Journal of Geosciences, 59 (2014), 145–158

DOI: 10.3190/jgeosci.159

Original paper

Bluelizardite, Na7(UO2)(SO4)4Cl(H2O)2, a new uranyl sulfate mineralfrom the Blue Lizard mine, San Juan County, Utah, USA
Jakub Plášil1*, Anthony R. Kampf2, Anatoly V. Kasatkin3, Joe Marty4
1

Institute of Physics, Academy of Sciences of the Czech Republic v.v.i, Na Slovance 2, 182 21, Prague 8, Czech Republic; plasil@fzu.cz
Mineral Sciences Department, Natural History Museum of Los Angeles County, 900 Exposition Boulevard, Los Angeles, CA 90007, USA
3
V/O “Almazjuvelirexport”, Ostozhenka str., 22, block 1, 119034 Moscow, Russia
45199 E. Silver Oak Rd., Salt Lake City, UT 84108, USA*
Corresponding author
2Bluelizardite (IMA 2013-062), Na7(UO2)(SO4)4Cl(H2O)2, is a new uranyl sulfate mineral from the Blue Lizard mine, San
Juan County, Utah (USA). It was found in a sandstone matrix and is associated with chalcanthite, copiapite, ferrinatrite,
gypsum, kröhnkite, johannite, and several other new, unnamed Na- and Mg-containing uranyl sulfates. Bluelizardite
is a supergene mineral formed by the post-mining weathering of uraninite. The mineral is monoclinic, C2/c, with a =21.1507(6), b = 5.3469(12), c = 34.6711(9) Å, β = 104.913(3)°, V = 3788.91(17) Å3 and Z = 8. Crystals are blades up to
0.4 mm long, flattened on {001}, elongated parallel to [010] and exhibiting the forms {100}, {001} and {111}. Bluelizardite is pale yellow and has a yellowish-white streak. It has good cleavage on {001} and uneven fracture. The Mohs
hardness is estimated at 2. The calculated density based on the empirical formula is 3.116 g/cm3. Bluelizardite exhibits
bright yellow-green fluorescence under both long- and short-wave UV radiation. The mineral is optically biaxial (–), with
α = 1.515(1), β = 1.540(1) and γ = 1.545(1) (measured with white light). The measured 2V is 48(2)° and the calculated
2V is 47.6°. The mineral does not exhibit any dispersion or pleochroism. The optical orientation is X = b, Y ≈ a, Z ≈ c*.
The empirical formula of bluelizardite is Na6.94(U1.02O2)(SO4)4.00Cl0.94O0.06(H2O)2 (based on 21 anions pfu). The Raman
spectrum is dominated by the symmetric stretching vibrations of the uranyl (UO22+) group and sulfate tetrahedra and by
the O–H stretching and bending vibrations of the H2O molecules. The eight strongest powder X-ray diffraction lines are[dobs Å(I )(hkl) ]: 17.08(52)(002), 10.31(60)(200), 5.16(100)(mult.), 4.569(22)(402,–114), 4.238(23)(–115, 310, 008),
3.484(27)(–602,–604,–2·0·10), 3.353(28)(mult.), 3.186(36)(mult.). The crystal structure of bluelizardite (R1 = 0.016
for 4268 reflections with Iobs > 3σI) is topologically unique among known structures of uranyl minerals and inorganic
compounds. It is based upon clusters of uranyl pentagonal bipyramids and sulfate tetrahedra. Two uranyl pentagonal
bipyramids are linked through the two vertices of SO4 groups. The remaining three vertices of each UO7 bipyramid areoccupied by SO4 groups, linked monodentately. The eight independent Na+ cations are linked through the Na–O bonds
along with hydrogen bonds (involving H…O and H…Cl bonds) into a 3D framework.
Keywords: bluelizardite, new mineral, uranyl sulfate, weathering, crystal structure, bond-valence
Received: 2 November 2013; accepted: 22 January 2014; handling editor: J. Sejkora
The online version of this article (doi: 10.3190/jgeosci.159) contains supplementary electronic material.

1. Introduction
Uranyl sulfate minerals are important alteration products
resulting from hydration–oxidation weathering of primaryuranium minerals, mainly uraninite. They are not uncommon because uraninite is often associated with sulfides
such as pyrite, marcasite and chalcopyrite (Finch andMurakami 1999; Krivovichev and Plášil 2013). During
hydration–oxidation weathering processes, acid solutions
are derived from the decomposition of sulfides underoxidizing conditions. As acid mine drainage (AMD), such
solutions can transport the uranyl ion in aqua-complexes
over long distances (Fernandes et al. 1995; Johnson 2003;
Johnson and Hallberg 2005). Uranyl sulfate minerals
form from such solutions under certain conditions (pH–Eh change, oversaturation, hydrolysis etc.) and in suitableenvironments, e.g. in old mining adits with moderate
relative humidity.
Bluelizardite is a new uranyl sulfate mineral foundat the Blue Lizard mine, San Juan County, Utah, USA.
The mineral is particularly interesting for its chemicalcomposition, as it is a uranyl sulfate hydrate containing
sodium and chlorine, and its crystal structure, which is
unique among uranyl minerals. The new mineral and thename were approved by the Commission on New Minerals, Names and Classification of the International Mineralogical Association (IMA 2013-062). The new mineral
was named after the type locality, the Blue Lizard mine.
One holotype and three cotype specimens of bluelizardite
were deposited in the collections of the Natural History
Museum of Los Angeles County under the catalogue
numbers 64060, 64061, 64062 and 64063.
www.jgeosci.org

Jakub Plášil, Anthony R. Kampf, Anatoly V. Kasatkin, Joe Marty

2. Occurrence
Bluelizardite was found underground in the Blue Lizard
mine, Red Canyon, White Canyon district, San JuanCounty, Utah, USA (37°33'26"N 110°17'44"W) by one of
the authors (JM). The detailed description of the locality
and its geological setting was provided by Kasatkin et al.
(2013) and Plášil et al. (2013a). The Blue Lizard mine is
the type locality for the recently described new minerals
manganoblödite, cobaltoblödite (Kasatkin et al. 2013),
belakovskiite (Kampf et al. 2013) and meisserite (Plášil
et al. 2013a). The mineral association described here isof supergene origin, related to post-mining processes (themine was closed in 1978), which include supergene oxidation of primary ores (uraninite, pyrite and chalcopyrite
disseminated in lenses of organic matter) in the humid
underground environment, which led to the formation ofa variety of secondary minerals, mainly sulfates, occurring as efflorescent crusts on the surfaces of mine walls.
Minerals found in direct spatial association with bluelizardite include chalcanthite, copiapite, ferrinatrite, gypsum,johannite, kröhnkite and several new, unnamed Na- andMg-containing uranyl sulfates. Primary minerals in thegeneral assemblage include barite, bornite, calcite, chalcopyrite, covellite, feldspar, pyrite, quartz and uraninite.
Supergene, post-mining minerals in the general assemblage
include atacamite, belakovskiite, blödite, cobaltoblödite
and manganoblödite, brochantite, chalcanthite, copiapite,
cyanotrichite, d’ansite-(Mn), ferrinatrite, gypsum, halotrichite, johannite, meisserite, metavoltine, natrozippeite,
pseudojohannite, römerite, rhomboclase, sideronatrite andtamarugite.

