American Mineralogist, Volume 104, pages 603–610, 2019

Meyrowitzite, Ca(UO2)(CO3)2·5H2O, a new mineral with a novel uranyl-carbonate sheet
Anthony R. Kampf1,*, Jakub Plášil2, Travis A. Olds3, Barbara P. Nash4, Joe Marty5, andHarvey E. Belkin6
Mineral Sciences Department, Natural History Museum of Los Angeles County, 900 Exposition Boulevard, Los Angeles, California 90007, U.S.A.
2
Institute of Physics ASCR, v.v.i., Na Slovance 1999/2, 18221 Prague 8, Czech Republic
3
Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, Indiana 46556, U.S.A.
4
Department of Geology and Geophysics, University of Utah, Salt Lake City, Utah 84112, U.S.A.
55199 East Silver Oak Road, Salt Lake City, Utah 84108, U.S.A.
6
U.S. Geological Survey (Ret.), Reston, Virginia 20190 U.S.A.

1

Abstract
Meyrowitzite, Ca(UO2)(CO3)2·5H2O, is a new mineral species from the Markey mine, Red Canyon,
San Juan County, Utah, U.S.A. It is a secondary phase found on calcite-veined asphaltum in association
with gypsum, markeyite, and rozenite. Meyrowitzite occurs as blades up to about 0.2 mm in length,
elongate on [010], flattened on {100}, and exhibiting the forms {100}, {001}, {101}, {110}, and {011}.
The mineral is yellow and transparent with vitreous luster and very pale yellow streak. Fluorescence
under a 405 nm laser is from weak greenish yellow to moderate greenish blue. The Mohs hardness is
ca. 2, tenacity is brittle, fracture is irregular, and there is one perfect cleavage, {101}. The measured
density is 2.70(2) g/cm3. The mineral is optically biaxial (+) with α = 1.520(2), β = 1.528(2), and γ= 1.561(2) (white light). The 2V(meas) = 53.0(6)°; weak dispersion, r > v; optical orientation: Z = b,
Y ^ a ≈ 19° in obtuse β; pleochroism pale yellow, X ≈ Y < Z. Electron microprobe analyses provided
the empirical formula Ca0.94(U1.00O2)(CO3)2·5(H2.02O) on the basis of U = 1 and O = 13 apfu, as indicated by the crystal structure determination. Meyrowitzite is monoclinic, P21/n, a = 12.376(3), b =16.0867(14), c = 20.1340(17) Å, β = 107.679(13)°, V = 3819.3(12) Å3, and Z = 12. The structure (R1= 0.055 for 3559 Io > 2σI) contains both UO7 pentagonal bipyramids and UO8 hexagonal bipyramids,
the latter participating in uranyl tricarbonate clusters (UTC). The two kinds of bipyramids and thecarbonate groups link to form a novel corrugated heteropolyhedral sheet. This is the first structuralcharacterization of a uranyl-carbonate mineral with a U:C ratio of 1:2. Meyrowitzite is apparently
dimorphous with zellerite.
Keywords: Meyrowitzite, new mineral species, uranyl tricarbonate, crystal structure, zellerite,
Markey mine, Red Canyon, Utah

Introduction
Carbonate minerals containing U are usually relatively
soluble in aqueous solutions. Aqueous uranyl-carbonate complexes are generally quite stable and are responsible for uranium
migration in the environment on a large scale (Langmuir 1978;
Clark et al. 1995). The most abundant complexes are uranyl
monocarbonate, [(UO2)(CO3)]0, uranyl dicarbonate, [(UO2)(CO3)2]2– and uranyl tricarbonate, [(UO2)(CO3)3]4–, with pKavalues of 5.5, 7, and 9, respectively (Langmuir 1978). The mostabundant uranyl carbonate minerals are those with a U:C ratioof 1:3, which crystallize from solutions of relatively high pH,from neutral to alkaline. However, very little data are available
for minerals with a U:C ratio of 1:2; for example, the mineralzellerite, Ca[(UO2)(CO3)2]·5H2O (Coleman et al. 1966), which
occurs commonly within the carbonate-rich alteration associations of supergene U minerals, has so far eluded crystallographic
characterization. Here, we present the description of the newuranyl-carbonate mineral, meyrowitzite, Ca(UO2)(CO3)2·5H2O,
6+* E-mail: akampf@nhm.org
0003-004X/19/0004–603$05.00/DOI: https://doi.org/10.2138/am-2019-6814

