (Ca1, Ca2, and Ca3) are eightfold-coordinated to O atoms in the sheets and to OW atoms, although Ca3 is effectively only sevenfold-coordinated because two of its ligands (OW15 and OW16) are only half-occupied. The Ca
polyhedra
In geometry, a polyhedron (plural polyhedra or polyhedrons; ) is a three-dimensional shape with flat polygonal faces, straight edges and sharp corners or vertices.
A convex polyhedron is the convex hull of finitely many points, not all on ...
do not link to one another; instead, they share edges and corners with the polyhedra in the uranyl carbonate heteropolyhedral sheets, thereby linking the sheets into a framework. The fully occupied OW9 through OW13 sites and the half-occupied OW14 and OW17 sites are located in the cavities in this framework.
See also
*
List of minerals
This is a list of minerals for which there are articles on Wikipedia.
Minerals are distinguished by various chemical and physical properties. Differences in chemical composition and crystal structure distinguish the various ''species''. Within a m ...
References
{{reflist
Carbonate minerals
Monoclinic minerals
Minerals in space group 14
Uranium minerals