Fig. 1 Aggregate of bluelizardite crystals. Blue Lizard mine, USA.
Width of the photograph 3.5 mm (photo J. Marty).

the calculated 2V is 47.6°. No dispersion or pleo­chroism
was observed. The optical orientation is X = b, Y ≈ a,
Z ≈ c*. The Gladstone-Dale compatibility, 1 – (Kp/Kc),
is excellent (0.033) for the empirical formula and thesingle-crystal cell.

4. Chemical composition
The chemical composition of bluelizardite was determined using a Jeol Superprobe 733 scanning electron

3. Physical and optical properties
Bluelizardite forms as long bladed crystals (Fig. 1) inhedgehog-like aggregates in association with other uranyl
sulfate minerals. Blades are up to 0.4 mm long, flattenedon {001} and elongated parallel to [010], and exhibit theforms {100}, {001} and {111} (Fig. 2). Bluelizardite ispale yellow and has a yellowish-white streak. Crystals
are transparent with a vitreous luster. They are brittle,
with good cleavage on {001}, and they have unevenfracture. The Mohs hardness is estimated at 2. There isinsufficient material for the direct determination of density. A density of 3.116 g/cm3 was calculated based on
the unit-cell dimensions from single-crystal X-ray dataand on the empirical formula from electron microprobe
results. Bluelizardite shows bright yellow-green fluorescence under both long- and short-wave UV radiation. The
mineral is optically biaxial negative, with α = 1.515(1),β = 1.540(1), γ = 1.545(1) (measured in white light).
The measured 2V using a spindle-stage is 48(2)° and
146

001

100

Fig. 2 Crystal drawing of bluelizardite (clinographic projection in
nonstandard orientation: [010] vertical).

Bluelizardite, a new uranyl sulfate mineral

Tab. 1 Results of chemical analysis (in wt. %) of bluelizardite
Mean (n = 5)
Range
24.15
23.40–24.55
Na2O
SO3
35.84
34.70–37.45
UO3
32.89
30.45–35.14
Cl
3.76
3.46–4.01
H 2O
4.05*
OH = Cl
0.85
total
99.94
* calculated from the structure
SD – standard deviation

SD
0.47
0.99
1.76
0.22

thermal analysis. Instead, the H2O content was calculated
by stoichiometry as indicated by the crystal-structure
determination.
The empirical formula of bluelizardite, calculated as
the mean of 5 representative spot analyses (Tab. 1), isNa6.94(U1.02O2)(SO4)4.00Cl0.94O0.06(H2O)2 (based on 21 anionspfu). The simplified formula, Na7(UO2)(SO4)4Cl(H2O)2,requires Na2O 24.46, UO3 32.31, SO3 36.07, Cl 4.00, H2O
4.06, O = Cl –0.90, total 100.00 wt. %.

Standard
AlbiteCu3VS4
UO2
Cs2ReCl6

5. Raman spectroscopy
microscope (SEM) equipped with an INCA energydispersive X-ray spectrometer (Fersman MineralogicalMuseum, Moscow). An operating voltage of 20 kV wasused with a beam current of 2 nA and a 1 μm beam
diameter. The EDS mode on the SEM was chosen for
the analysis instead of the WDS mode on the electron
microprobe (EMP) because bluelizardite is very unstable
under the higher current of the EMP beam, clearly due toits high content of easily volatilized components (Na, Cl
and H2O). The content of molecular H2O was not determined directly, because of the paucity of pure material for

A Raman spectrum (Fig. 3) was collected using a DXR
dispersive Raman spectrometer (Thermo Scientific)
mounted on a confocal Olympus microscope (100×objective). The Raman signal was excited by a 532 nm
diode-pumped solid-state laser and detected by a CCD
detector. The experimental parameters were: 5 s exposure
time, 32 exposures, 400 lines/mm grating, 50 mm slit
spectrograph aperture, and 3.0 mW laser power level.
The instrument was calibrated by a software-controlledcalibration procedure using multiple neon emission lines

Raman Intensity (a.u.)

ν1 UO22+

ν1+ ν3 SO4

3500

3000

2500

2000

1500

ν2 UO22+

ν3 UO22+
Stretching O–H(ν1 + ν3)

Bending O–H–O(ν2)
ν4 SO4

6000

4000

2000

1000
1000

ν2 SO4500

Raman shift (cm–1)
Fig. 3 Raman spectrum of bluelizardite.

147

Jakub Plášil, Anthony R. Kampf, Anatoly V. Kasatkin, Joe Marty(wavelength calibration), multiple polystyrene Raman
bands (laser frequency calibration) and standardized
white-light sources (intensity calibration).
Many well-documented and rigorously-assigned Raman or infrared spectra of uranyl–sulfate minerals havebeen published. The general features of the vibration
spectra of uranyl–sulfate minerals were reviewed byČejka (1999). Recently, the Raman spectrum of meisserite, which is structurally very similar to bluelizardite, waspublished (Plášil et al. 2013a). We based the assignment
and interpretation of the bluelizardite Raman spectrum on
the similarities with the meisserite spectrum and also
on the well-resolved Raman spectrum of natural zippeite(Plášil et al. 2010).
The dominant features in the Raman spectrum ofbluelizardite are U–O symmetric and S–O symmetricstretching vibrations, with expected highest intensities
in the Raman (Čejka 1999; Plášil et al. 2010). The O–H
vibrations, which are generally weak in un-polarized
Raman spectra, are easily observable in the bluelizardite
spectrum (Fig. 3).
The U–O stretching region is dominated by a sharpband at ~860 cm–1, which is attributable to the ν1 symmetric stretching U–O vibration of the (UO 2) 2+ ion.
Closer inspection and band-component analysis of thespectrum show that the band is composed of two overlapping vibrations at 854 and 848 cm–1. It is interesting
that, in the bluelizardite spectrum, the ν3 antisymmetricstretching U–O vibration is observable, while it is not in
the meisserite spectrum (Plášil et al. 2013a). In general,
ν3 UO22+ is not active in Raman for C∞v point symmetry;however, for bluelizardite, the symmetry of the uranyl ion
is lowered by the symmetry of the U and corresponding
O sites (factor-group symmetry) and forbidden modes
become active. The low-intensity bands at 918 and 912
cm–1 were assigned to the ν3 antisymmetric stretching
U–O vibrations. The inferred U–O uranyl bond-lengths,
using the equations of Bartlett and Cooney (1989), are1.76 Å (ν1) and 1.77 Å (ν3). These values perfectly match
the U–O bond-lengths obtained in our refinement of thecrystal structure (see below). The Raman bands at 260,
252, 237 and 208 cm–1 were assigned to the ν2 (δ) O–U–O
bending vibrations. The number of observed bands is inagreement with there being two U atoms in the primitive
unit-cell (the unit-cell of bluelizardite is C-centered).
The group of Raman bands with the second-highest
intensity corresponds to the S–O symmetric stretchingvibrations (ν1) of SO4 tetrahedra, located at around ~1060
cm–1. The large number of bands that can be assigned tothe symmetric stretching modes (those at 1061, 1050,
1012, 1003, 998, 986, 951 and 941 cm–1) is caused by
the presence of 8 independent SO4 groups in the primitivecell. The bands at higher energy, 1216, 1189, 1156, 1143
and 1090 cm–1, were assigned to the (ν3) antisymmetric148