a dimorph of zellerite, and the first structural characterization ofa uranyl-carbonate mineral with a U:C ratio of 1:2.
Meyrowitzite is named in honor of American analyticalchemist Robert Meyrowitz (1916–2013). Meyrowitz received
his bachelor’s degree in chemistry from the City College of New
York in 1936, after which he conducted research in microchemical analysis at Brooklyn College (New York). During WorldWar II, he served in the U.S. Army and, because of his skills asa chemist, he was assigned to work on the Manhattan Project.
After the war, he joined the U.S. Geological Survey (USGS),
from which he retired in 1973. In his years at the USGS, he was
especially known for his knack for developing innovative new
methods for analyzing small and difficult to study mineralogical samples and is also well known for his formulation of thehigh-index immersion liquids (1.74 to 2.00) that are still in use
for optical determinations (Meyrowitz and Larsen 1951). He
published prolifically, often collaborating on the descriptions of
new minerals (e.g., brockite, duttonite, goldmanite, hendersonite,metazellerite, ningyoite, sahamalite, sherwoodite, simplotite,
weeksite, and zellerite). Many of the new minerals species that
he worked on were from the uranium deposits of the western
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U.S. Among them was zellerite, the dimorph of the meyrowitzite.
Robert Meyrowitz’ son Alan has approved of the naming of themineral in his father’s honor.
The new mineral and name were approved by the Commission on New Minerals, Nomenclature and Classification of
the International Mineralogical Association (IMA 2018-039).
Two co-type specimens of meyrowitzite are deposited in thecollections of the Natural History Museum of Los Angeles
County, Los Angeles, California, U.S.A., catalog numbers
66789 and 66790.

Occurrence
Meyrowitzite was discovered on specimens collectedunderground in the Markey mine, Red Canyon, White Canyon District, San Juan County, Utah, U.S.A. (37°32′57″N110°18′08″W). The Markey mine is located about 1 km southwest of the Blue Lizard mine, on the east-facing side of Red
Canyon, about 72 km west of the town of Blanding, Utah, andabout 22 km southeast of Good Hope Bay on Lake Powell. The
geology of the Markey mine is quite similar to that of the Blue
Lizard mine (Chenoweth 1993; Kampf et al. 2015), although
the secondary mineralogy of the Markey mine is notably richer
in carbonate phases. The information following is taken largely
from Chenoweth (1993).
Jim Rigg of Grand Junction, Colorado began staking claims
in Red Canyon in March of 1949. The Markey group of claims,
staked by Rigg and others, was purchased by the Anaconda Copper Mining Company on June 1, 1951. After limited explorationand production, the mine closed in 1955. The mine was subsequently acquired from Anaconda by Calvin Black of Blanding,
Utah under whose ownership the mine operated from 1960 to1982 and was a leading producer in the district for nearly thatentire period.
Mineralized channels are in the Shinarump member of the
Chinle Formation. The Shinarump member consists of mediumto coarse-grained carbonaceous sandstone, conglomeratic
sandstone beds, and thick siltstone lenses. Ore minerals were
deposited as replacements of wood and other organic material
and as disseminations in the enclosing sandstone. Since the mineclosed, oxidation of primary ores in the humid undergroundenvironment has produced various secondary minerals, mainly
carbonates and sulfates, as efflorescent crusts on the surfacesof mine walls.
Meyrowitzite is a very rare mineral, found on calcite-veinedasphaltum in association with gypsum, markeyite (Kampf et al.
2018), and rozenite. See Kampf et al. (2018) for a more complete
list of the secondary minerals identified from the Markey mine,
including several that are recently described new species.

hardness of about 2, brittle tenacity, irregular fracture, and one
perfect cleavage on {101}. The density measured by flotation ina mixture of methylene iodide and toluene is 2.70(2) g/cm3. The
calculated density is 2.702 g/cm3 using the empirical formulaand 2.714 g/cm3 using the ideal formula. The mineral is easily
soluble in H2O at room temperature.
Meyrowitzite 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(Gunter et al. 2004) 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 in shadesof pale yellow, X ≈ Y < Z. The Gladstone–Dale compatibility,
1 – (KP/KC) (Mandarino 2007) is –0.039 (excellent) using theempirical formula, and –0.035 (excellent) using the ideal formula,where k(UO3) = 0.134 as provided by Larsen (1921).

Figure 1. Meyrowitzite on asphaltum. The field of view is 0.5 mm
across. (Color online.)

Physical and optical properties
Crystals of meyrowitzite are blades up to about 0.2 mm inlength, commonly in irregular and radiating intergrowths (Fig. 1).
Blades are elongate on [010], flattened on {100} and exhibit
the forms {100}, {001}, {101}, {110}, and {011} (Fig. 2). No
twinning was observed. The mineral is yellow and transparent
with vitreous luster and very pale-yellow streak. Meyrowitzite
exhibits variable fluorescence from weak greenish yellow tomoderate greenish blue under a 405 nm laser. It has a Mohs

Figure 2. Crystal drawing of meyrowitzite, clinographic projection
in nonstandard orientation, b vertical.

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605

Figure 3. Raman spectrum of meyrowitzite recorded using a 785 nm diode laser.

Raman spectroscopy
Raman spectroscopy was conducted on a Horiba XploRA
PLUS. Because of significant fluorescence using a 532 nm
diode laser, the spectrum was recorded using a 785 nm diodelaser. The spectrum from 1800 to 80 cm–1 is shown in Figure 3.
In general, the measured meyrowitzite spectrum is similar to thespectrum of zellerite (Frost et al. 2008); however, the spectrumof meyrowitzite contains larger number of bands (especially inthe region of UO2+
2 stretching vibrations), most probably due
to lowering of the corresponding site-symmetry: orthorhombic(zellerite) → monoclinic (meyrowitzite).
A broad band composed of two overlapping bands at 1450
and 1380 cm–1 results from the split doubly degenerate ν3 (CO3)2–
antisymmetric stretching vibrations of the (CO3)2– polyhedra.
Medium to strong bands at 1100, 1095, 1080, and 1065 cm–1
are associated with the ν1 (CO3)2– symmetric stretching vibrations. Splitting of these bands is consistent with the presence ofstructurally non-equivalent carbonate units (Koglin et al. 1979;
Anderson et al. 1980; Čejka 1999, 2005, and references therein);
there are six independent C sites in the structure of meyrowitzite(see below). A multi-component band of high intensity, composedof overlapping bands at 850, 840, 835, and 825 cm–1, is attributable to the ν2 (δ) (CO3)2– bending vibrations, and (in overlap)
to the ν1 (UO2)2+ symmetric stretching vibrations. Using theempirical relation of Bartlett and Cooney (1989), we can infer
the corresponding U–O bond lengths from the above-mentioned
wavenumbers (in the order as given above): 1.76, 1.77, 1.78, and1.79 Å. The structure refinement provided U–O bond-lengths in
the range of 1.75–1.80 Å; therefore, it is possible that all observed
overlapping bands in the region 850–825 cm–1 belong to the ν1(UO2)2+ symmetric stretching vibration. A strong component
band, composed of overlapping bands at 760 and 745 cm–1, andTable 1. Analytical results for meyrowitzite
Constituent Mean
Range
St.dev. Probe standard Normalized
CaO
12.67 12.51–12.93
0.22
diopside
10.18
UO3
68.77 68.14–69.86
0.95
syn. UO2
55.23
CO2a					 17.00
H2Oa					 17.60
Total					100.01aBased on structure.

Table 2. Data collection and structure refinement details for meyrowitzite
Diffractometer
X-ray radiation/power
Temperature
Structural formulaSpace group
Unit-cell dimensions

Rigaku R-Axis Rapid II
MoKα (λ = 0.71075 Å)/50 kV, 40 mA
293(2) K
Ca(UO2)(CO3)2·5H2O
P21/n
a = 12.376(3) Å
b = 16.0867(14) Åc = 20.1340(17) Å
β = 107.679(13)°V
3819.3(12) Å3
Z
12
Density (for above formula)
2.714 g/cm3
Absorption coefficient13.207 mm–1
F(000)
2796
Crystal size
80 × 80 × 30 µm
θ range
3.07 to 22.44°
Index ranges–13 ≤ h ≤ 13, –17 ≤ k ≤ 16, –21 ≤ l ≤ 21
Frames collected/exposure
36/25 minReflections collected/unique
17068/4874; Rint = 0.085
Reflections with I > 2σI
3559
Completeness to θ = 22.44°
98.1%
Refinement method
Full-matrix least-squares on F2Parameter/restraints
459/0
GoF
1.052
Final R indices [I > 2σI]R1 = 0.0553, wR2 = 0.1296
R indices (all data)
R1 = 0.0818, wR2 = 0.1469
Largest diff. peak/hole+2.05/–1.37 e A–3
Notes: Rint = Σ|Fo2 – Fo2(mean)|/Σ[Fo2]. GoF = S = {Σ[w(Fo2 – F2c)2]/(n–p)}1/2. R1 = Σ||Fo| – |Fc||/Σ|Fo|.
wR2 = {Σ[w(Fo2 – Fo2)2]/Σ[w(Fo2)2]}1/2; w = 1/[σ2(Fo2) + (aP)2 + bP] where a is 0.057, b is98.855, and P is [2F2c + Max(Fo2,0)]/3.

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a weak composite band at 687 cm–1 are attributable to the ν4(δ) (CO3)2– bending vibrations. Medium to strong bands at 270
and 240 cm–1 are attributable to split doubly degenerate ν2 (δ)(UO2)2+ bending vibrations. Medium-strong bands at 218, 145,
and 125 cm–1 are attributable to the lattice modes (Koglin et al.
1979; Anderson et al. 1980; Čejka 1999, 2005).