stretching vibrations of the SO4 tetrahedra. The bending
modes of the SO4 groups are responsible for the Raman
bands at 651, 641, 620 and 619 cm–1 (triply degenerate ν4
bending mode) and at 607, 592 cm–1 (doubly degenerateν2 bending mode).
The highest-energy bands (~3600 to 3200 cm–1) in the
Raman spectrum are dominated by the O–H stretchingvibrations of the H2O molecules. Band-component analysis indicated bands at 3606, 3576, 3475, 3422, 3343 and3219 cm–1. Using the correlation of Libowitzky (1999),
it is possible to infer the approximate O…O (donor–acceptor) distances and also H…O (hydrogen–acceptor)
distances for the corresponding hydrogen-bonds, basedon the wavenumbers of the O–H stretching frequencies.
The inferred distances from the observed frequencies forbluelizardite vary between 2.7 and 3.1 Å (O…O). The inferred H–A distances match the range 1.8 to 2.4 Å; thesenumbers correspond with the bond-lengths obtained for
the H-bonds from the structure refinement (see below),
although the low end of the range is somewhat lower thanthe value from X-rays (~1.9 Å).
The bands at the lowest frequencies are attributable tolattice modes. The Na–O stretching and Na–Cl stretchingvibrations could not be assigned to Raman bands becauseof overlap with other fundamental vibrations.

6. X-ray crystallography and structure
determination

6.1. Powder diffraction
Powder X-ray diffraction data for bluelizardite wereobtained using a Rigaku R-Axis Rapid II curved imaging plate microdiffractometer utilizing monochromatized
MoKα radiation (Gandolfi method). Observed powderdhkl values and intensities were derived by profile fitting using JADE 2010 software. Data (in Å) are given
in Tab. 2. Unit-cell parameters refined from the powder
data using JADE 2010 with whole-pattern fitting are:a = 21.1822(6), b = 5.3544(1), c = 34.730(3) Å, β =104.879(7)° and V = 3806.9(3) Å3.

6.2.	Single-crystal X-ray diffraction andstructure solution
A single crystal of bluelizardite, with dimensions 0.12 ×
0.03 × 0.02 mm, was examined using an Oxford Diffraction Gemini single-crystal diffractometer with an Atlas
CCD detector using monochromatized MoKα radiation,with a fibre-optic Mo-Enhance collimator. The unit-celldimensions were refined from 13395 reflections by leastsquares with the CrysalisPro package (Agilent Technologies 2012). According to the single-crystal data, blueliz-Bluelizardite, a new uranyl sulfate mineral

Tab. 2 Powder diffraction data for bluelizardite
Iobs

dobs

52
60
10
9

17. 08
10.31
8.39
7.56

dcalc

Icalc

hkl

Iobs

dobs

dcalc

Icalc

hkl

Iobs

16.7828 100002
2.8696
6
5̄ 1 818 2.859
10.2360 92
200
2.8549 143̄ 1 1078.3914 13004
2.84358514
7.5023 10
2̄ 0 42.7971
90 0 125.5943 18006
2.77553
6̄ 0 10185.61
18
5.5445 122̄ 0 62.71764515
5.1801 58
110
2.7072
4
1̄ 1 115.1704 191̄ 1 12.68135
3̄ 1 11100
5.16
20 2.674
5.11809400
2.6772
3020
5.0701 35
111
2.6687 12021
85.04293
1̄ 1 22.64388022
4.973994̄ 0 42.63443
7̄ 1 34.86155112
2.63253
8̄ 0 2
4.57848402
2.6272
5
7̄ 1 222
4.569
4.5418 181̄ 1 418 2.619
2.6255 10
7̄ 1 44.3772
6
4̄ 0 62.5925
6
8̄ 0 613
4.28523114
2.56963221
4.2364
7
1̄ 1 52.5590
6
800
23
4.238
4.2124 10310
2.52175
3̄ 1 12
4.1957
4008
2.51643711
4.10013311
2.50083
6̄ 0 1218 2.499
3.97805115
2.49363
5̄ 1 1122
3.942
3.94098312
2.4867 10025
283.9303 141̄ 1 62.46803517
3.8537
7
3̄ 1 52.45586712
3.7512
4
4̄ 0 82.37963
7̄ 1 93.6550
6
3̄ 1 62.34904518
3.6387
3
1̄ 1 72.3468
6
421
10
9
3.603
16 2.339
3.5735 12208
2.33754027
3.5250 13
6̄ 0 22.32536
4̄ 2 527
3.484
3.4887 12
6̄ 0 42.30497
7̄ 1 10112.23533715
3.4636 152̄ 0 103.4120 18600
2.23182
1̄ 1 145 2.233
3.3697 15406
2.22693
7̄ 1 1128
3.353
3.33794315
2.21943227
113.32215
5̄ 1 22.17664
3 1 122.14814
9̄ 1 53.31608
6̄ 0 615 2.135
3.30936
5̄ 1 3
2.14393
4̄ 0 16
3.25254510
2.12943806
3.2101 14
4̄ 0 10
2.10735
6̄ 2 5173.19385
5̄ 1 52.09363910
3.187611602
2.0816
5
621
36
3.186
3.17575511
2.07652717
3.1615 18118
2.06542229
13 2.06610
3.13486316
2.06014
1¯0 0 83.09998
5̄ 1 62.05602
4̄ 2 1013
3.079
3.0779 10512
2.04333
9̄ 1 96
3.04198
3̄ 1 92.03235427
2.98996
5̄ 1 72.0124 13
0 2 112.94198317
1.99824718
24 2.007
7
2.93753119
1.99124
4̄ 2 1120
2.916
2.9043
91̄ 1 101.98965
1¯0 0 102.9001 12408
1.97228
10 0 22.8937
5
2̄ 0 121.93343
6 0 12* Calculated lines with intensities less than 3 are not included unless they correspond to observed lines

dobs
1.924

1.871

1.809

1.766

1.716

1.656

1.619

1.556

1.518

1.473

1.424

1.390

dcalc

Icalc

hkl

1.92371.92171.91381.87811.87471.86481.85851.82481.81501.81101.80631.80501.79201.7734
1.7713
1.76951.76551.76361.76051.73381.7284
1.7193
1.71361.7094
1.70831.70631.65931.65501.65171.62851.62611.62191.61641.56451.5533
1.54651.5444
1.52551.51841.51341.51281.50781.50571.47451.46491.45201.42511.42201.4004
1.39411.3904
1.3810