Chemical analysis
Chemical analyses (3) were performed at the Universityof Utah on a Cameca SX-50 electron microprobe with four
wavelength-dispersive spectrometers and using Probe for EPMA
software (Probe Software, Inc., Eugene, Oregon). Analyticalconditions were 15 keV accelerating voltage, 10 nA beam current, and a beam diameter of 5 μm. Raw X‑ray intensities werecorrected for matrix effects with a φρ(z) algorithm (Pouchou andPichoir 1991). Concentrations of total oxygen and carbon, calcu-

lated from the ideal formula, were used in the matrix correction.
It was impossible to obtain a good polish and crystal surfaces
suffered further because of crystal dehydration; however, thebeam produced no damage to the sample. Because insufficientmaterial is available for direct determination of H2O and CO2,
they are calculated based upon the structure determination (2 C
and 13 O apfu). Analytical data are given in Table 1. The empirical formula is Ca0.94(U1.00O2)(CO3)2·5(H2.02O). The ideal formula
is Ca(UO2)(CO3)2·5H2O, which requires CaO 10.78, UO3 54.98,
CO2 16.92, and H2O 17.32, total 100 wt%.

X‑ray crystallography and structure
determination

Both powder and single-crystal X‑ray studies were carried out using a Rigaku R-Axis Rapid II curved imaging plate
microdiffractometer with monochromatized MoKα radiation. For

Table 3. Atom coordinates and displacement parameters (Å2) for meyrowitzite
x/a
y/b
Ca1
0.7593(4)0.3457(2)Ca20.6749(4)0.5508(2)Ca30.1484(5)0.1091(3)U10.60111(7)0.34393(4)U20.05568(7)0.33897(5)U30.76212(6)0.59814(4)C1
0.5974(16)0.1959(12)C20.5142(19)0.6277(15)C30.7143(18)0.4874(12)C40.9818(18)0.4932(12)C50.253(2)0.3137(14)C60.5804(19)0.6933(13)O10.8909(12)0.6293(7)O2
0.5428(13)0.2016(8)O30.6485(12)0.2641(7)O40.5196(13)0.6974(8)O50.5694(10)0.6083(8)O60.4405(12)0.5750(8)O70.7502(12)0.5550(7)O80.6969(12)0.4220(8)O90.6874(12)0.4815(8)O100.0716(13)0.4899(8)O110.9489(12)0.5639(8)O120.9290(12)0.4250(8)O131.3390(14)0.3058(9)O140.1918(13)0.2544(9)O150.2133(13)0.3884(8)O160.6442(12)0.6321(8)O170.9005(12)0.2643(8)O180.0126(13)0.1893(8)O190.7239(12)0.3057(8)O20
0.4758(12)0.3843(9)O210.1367(14)0.3260(8)O220.9722(14)0.3546(9)O23
0.7814(12)0.7007(7)O240.7443(11)0.4941(7)OW10.8697(14)0.3414(8)OW20.4310(12)0.4793(9)OW30.5835(14)0.3514(9)OW40.7873(15)0.6445(10)OW50.2297(14)0.0784(11)OW60.3441(18)0.1329(14)OW70.981(2)0.0218(13)OW80.832(2)0.4624(15)OW90.225(3)–0.0284(16)OW100.455(3)0.2152(16)OW110.241(4)0.1914(18)OW120.505(3)0.0168(16)OW130.290(3)0.1861(15)aOW140.966(5)0.325(3)aOW15
0.011(7)0.186(5)OW16a0.101(5)0.128(4)aOW17
0.046(7)0.160(5)a
0.5 assigned occupancy.

z/c0.7368(2)0.4255(2)0.6308(3)0.52659(4)0.68741(5)0.74902(4)0.6060(10)0.6177(11)0.6019(11)0.7280(10)0.6425(13)0.8124(12)0.8609(7)0.5410(7)0.6336(6)0.5892(7)0.6814(7)0.5799(6)0.6335(6)0.6329(6)0.5351(6)0.7085(8)0.7482(8)0.7304(8)0.6225(8)0.6539(9)0.6514(8)0.8209(7)0.7108(8)0.6706(9)0.5103(7)0.5419(7)0.7743(8)0.5997(8)0.7220(7)0.7771(6)0.8553(7)0.6980(7)0.7589(9)0.5215(9)0.7529(9)0.6280(13)0.6179(14)0.4427(15)0.6251(17)0.7872(19)0.8534(16)0.4186(17)0.4748(15)0.465(3)0.517(4)0.514(3)0.374(4)