3
2
3
3
6
4
7
3
2
2
2
2
2
4
2
2
3
3
3
6
5
6
2
2
6
5
2
5
3
3
3
2
3
3
2
2
2
3
3
2
2
2
2
2
2
2
2
2
2
2
3
2

2̄ 0 18719
7̄ 1 156̄ 2 118̄ 2 50 0 180 2 13627
3̄ 1 18
1¯1 1 41 1 171¯1 1 31̄ 1 18
4 2 11917
7̄ 1 175 1 141¯1 1 96 0 148̄ 0 181̄ 3 51 1 181¯1 1 11135
1¯2 0 101̄ 1 193̄ 3 7
12 0 24 2 135̄ 3 5531
2̄ 2 171¯0 2 910 2 3535
3̄ 3 111¯1 1 161¯3 1 106 2 133̄ 1 22731
5̄ 3 112̄ 2 19
0 2 19734
1¯2 2 96 2 15
11 1 101¯3 1 16
3 3 13
10 2 95 1 20149

Jakub Plášil, Anthony R. Kampf, Anatoly V. Kasatkin, Joe Marty

Tab. 3 Crystallographic data and refinement details for bluelizardite
Crystal data
FormulaCrystal system
Space group
Unit-cell parameters: a, b, c [Å]β [°]Unit-cell volume [Å3]Z
Calculated density [g/cm3]
Crystal size [mm3]Na7(UO2)(SO4)4Cl(H2O)2
monoclinic
C2/c
21.1507(6), 5.3469(12), 34.6711(9)104.913(3)3788.91(17)83.108
0.12 × 0.03 × 0.02

Data collection
Diffractometer
Temperature [K]Radiation, wavelength [Å]θ range for data collection [º]Limiting Miller indicesAxis, frame width (º), time per frame (s)Total reflections collected
Unique reflections
Unique observed reflections, criterion
Absorption coefficient [mm-1], type
Tmin/Tmax
Data completeness to θmax (%), Rint

Oxford Diffraction Gemini with Atlas detector
320
MoKα, 0.71073 (50 kV, 30 mA)
3.50–29.40
h = 2¯5 → 26, k = 7̄ → 7, l = 4¯6 → 43
ω, 0.5, 130
24440
4715
4268, [I > 3σ(I)]9.41; multi-scan
0.514/1
99.47, 0.025

Structure refinement by Jana2006
Full-matrix least-squares on F2
Number of refined parameters, restraints, constraints 312, 6, 4
Data/restraints/parameters4268/6/312
R1, wR2 (obs)
0.0163, 0.0383
0.0205, 0.0398
R1, wR2 (all)
GOF obs/all
1.17, 1.15
Weighting scheme, weights
σ, w =1/(σ2(I)+0.0004I2)–
30.70, –0.86
Largest diffraction peak and hole (e /Å )ardite is monoclinic with a = 21.1507(6), b = 5.3469(12),c = 34.6711(9) Å, β = 104.913(3)°, V = 3788.91(17) Å3
and Z = 8. Of the 24,440 measured reflections, 4715
were independent and 4268 were classified as observed
based on the criterion [Iobs > 3σ(I)]. Data were correctedfor Lorentz effect, polarization factor and background.
An empirical (multi-scan) correction for absorption wasapplied to the dataset using the ABSPACK3 algorithm
implemented in the RED routine of the CrysAlis software(Agilent Technologies 2012), leading to Rint of 0.0250.
Other details of the data collection are given in Tab. 3.
The crystal structure of bluelizardite was solved by the
charge-flipping algorithm (Oszlányi and Sütö 2004, 2008;
Palatinus 2013) implemented in the Superflip program(Palatinus and Chapuis 2007) and subsequently refinedusing the software Jana2006 (Petříček et al. 2006) withthe full-matrix least-squares refinement based on F2. The
reflection conditions and statistics clearly indicated themonoclinic space group C2/c. This space group was alsosuggested by the Superflip program, based on the symme150

try operators deduced from theflipped electron-density (Palatinus and van der Lee 2008). All
atoms except hydrogen wererefined using harmonic atomicdisplacement parameters. Hydrogen atoms, which were located in the difference-Fouriermaps, were treated using soft
constraints on bond lengths,
0.90 Å, with a constraint weightof (0.02), resulting in donor–
hydrogen lengths of 0.87(3) Å,and their isotropic-displacement
parameters were set to 1.2×Ueq
of the donor O atoms. The refinement converged smoothlywith final indices of agreement
R1 = 0.0163 and wR2 = 0.0383
for 4715 observed reflections
with GOF = 1.17 (Tab. 2). The
atom coordinates and the displacement parameters are given
in Tab. 4 and selected interatomic distances in Tabs 5 and6. Bond-valences are presented
in Tab. 7.

6.3. Description of the    crystal structure

The asymmetric unit of thebluelizardite structure contains
one U site, four S sites, eight Nasites, twenty O sites (including two positions occupied
by O atoms of H2O molecules) one Cl site and four H
sites (Tab. 4). The U atom is strongly bonded to two O
atoms (OUr), forming a nearly linear uranyl ion, UO22+. It
is further coordinated by five O atoms (Oligand) arranged as
equatorial vertices of a pentagonal uranyl bipyramid withOUr at the two vertical apices. The U–OUr and U–Oligandbond-lengths (Tab. 5) closely match the typical values for[7]-coordinated U atoms provided by Burns et al. (1997).
Uranyl pentagonal bipyramids form clusters in which twouranyl bipyramids are bridged by sharing vertices of two
sulfate tetrahedra, and three additional SO4 groups arelinked monodentately to each bipyramid, resulting in dimers of composition [(UO2)2(SO4)8]12– (Fig. 4). The Naϕnpolyhedra are located between the uranyl sulfate clusters
and link them into sheets stacked perpendicular to [010];
adjacent sheets (a short periodicity with the b = 5.35 Å)link through a dense network of Na–O and Na–Cl bonds
into a three-dimensional framework (Fig. 4). Additional
linkage is provided through hydrogen bonds from H 2O

x/a
0.519790(4)0.39880(3)0.19437(3)0.35667(3)0.52816(3)0.5
0.5
0.24344(6)0.31919(7)0.37872(6)0.69460(6)0.43332(6)0.34817(6)0.35728(4)0.39670(10)0.45053(9)0.33715(9)0.41507(9)0.19330(11)0.22590(10)0.22999(10)0.12656(9)0.29776(9)0.36035(11)0.36047(10)0.41380(9)0.50291(10)0.48627(10)0.59554(9)0.52671(9)0.50283(9)0.53365(10)0.64780(11)0.23476(12)0.6169(11)0.2691(13)0.2391(15)0.6332(12)

Atom
U
S1
S2
S3
S4
Na1
Na2
Na3
Na4
Na5
Na6
Na7
Na8
Cl
O1
O2
O3
O4
O5
O6
O7
O8
O9
O10
O11
O12
O13
O14
O15
O16
O17
O18
Ow19
Ow20
H1
H2

H3
H4

0.674(4)0.290(5)y/b0.889263(17)0.82919(12)0.38979(12)0.93456(12)0.97992(12)0.50.3688(3)0.8755(2)0.4131(2)0.9872(2)0.7427(2)0.4189(2)0.3812(2)1.49234(14)1.1009(3)0.7322(4)0.7135(4)0.7338(3)0.6255(4)0.4217(4)0.1999(4)0.2995(4)1.0279(4)1.0275(4)0.6618(4)1.0459(3)0.7262(4)1.1551(4)0.9962(4)1.0643(3)0.5996(3)1.1801(4)0.4223(4)0.5150(5)0.483(5)0.463(5)Ueq
0.00965(3)0.01116(19)0.0128(2)0.0124(2)0.01085(19)0.0168(5)0.0261(6)0.0236(4)0.0293(4)0.0213(4)0.0273(4)0.0230(4)0.0268(4)0.0255(2)0.0211(7)0.0211(7)0.0187(6)0.0161(6)0.0263(8)0.0204(7)0.0290(7)0.0206(6)0.0199(7)0.0259(7)0.0221(7)0.0167(6)0.0218(7)0.0189(6)0.0193(7)0.0156(6)0.0160(6)0.0176(6)0.0264(8)0.0400(10)0.0316*
0.048*
0.048*
0.0316*z/c
0.666875(3)0.725237(18)0.679982(19)0.605180(19)0.565139(18)0.5
0.75
0.66014(4)0.75567(4)0.50389(3)0.58061(3)0.57801(4)0.65853(4)0.49530(2)0.72350(6)0.70702(6)0.70406(6)0.76693(5)0.70048(7)0.64714(6)0.70751(6)0.66314(6)0.61533(6)0.56665(6)0.60765(6)0.63616(6)0.55835(6)0.53732(6)0.56187(6)0.60633(5)0.64233(6)0.69168(5)0.60943(7)0.53951(8)0.6193(9)0.5323(12)0.5454(12)0.5952(9)U110.01006(6)0.0104(3)0.0105(3)0.0113(3)0.0133(3)0.0311(9)0.0300(10)0.0224(7)0.0437(8)0.0293(7)0.0294(7)0.0263(7)0.0345(8)0.0335(4)0.0297(12)0.0185(11)0.0125(10)0.0198(11)0.0339(13)0.0173(11)0.0221(12)0.0115(10)0.0126(10)0.0320(13)0.0220(11)0.0125(10)0.0319(12)0.0208(11)0.0134(10)0.0219(11)0.0176(11)0.0242(11)0.0215(12)0.0290(15)Tab. 4 Atom coordinates and displacement parameters for the crystal structure of bluelizardite
U22
0.01104(5)0.0136(3)0.0145(3)0.0149(3)0.0110(3)0.0102(7)0.0226(9)0.0245(6)0.0263(7)0.0177(6)0.0288(7)0.0214(6)0.0218(6)0.0164(3)0.0148(10)0.0287(12)0.0238(11)0.0188(10)0.0214(12)0.0269(11)0.0300(12)0.0324(11)0.0238(11)0.0344(12)0.0146(10)0.0177(10)0.0146(10)0.0213(10)0.0244(11)0.0159(10)0.0141(10)0.0128(9)0.0230(12)0.0399(15)U330.00808(5)0.0095(3)0.0135(3)0.0112(3)0.0089(3)0.0121(7)0.0248(9)0.0246(6)0.0207(6)0.0180(6)0.0214(6)0.0241(6)0.0268(7)0.0239(4)0.0184(10)0.0198(10)0.0170(10)0.0089(9)0.0289(12)0.0199(10)0.0303(12)0.0180(10)0.0247(11)0.0130(10)0.0296(11)0.0179(10)0.0214(10)0.0137(9)0.0223(10)0.0102(9)0.0160(9)0.0146(9)0.0336(13)0.0517(16)U120.00043(4)−0.0013(2)0.0001(2)0.0011(2)−0.0004(2)−0.0020(6)0−0.0006(5)−0.0127(5)−0.0013(5)0.0031(5)−0.0028(5)−0.0015(5)0.0010(3)−0.0010(8)0.0068(9)−0.0047(8)−0.0037(8)−0.0050(9)−0.0033(8)0.0055(9)−0.0028(8)0.0036(8)−0.0002(10)−0.0001(8)0.0013(8)−0.0092(9)0.0033(8)−0.0018(8)−0.0020(8)0.0000(7)−0.0001(8)−0.0033(9)−0.0091(12)U130.00274(4)0.0025(2)0.0031(2)0.0033(2)0.0039(2)0.0112(6)0.0054(7)0.0074(5)0.0131(6)0.0080(5)0.0022(5)0.0116(5)0.0127(5)0.0025(3)0.0055(9)0.0118(8)−0.0016(8)0.0024(7)0.0179(10)0.0102(8)−0.0016(9)0.0040(8)0.0074(8)0.0089(9)0.0068(9)0.0001(7)0.0113(9)0.0031(8)0.0086(8)0.0066(8)0.0041(8)0.0031(8)0.0053(9)0.0113(12)U230.00091(3)0.0007(2)−0.0010(2)0.0001(2)0.0001(2)−0.0005(6)00.0038(5)0.0016(5)−0.0009(5)0.0034(5)−0.0050 (5)−0.0057(5)−0.0008(3)0.0011(8)0.0065(9)−0.0006(8)0.0015(7)−0.0105(9)−0.0073(8)0.0109(10)−0.0050(9)−0.0014(9)0.0029(9)−0.0033(9)−0.0017(8)−0.0045(8)0.0056(8)−0.0013(9)−0.0022(7)−0.0004(7)−0.0019(8)−0.0073(9)−0.0017(13)Bluelizardite, a new uranyl sulfate mineral151