Ueq
U11
U22
U33
U23
U13
U12
0.0290(10)0.036(3)0.019(2)0.030(2)0.0017(18) 0.0074(19)0.0002(18)0.0331(10)0.046(3)0.018(2)0.039(2)0.0028(19) 0.019(2)0.0009(19)0.0581(14)0.075(4)0.030(3)0.080(4)–0.001(3)0.040(3)0.005(3)0.0276(2)0.0375(5)0.0153(4)0.0270(4)0.0009(3)0.0054(4)–0.0003(3)0.0377(3)0.0420(6)0.0198(4)0.0570(6)–0.0047(4)0.0237(4)–0.0035(4)0.0262(2)0.0357(5)0.0129(4)0.0273(4)–0.0021(3)0.0056(3)0.0001(3)0.028(5)0.031(13)0.025(12)0.023(11)0.015(10)0.000(9)–0.018(9)0.042(6)0.044(15)0.049(15)0.027(13)–0.015(12)0.001(11)–0.002(12)0.035(5)0.037(14)0.020(12)0.034(13)–0.008(11)–0.012(10)0.006(10)0.031(5)0.033(14)0.028(13)0.032(12)0.001(10)0.008(10)–0.012(10)0.051(7)0.058(18)0.033(14)0.068(17)–0.010(12)0.027(14)–0.020(13)0.040(6)0.033(15)0.026(13)0.059(15)–0.006(11)0.012(12)0.006(11)0.039(4)0.059(10)0.008(7)0.041(8)–0.013(6)0.003(7)0.014(6)0.042(4)0.066(11)0.020(7)0.035(9)0.001(7)0.009(8)–0.014(7)0.036(4)0.058(10)0.016(7)0.024(7)0.016(6)–0.004(7)–0.005(7)0.040(4)0.060(11)0.025(8)0.030(8)0.003(7)0.005(7)–0.012(7)0.034(3)0.016(7)0.030(8)0.047(9)0.015(7)–0.002(7)–0.008(6)0.035(3)0.043(9)0.029(8)0.028(8)0.004(7)0.003(7)–0.008(7)0.034(3)0.062(10)0.009(7)0.029(7)–0.002(6)0.013(7)0.002(6)0.036(4)0.068(11)0.014(7)0.020(7)–0.006(6)0.006(7)–0.024(7)0.034(3)0.054(10)0.024(7)0.022(8)–0.010(6)0.008(7)–0.003(7)0.047(4)0.051(11)0.025(8)0.069(11)–0.009(7)0.024(9)–0.005(7)0.042(4)0.044(10)0.011(7)0.070(11)0.003(7)0.014(8)0.009(6)0.044(4)0.045(10)0.023(8)0.071(11)–0.009(8)0.029(8)0.005(7)0.052(4)0.056(11)0.035(9)0.079(12)0.018(8)0.041(10)0.010(8)0.052(4)0.046(10)0.033(9)0.095(13)–0.006(9)0.048(10)–0.003(8)0.045(4)0.056(10)0.014(7)0.077(11)–0.001(7)0.039(9)0.002(7)0.037(4)0.039(9)0.025(8)0.051(9)0.006(7)0.022(7)0.010(7)0.045(4)0.043(10)0.025(9)0.074(11)–0.015(8)0.031(8)–0.013(7)0.050(4)0.036(10)0.020(8)0.104(13)–0.010(8)0.036(9)–0.013(7)0.038(4)0.040(9)0.031(8)0.041(8)–0.015(7)0.007(7)–0.008(7)0.041(4)0.047(10)0.041(9)0.034(8)0.005(7)0.014(7)–0.001(7)0.052(4)0.068(12)0.017(8)0.076(11)–0.008(8)0.032(9)0.001(7)0.052(4)0.063(12)0.036(9)0.057(10)–0.007(8)0.020(9)–0.016(8)0.038(4)0.056(10)0.009(7)0.047(9)0.005(6)0.011(8)0.005(6)0.026(3)0.039(9)0.011(6)0.021(7)–0.002(5)0.000(6)0.001(6)0.050(4)0.077(12)0.021(8)0.044(9)–0.005(7)0.008(8)0.014(8)0.039(4)0.034(9)0.042(9)0.043(9)–0.003(7)0.015(7)–0.006(7)0.060(5)0.056(11)0.037(9)0.097(13)0.013(9)0.040(10)0.004(8)0.069(5)0.065(13)0.047(10)0.076(12)0.014(9)–0.005(10)–0.026(9)0.071(5)0.058(12)0.073(13)0.091(14)0.030(11)0.034(10)0.017(10)0.102(8)0.089(17)0.094(16)0.15(2)–0.015(15)0.082(16)0.000(13)0.116(9)0.099(18)0.075(14)0.19(3)–0.056(16)0.074(17)–0.031(13)0.130(9)0.11(2)0.100(18)0.18(3)–0.006(18)0.032(18)0.043(16)0.162(12)0.21(3)0.082(18)0.21(3)–0.031(19)0.08(3)0.05(2)0.166(13)0.15(3)0.080(18)0.29(4)0.00(2)0.10(3)–0.014(18)0.193(16)0.31(5)0.10(2)0.14(3)0.027(19)0.02(3)0.08(3)0.199(18)0.24(4)0.086(19)0.18(3)0.00(2)–0.07(3)–0.05(2)0.141(11)0.21(3)0.079(17)0.16(3)–0.001(17)0.10(2)–0.019(18)0.127(18)						0.21(3)						0.14(2)						0.20(3)						American Mineralogist, vol. 104, 2019
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KAMPF ET AL.: MEYROWITZITE, A NEW URANYL-CARBONATE MINERAL
Table 4. Selected bond distances (Å) for meyrowitzite
Ca1-O8
Ca1-OW3
Ca1-OW1
Ca1-O17
Ca1-O3
Ca1-O12
Ca1-O24
Ca1-O23<Ca1-O>U1-O19U1-O20
U1-O3
U1-O6
U1-O9
U1-O2
U1-O4
U1-O8
<U1-OUr><U1-Oeq>
C1-O1
C1-O2
C1-O3
<C1-O>
C4-O12
C4-O10C4-O11<C4-O>