Jakub Plášil, Anthony R. Kampf, Anatoly V. Kasatkin, Joe Marty

Tab. 5 Selected interatomic distances (Å) and angles (°) in bluelizardite
U–O17
U–O18
U–O2
U–O4v
U–O8xi
U–O12
U–O16<U–OUr><U–Oeq>1.7590(17)1.765(2)2.416(2)2.4958(16)2.345(2)2.3732(17)2.3371(18)
1.762
2.393

Na1–O13
Na1–O13iii
Na1–O14i
Na1–O14ii<Na1–O>
Na1–Cli
Na1–Clii

2.344(2)2.344(2)2.313(2)2.313(2)2.329
2.9811(9)2.9811(9)Na4–O1i
Na4–O3Na4–O4Na4–O5viii
Na4–O7
Na4–O7ix<Na4–O>2.768(3)2.505(3)2.607(2)2.225(3)2.455(2)2.397(3)2.493

Na7–O10i
Na7–O11
Na7–O12i
Na7–O13
Na7–O14i
Na7–O16i
Na7–O17<Na7–O>
Na7–Cli
O1–O2
O1–O3
O1–O4
O1–O18v
O2–O3
O2–O4
O2–O4v
O2–O12O2–O17
O3–O4
O4–O8ix
O4–O18v
O5–O6
O5–O7

2.569(2)2.435(3)2.940(2)2.418(3)2.460(3)2.732(2)2.526(2)2.583
2.9309(13)2.417(3)2.428(3)2.443(2)2.961(2)2.376(3)2.383(3)2.752(3)2.911(3)2.834(3)2.373(2)2.806(3)2.851(3)2.396(3)2.396(3)

S1–O1
S1–O2
S1–O3
S1–O4
<S1–O>

1.4542(17)1.490(2)1.4592(19)1.4872(6)
1.473

S3–O9
S3–O10S3–O11
S3–O12<S2–O>

1.467(2)1.446(2)1.462(2)1.5164(18)
1.473

S2–O5
S2–O6
S2–O7
S2–O8
<S2–O>
Na2–O1iNa2–O1iv
Na2–O2Na2–O2v
Na2–O4
Na2–O4v
Na2–O18i
Na2–O18iv<Na2–O>
Na5–O10
Na5–O14
Na5–O15ii
Na5–Ow20x<Na5–O>
Na5–Cli
Na5–Cl<Na5–Cl>

1.450(2)1.470(2)1.463(2)1.4834(19)1.467
2.576(2)2.576(2)2.507(2)2.507(2)2.815(2)2.815(2)2.520(2)2.520(2)2.605
2.316(3)2.443(2)2.479(3)2.484(2)2.431
2.6883(12)2.7420(12)2.715

S4–O13S4–O14S4–O15S4–O16<S4–O>
Na3–O3Na3–O5
Na3–O6
Na3–O6vi
Na3–O7vi
Na3–O9Na3–Ow19vii<Na3–O>1.455(2)1.467(2)1.461(2)1.5055(19)1.472
2.333(2)2.373(3)2.478(2)2.964(2)2.455(3)2.306(3)2.327(2)2.462

Na6–O6xi
Na6–O9xii
Na6–O15
Na6–Ow19
Na6–Ow20xi<Na6–O>
Na6–Clii

2.427(2)2.485(2)2.439(2)2.329(3)2.345(3)2.405
2.8676(12)Na8–O1i
Na8–O3Na8–O6
Na8–O9iNa8–O11
Na8–O12i<Na8–O>

2.680(2)2.427(3)2.523(2)2.475(2)2.381(3)2.509(2)2.499

O11–O17
O12–O16
O12–O18
O13–O14O13–O15
O13–O16
O13–O17
O14–O15
O14–O16
O15–O16
O15–Ow19vi
O16–O17
O16–O18
O17–O18i

2.959(3)2.838(3)2.851(2)2.405(3)2.411(3)2.420(3)2.990(3)2.403(3)2.375(3)2.405(3)2.862(3)2.883(2)2.990(3)2.794(3)

O5–O8
O6–O7
O6–O8
O6–O9iO7–O8
O8–O16xiii
O8–O17xiii
O8–Ow19xiii
O9–O10O9–O11
O9–O12
O10–O11
O10–O12
O11–O122.401(3)2.388(3)2.398(3)2.970(3)2.388(3)2.864(2)2.746(3)2.858(3)2.399(3)2.418(3)2.375(3)2.417(3)2.386(3)2.427(3)Symmetry codes: (i) x, y-1, z; (ii) -x+1, -y+2, -z+1; (iii) -x+1, -y+1, -z+1; (iv) -x+1, y-1, -z+3/2; (v) -x+1,
y, -z+3/2; (vi) x, y+1, z; (vii) x-1/2, y+1/2, z; (viii) -x+1/2, y-1/2, -z+3/2; (ix) -x+1/2, y+1/2, -z+3/2; (x)-x+1/2, -y+3/2, -z+1; (xi) x+1/2, y+1/2, z; (xii) x+1/2, y-1/2, z; (xiii) -x+1/2, -y+5/2, -z+1; (xiv) x-1/2,
y-1/2, z.

152

molecules to O atoms (O8, O15)
and Cl atoms (Tab. 6, Fig. 5).

7. Discussion

7.1. Structure topology   and related   structures
The bluelizardite structure contains [(UO 2 ) 2 (SO 4 ) 8 ] 4– uranyl
sulfate clusters (Fig. 6a); in contrast, the structure of meisserite(Plášil et al. 2013a), another Nauranyl sulfate from the same locality, is based on uranyl sulfate
chains (Fig. 6b). In the blue­
lizardite structure, the bridging
sulfate tetrahedra between two
uranyl pentagonal bipyramids
are oriented down and down,
or up and up (Fig. 6a) with respect to the plane of the sheets,
whereas in meisserite, the SO4groups that link the chains areoriented up and down (Fig. 6b).
The similar infinite chain as inmeisserite occurs in the structure of synthetic Na3Tl5[(UO2)(MoO4)3]2(H2O)3 (Krivovichev
and Burns 2003). While thebluelizardite structure is characterized by two-memberedclusters, the meisserite structureis characterized by chains, andthe structure of belakovskiite(Kampf et al. 2013) is based onclusters of composition [(UO2)(SO 4) 4] 6– (Fig. 6c). The twomembered clusters topologically similar to these found in
bluelizardite were observed in
the structures of the synthetic
compounds: Na6[(UO2)(MoO4)4](Krivovichev and Burns 2001)
and Na 3 Tl 3 [(UO 2 )(MoO 4 ) 4 ](Krivovichev and Burns 2003).
Uranyl sulfate clusters of thesame stoichiometry as in blue­
lizardite occur in synthetic
compounds (Burns and Hayden
2002; Hayden and Burns 2002a,b). However, these compounds

Bluelizardite, a new uranyl sulfate mineral

S1
S2
Na7

Na6

S4

S3

Na1 Na5

Na3
Fig. 4 Crystal structure of bluelizardite
viewed along [010]. [(UO 2) 2(SO 4) 8] 12–
clusters (U-polyhedra are blue, SO 4groups yellow) are linked into a 3D
framework through Na–O (Na atoms arepink) and Na–Cl bonds (Cl atoms aregreen). Atoms labelled Ow19 and Ow20
are H2O molecules, H atoms are shownin black color, O–H…O bonds are blue
dashed, O–H…Cl bonds are two-coloreddashed lines.

are topological isomers, as they contain a bidentately
linked SO 4 group (Figs 6d–f). A very similar cluster
to that in bluelizardite occurs in the structure of thehigh-temperature synthetic compound K4[(UO2)(SO4)3](Mikhailov et al. 1977). This structure, however, contains
two bidentately linked SO4 groups (Fig. 6g).

7.2.	Notes on origin
Bluelizardite is a uranyl sulfate mineral found in asandstone matrix together with a diverse suite of othersulfate minerals of supergene origin. They formed from
low-temperature, SO4-bearing, acidic aqueous solutions,which can be linked to acid-mine drainage (AMD) waters originating from the dissolution of hypogene sulfide
minerals (Fernandes et al. 1995; Johnson 2003; Johnson
and Hallberg 2005). The occurrences of such mineral-richalteration assemblages, including uranyl sulfates related
in origin to AMD processes, are widespread (Ondruš et

Na8
Na2

al. 1997, 2003; Brugger et al. 2003, 2006; Plášil et al.
2011a, b, 2012, 2013a, b). At the Blue Lizard mine, themineral assemblage is inferred to have formed at very
low pH. Although we did not sample the mine waters at
the site or measure their pH, we can draw some conclusions concerning the pH based on the known thermodynamic properties of selected minerals in the association(e.g., Majzlan 2010 and references therein; Grevel and
Majzlan 2011) and from the bond-valence approach(Schindler et al. 2006; Hawthorne and Schindler 2008;
Schindler and Hawthorne 2008; Hawthorne 2012). Minerals that are very characteristic of this weathering association, including römerite, rhomboclase and copiapite, arepredicted to form under very low pH and at moderately
oxidizing conditions (Majzlan 2010). It is also significant
that the assemblage includes minerals that are stable atambient temperature (~15–20 °C) and very low relative humidity, such as rhomboclase, as well as phasesthat are characteristic of higher relative humidity, such

Tab. 6 Hydrogen-bond geometry for the structure of bluelizardite
Bond
D–H
Ow19–H1···O8xi
0.87 (3)Ow20–H2···Cli0.87 (3)Ow20–H3···Clxiii
0.87 (2)Ow19–H4···O15i
0.87 (3)Symmetry codes: (i) x, y-1, z; (xi) x+1/2, y+1/2, z; (xiii) -x+1/2, -y+5/2, -z+1.

H···A
2.25 (3)2.52 (3)2.80 (3)1.99 (3)D···A
2.858 (3)3.335 (3)3.314 (3)2.862 (3)

D–H···A
126.8 (19)155 (2)120 (3)177 (2)

153

U
S1
S2
S3
S4
Na1
Na2
Na3
Na4
Na5
Na6
Na7
Na8
∑BV
H1
H2
H3
H4
∑BV+H
O1
1.58
0.12×2↓
0.07
0.09
1.86
1.86
O2
0.48
1.44
0.15×2↓
2.07
2.07
O3
1.56
0.24
0.15
0.19
2.14
2.14
O4
0.41
1.45
0.15×2↓
0.11
2.12
2.12
O5
1.60
0.21
0.32
2.13
2.13
O6
1.52
0.16, 0.04
0.19
0.14
2.05
2.05
O7
1.55
0.17
0.17, 0.20
2.09
2.09
O8
0.56
1.46
2.02
0.17
2.19
O9
1.53
0.26
0.16
0.17
2.12
2.12
O10
1.62
0.25
0.13
2.00
2.00
O11
1.55
0.18
0.21
1.94
1.94
O12
0.53
1.34
0.05
0.15
2.07
2.07
O13
1.58
0.23×2↓
0.19
2.00
2.00
O14
1.53
0.25×2↓
0.18
0.17
2.13
2.13
O15
1.55
0.16
0.18
1.89
0.22
2.11
O16
0.56
1.38
0.08
2.02
2.02
O17
1.72
0.14
2.09
2.09
O18
1.72
0.06×2↓
1.92
1.92
Ow19
0.24
0.24
0.48
0.73
0.73
1.94
Ow20
0.16
0.23
0.39
0.73
0.73
1.85
Cl
0.11×2↓
0.44
0.14
0.12
0.81
0.11
0.06
0.98
∑BV
5.98
6.03
6.13
6.04
6.04
1.18
0.97
1.32
1.02
1.19
1.14
1.06
0.95
0.90
0.84
0.79
0.95
Notes: Values are expressed in valence units (vu). ΣBV = sum of bond-valences incident at the atom site; ΣBV + H = sum of the bond-valence with the contribution of the H-bonds; ×2↓ = multiplicity.
U 6+–O bond-valence parameters (r0 = 2.045, b = 0.51) taken from Burns et al. (1997); Na+–O, Na+–Cl-, S6+–O bond-valence parameters taken from Brown and Altermatt (1985), H +1–O bond-valence
parameters from Brown (2002) and H+1–Cl bond-valence parameters from Malcherek and Schlüter (2007).