2.345(13)2.351(16)2.362(15)
2.365(15)2.489(13)2.494(15)2.546(12)2.575(13)2.441
1.760(14)1.792(14)2.422(11)2.428(12)2.440(13)2.444(13)2.448(13)2.454(11)
1.776
2.439
1.25(2)
1.28(2)1.30(2)1.28
1.29(2)
1.29(2)
1.31(2)1.30

Ca2-OW8
Ca2-O20
Ca2-O9Ca2-O6
Ca2-OW2
Ca2-O13
Ca2-OW4
Ca2-O15<Ca2-O>U2-O21
U2-O22
U2-O15
U2-O14
U2-O17
U2-O12
U2-O10U2-O18<U2-OUr><U2-Oeq>
C2-O4
C2-O5
C2-O6
<C2-O>
C5-O13C5-O14C5-O15<C5-O>

2.35(2)Ca3-OW16
2.396(15)Ca3-OW5
2.435(13)Ca3-O142.461(14)Ca3-OW92.482(14)Ca3-O18
2.487(15)Ca3-OW7
2.512(17)Ca3-OW6
2.565(14)Ca3-OW15
2.461<Ca3-O>1.745(17)
U3-O231.773(16)
U3-O242.412(14)U3-O5
2.415(14)U3-O112.430(13)U3-O1
2.438(13)U3-O7
2.463(13)
U3-O162.467(13)<U3-OUr>
1.759<U3-Oeq>2.438		1.27(3)C3-O7
1.29(2)C3-O8
1.31(2)C3-O9
1.29<C3-O>
1.25(3)C6-O16
1.28(3)C6-O171.33(3)C6-O18
1.29<C6-O>

2.27(5)2.409(18)2.412(15)2.43(2)2.439(16)2.45(2)2.47(2)2.81(8)2.461
1.775(12)1.801(11)2.366(12)2.382(14)2.385(13)2.388(12)2.410(13)
1.788
2.386
1.27(2)
1.27(2)
1.29(2)1.28
1.24(2)
1.28(2)1.30(3)
1.27

the powder study, a Gandolfi-like motion on the φ and ω axes wasused to randomize the sample, which consisted of several crystals. Observed d values and intensities were derived by profile fitting using JADE 2010 software (Materials Data, Inc. Livermore,
California). Data are given in Supplemental1 Table 1. Unit-cellparameters refined from the powder data using JADE 2010 withwhole pattern fitting are a = 12.417(17), b = 16.127(17), c =20.123(17) Å, β = 107.53(4)°, and V = 3842(7) Å3.
Crystals of meyrowitzite are of relatively poor quality forsingle-crystal study. The best crystal fragment, which wasused for the collection of structure data, exhibited significant
mosaicity, some spot streaking and some extra spots indicative607

of one or more satellite crystals. This fragment, measuring only
80 × 80 × 30 μm, provided usable data only to a resolution of
0.88 Å. The Rigaku CrystalClear software package was used forprocessing the structure data, including Lorentz and polarization
corrections, and the application of an empirical absorption correction using the multi-scan method with ABSCOR (Higashi2001). The space group P21/n was suggested by the Rigaku
XPlain program, which readily led to a structure solution using
SIR2011 (Burla et al. 2012). It should be noted that numerous
reflections violated the extinction conditions for space group
P21/n, and particularly for the n glide; however, efforts to obtain
viable structure models in other space groups were unsuccessful.
We attribute the space-group violations to the imperfect natureof the crystal fragment, as noted above, and this also led us toomit five poorly fitting reflections that did not violate the extinction conditions. SHELXL-2013 (Sheldrick 2015) was used
for the refinement of the structure. The limited data set allowedrefinement with anisotropic displacement parameters for all fully
occupied sites, but not for four approximately half-occupied H2O
sites (OW14, OW15, OW16, and OW17). It also did not allow
the location of H sites in difference Fourier maps. Data collection
and refinement details are given in Table 2, atom coordinates anddisplacement parameters in Table 3, selected bond distances inTable 4, and a bond valence analysis in Table 5.

Discussion
There are three U sites in the structure of meyrowitzite.
Two (U1 and U2) are surrounded by eight O atoms forming asquat UO8 hexagonal bipyramid; the other (U3) is surroundedby seven O atoms forming a squat UO7 pentagonal bipyramid.
The two short apical bonds of all three bipyramids constitute the2–
UO2+
2 uranyl group. Of the six CO3 groups in the structure, threecentered by C1, C2, and C3 share alternating equatorial edges of
the U1 hexagonal bipyramid, thereby forming the well-known

Table 5. Bond-valence analysis for meyrowitzite (values are expressed in valence unitsa)
Ca1
Ca2
Ca3
U1
U2
U3
C1
C2
C3
C4
C5
C6
H bonds
ΣO1						0.531.46						
0.18
2.17
O2				
0.47			1.35						
0.13
1.94
O3
0.23			0.49			1.28							
1.99O4				
0.47				1.38					0.202.05O5						0.55		 1.31					 0.19
2.05
O6		
0.24		
0.48				1.24						
1.97O7						0.52			1.38				 0.17
2.08
O8
0.34			0.46					1.38					2.18
O9		0.26		
0.47					1.31					2.05
O10					 0.45					1.31			 0.21
1.97
O11						0.53				1.31			 0.16
1.99
O12
0.22				 0.47					1.24				1.94
O13		
0.23									1.46		
0.19
1.88
O14			
0.28		
0.50						1.35			2.12O15		0.18			0.50						1.18		0.13
1.99
O16						0.50						1.50		2.00
O17
0.32				0.48							1.35		
2.15
O18			
0.26		
0.45							1.28		
1.98
O19				1.75										
1.75
O20		
0.29		
1.65										
1.94O21					1.80								
0.20
2.00
O22					1.71								
0.11
1.81
O23
0.18					1.70							 0.15
2.03
O24
0.19					1.62							 0.13
1.94
OWtotal 0.65
0.77
1.30											
Σ
2.13
1.98
1.84
6.24
6.36
5.94
4.08
3.93
4.08
3.86
3.98
4.12		aCation-O bond valence parameters are from Gagné and Hawthorne (2015). The OW sites are not listed individually; however, their hydrogen bond contributions
to other O sites are included, as are their total bond strength contributions to the Ca sites. Hydrogen-bond strengths are based on O-O bond lengths from Ferraris
and Ivaldi (1988).
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KAMPF ET AL.: MEYROWITZITE, A NEW URANYL-CARBONATE MINERAL

Figure 4. The uranyl carbonate sheet in the structure of meyrowitzite
viewed down [101]. (Color online.)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 are shared with O atomsof the C1, C2, C3, C4, and C6 carbonate groups. These linkages
create a unique corrugated uranyl carbonate heteropolyhedral
sheet parallel to {101} (Fig. 4). The U2 UTCs are oriented perpendicular to the plane of the sheet (Fig. 5) with the unsharedcorner of the C5 carbonate group pointing away from the sheet.
Three Ca atoms (Ca1, Ca2, and Ca3) are eightfold-coordinatedto 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 do

Figure 5. The structure of meyrowitzite viewed down [010]. The
O atoms of isolated H2O groups are shown as white balls. The unit-cell
outline is shown by dashed lines. (Color online.)

Figure 6. The structure of meyrowitzite viewed down [100]. The
O atoms of isolated H2O groups are shown as white balls. The unit-cell
outline is shown by dashed lines. (Color online.)

not link to one another; instead, they share edges and corners withthe polyhedra in the uranyl carbonate heteropolyhedral sheets,
thereby linking the sheets into a framework (Fig. 6). The fully
occupied OW9 through OW13 sites and the half-occupied OW14
and OW17 sites are located in the cavities in this framework.
Minerals with structures containing both UO7 pentagonal
bipyramid and UO8 hexagonal bipyramid are rare. Other
examples include ewingite, Mg8Ca8(UO2)24(CO3)30O4(OH)12(H2O)138 (Olds et al. 2017) and fontanite, Ca[(UO2)3(CO3)2O2](H2O)6 (Hughes and Burns 2003). The structure of ewingite
is based on a large and complex uranyl carbonate polyhedralcluster that bears no similarity to the structure of meyrowitzite.
Fontanite has uranyl carbonate sheets that are linked by CaO8
polyhedra; however, the UO7 and UO8 polyhedra form edgesharing chains within these sheets and there are no UTC units,
but instead uranyl dicarbonate units.

Figure 7. Comparison of powder X‑ray diffraction patterns formeyrowitzite and zellerite. (Color online.)

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KAMPF ET AL.: MEYROWITZITE, A NEW URANYL-CARBONATE MINERAL

Meyrowitzite has a crystal structure based on a unique corrugated uranyl carbonate heteropolyhedral sheet. Meyrowitzite
is apparently dimorphous with zellerite (Coleman et al. 1966);
however, the structure of zellerite is not known. The PXRD
patterns for meyrowitzite and zellerite, compared graphicallyin Figure 7, are quite different. Although the strongest peaks inthe zellerite pattern are represented in the meyrowitzite pattern,
the four strongest lines in the meyrowitzite pattern are not in thezellerite pattern. Comparative data for meyrowitzite and zellerite
are provided in Table 6.

Implications
Numerous studies conducted over the past 50 years have led
to a well-developed understanding of the geochemistry of U-CO3
systems (Langmuir 1978; Choppin and Jensen 2010; Maher et al.
2013). All acknowledge that carbonate binds to uranium strongly
and that uranyl-carbonate complexes are among those most
relevant to the environmental chemistry of uranium. One of themost common species, the uranyl-tricarbonate complex (UTC), is
exceptionally stable in aqueous solutions and it is known to occurin 33 different uranyl-carbonate minerals. Significant evidence
suggests that additional polymeric UTC-hydrolyzed U complexes
are prevalent species in some systems (Ciavatta et al. 1981; Sainiet al. 1989; Müller et al. 2008), and this combination is known
in several exceptionally rare minerals, including fontanite,
Ca[(UO2)3(CO3)2O2](H2O)6 (Hughes and Burns 2003), roubaultite,
Cu2(UO2)3(CO3)2O2(OH)2(H2O)4 (Ginderow and Cesbron 1985),
wyartite, Ca(CO3)[U5+(U6+O2)2O4(OH)](H2O)7 (Burns and Finch1999), bijvoetite-Y, [Y8(H2O)25(UO2)16O8(OH)8(CO3)16](H2O)14(Li et al. 2000), kamotoite-(Y), Y2(UO2)4O2(OH)2(CO3)4(H2O)12.54(Plášil and Petříček 2017), above-mentioned ewingite (Olds et al.
2017), and herein with the description of meyrowitzite. The structure of ewingite suggests that relatively large polynuclear species
containing hydrolyzed uranium and UTC may have assembled insolution prior to crystal growth, or possibly at the crystal-solution
interface. Though we recognize the conditions required for theirformation are very narrow, these minerals reveal definite gaps
in our understanding of uranyl-carbonate-hydroxide equilibria
that can be better determined through crystal-chemical studies
of natural systems. Crystallization of these minerals offers a diagnostic view into the conditions and speciation of the solutions
from which they crystallize. These missing data are necessary
for producing accurate models of contamination speciation in
repositories for nuclear waste.
Table 6. Comparative data for meyrowitzite and zellerite
Ideal formulaSpace group
a (Å)
b (Å)
c (Å)
β (°)
V (Å3)
Z
Densitymeas (g/cm3)
Optical characterαβγ2V (°)
Reference

Meyrowitzite
Ca(UO2)(CO3)2·5H2O
P21/n
12.376(3)16.0867(14)20.1340(17)107.679(13)3819.3(12)122.70(2)
biaxial (+)
1.520(2)1.528(2)1.561(2)53.0(6)This study

Zellerite
Ca(UO2)(CO3)2·5H2O
Pmn21 or Pmnm (probable)
11.220(15)19.252(16)4.933(16)1065(2)4
3.25(1)
biaxial (+)
1.536(5)1.559(5)1.697(5)30–40
Coleman et al. (1966)

609

The fact that meyrowitzite contains a heretofore-unreported
type of uranyl-carbonate heteropolyhedral sheet makes its reported occurrence in a natural setting of significant importancein expanding our understanding of uranyl-carbonate interactions in natural systems. Furthermore, although based upon
composition alone, meyrowitzite, with a U:C ratio of 1:2, might
have been expected to contain the uranyl-dicarbonate complex,[(UO2)(CO3)2]2–, it is noteworthy that the determination ofits structure shows it to contain instead a uranyl-tricarbonate
complex. Based upon this, it is reasonable to conjecture that its
dimorph zellerite may also contain a uranyl-tricarbonate complex, rather than a uranyl-dicarbonate complex.

Acknowledgments and Funding
Two anonymous reviewers and the Technical Editor are thanked for constructive comments, which improved the manuscript. Associate Editor G. Diego
Gatta is thanked for shepherding the manuscript through the review process. Alan
Meyrowitz is thanked for providing background information about his father,
Robert Meyrowitz. This study was funded, in part, by the John Jago Trelawney
Endowment to the Mineral Sciences Department of the Natural History Museumof Los Angeles County, and, in part, through the project Ministry of Education,
Youth and Sports National sustainability program I of the Czech Republic (project
No. LO1603) to J.P.

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Manuscript received September 14, 2018
Manuscript accepted January 9, 2019
Manuscript handled by G. Diego Gatta

Endnote:Deposit item AM-19-46814, Supplemental Figure and CIF. Deposit items are free
to all readers and found on the MSA website, via the specific issue’s Table of Contents (go to http://www.minsocam.org/MSA/AmMin/TOC/2019/Apr2019_data/
Apr2019_data.html).
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