Tab. 7 Bond-valence analysis for the structure of bluelizardite

Jakub Plášil, Anthony R. Kampf, Anatoly V. Kasatkin, Joe Marty154

as chalcanthite (Majzlan 2010 andreferences therein). However, this is
not unreasonable, because these minerals form by evaporative processes
at the surface of a rock with highrelative porosity. There are no reliabledata on the stability of uranyl sulfate
minerals (including these newly described minerals from the Blue Lizardmine); however, some assumptions
can be made using the bond-valence
approach. An in-depth explanationof the basic principles and terminology of this approach can be found in
Schindler and Hawthorne (2008). For
borate aqueous species, Schindler and
Hawthorne (2001) documented that thevalue of CDA, the charge deficiency
per anion (called average basicity intheir earlier papers), of the particularspecies correlates with the pH of thesolution from which they formed.
Therefore, it can be expected thatminerals with structures having higher
values of CDA will have formed fromsolutions of higher pH. This has been
well documented by crystal-chemicaland paragenetic observations for hydrated oxysalts (Schindler et al. 2000,
2006; Schindler and Hawthorne 2004,
2008). The minerals occurring in thegeneral bluelizardite association at theBlue Lizard mine with the CDA valuesof their structural units are provided
in Tab. 8 [values for natrozippeite,
copiapite, rhomboclase, metavoltine,römerite, sideronatrite, ferrinatrite,
kröhnkite and blödite were taken from
Schindler et al. (2006)] A wide rangeof CDA values is apparent in this list.
We believe that these CDA values canbe readily correlated with the observed
paragenetic relations, in particular, forthe recently-described uranyl sulfates.
In general, a temporal developmentfrom low to high CDA values is inferred from growth relations, indicating a progressively higher pH in thisassemblage. For example, meisserite(0.29 vu) is usually overgrown by
belakovskiite (0.36 vu), the latter apparently being the younger phase. In
the typical association of meisseriteand belakovskiite, several additional

Bluelizardite, a new uranyl sulfate mineral

Ow20
0.06

Na5
O15 (1.89)

H3

0.22

Ow20

Na5

0.11

S3

S4

H4

H2
O9 (2.12) (0.98)

Ow19
H1

Na6

Na5

Ow20

O8 (2.02)

Fig. 5 Hydrogen-bonding scheme in thebluelizardite structure. The bond-valencesums associated with anions without thecontribution of H–bonds are black-labelled and printed in italics. The bond-valence associated with the particular
H…O or H…Cl bond is shown in colour.

S2

minerals were identified, including ferrinatrite (0.25 vu),
sideronatrite (0.24 vu), metavoltine (0.22 vu), “blödites”(0.30 vu), kröhnkite (0.28 vu) andd’ansite-(Mn) (0.53 vu). In all (a)observed cases, bluelizardite wasinferred to be younger than allminerals except d’ansite-(Mn),which was clearly the last of thesephases to form. The new Na-bearing uranyl sulfates are spatially
isolated from other uranyl sulfates(natrozippeite, johannite and pseudojohannite), as well as from otherminerals, either those characterized (c)by low CDA (e.g. rhomboclase)or those with high CDA values
Fig. 6 Structural units of selected uranyl–
sulfates. a – The [(UO2)2(SO4)8]12– cluster inthe structure of bluelizardite. b – The infinite [(UO2)(SO4)3]4– chain in the structure ofmeisserite (Plášil et al. 2013). c – The isolated [(UO2)(SO4)4]6– cluster in the structureof belakovskiite (IMA 2013–075; Kampf etal. 2013). d – Isolated cluster in synthetic
Na6(UO2)(SO4)4(H2O)2 (Hayden and Burns
2002a, b). e – Isolated cluster in synthetic
Na10[(UO2)(SO4)4](SO4)2(H2O)3 (Burns andHayden 2002). f – Isolated cluster in synthetic KNa5[(UO2)(SO4)4](H2O). g – The clusterin synthetic K4[(UO2)(SO4)3] (Mikhailov etal. 1977).

0.17(e.g. halotrichite). Interestingly, the minerals containing
structural units with low CDA values (copiapite, römerite,

(b)

50 μm

(d)

(e)

(f)

(g)

155

Jakub Plášil, Anthony R. Kampf, Anatoly V. Kasatkin, Joe Marty

Tab. 8 Overview of the chemical composition of studied weathering
association and the CDA values (in valence units, vu) of the structure
units
Mineralbrochantite
natrozippeite
atacamite
copiapitejohanniterhomboclase
pseudojohannite
römerite
metavoltine
sideronatrite
ferrinatrite
kröhnkitemeisserite
blöditebelakovskiite
bluelizardite
tamarugite
halotrichitechalcanthited’ansite-(Mn)Composition
Cu(SO4)(OH)6
Na5[(UO2)8(SO4)4O5(OH)3](H2O)12
Cu2Cl(OH)3
Fe2+Fe3+4(SO4)6(OH)2(H2O)20
Cu[(UO2)2(SO4)2(OH)2](H2O)8(H3O)Fe3+(SO4)2(H2O)3
Cu3(OH)2[(UO2)4O4(SO4)2](H2O)12Fe2+Fe3+(SO4)4(H2O)14
K2Na6 Fe3+6 Fe2+(SO4)12O2(H2O)18
Na2Fe3+(SO4)2(OH)(H2O)3
Na3Fe(SO4)3(H2O)3
Na2Cu(SO4)2(H2O)2
Na5(UO2)(SO4)3(SO3OH)(H2O)
Na2Mg(SO4)2(H2O)4
Na7(UO2)(SO4)4(SO3OH)(H2O)3
Na7(UO2)(SO4)4Cl(H2O)2
NaAl(SO4)2(H2O)6
Fe2+Al2(SO4)4(H2O)22
Cu(SO4)(H2O)5
Na21Mn2+(SO4)10Cl3

CDA [vu]
0.12
0.14
0.15
0.16
0.17
0.18
0.20
0.22
0.22
0.24
0.25
0.28
0.29
0.30
0.36
0.37
0.50
0.50
0.50
0.53

rhomboclase, pseudojohannite and natrozippeite) have ahigh molar proportion of H2O. These phases probably
formed directly from oversaturated solutions by precipitation and hydrolysis. Minerals with higher CDA values
grew under more alkaline conditions, have a lower molar
proportion of H2O and probably crystallized from solutions by evaporation.
Acknowledgements. We are delighted to contribute thispaper to the volume dedicated to our friend and colleague Jiří Čejka, on the occasion of his 85 th birthday
anniversary. Many thanks, Jiří, for your hard and careful scientific work and your friendship. We are grateful for help of Ladislav Lapčák (Institute of Chemical
Technology, Prague) with the Raman spectroscopic
measurements. The early version of the manuscript
benefited from the constructive reviews of Frank Hawthorne and an anonymous reviewer. The editorial handling and care by Editor-in-chief is much appreciated.
This work was financially supported by the Premium
Academiae grant of the ASCR and by the post-doctoral
grant of the GAČR no. 13-31276P to JP and by the John
Jago Trelawney Endowment to the Mineral Sciences
Department of the Natural History Museum of Los
Angeles County.
Electronic supplementary material. Supplementary
crystallographic data for this paper are available online at the Journal web site (http://dx.doi.org/10.3190/
jgeosci.159).

156

References
Agilent Technologies (2012) CrysAlis CCD and CrysAlis
RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, UK
Bartlett JR, Cooney RP (1989) On the determination of
uranium–oxygen bond lengths in dioxouranium(VI)compounds by Raman spectroscopy. J Mol Struct 193:
295–300
Brown ID (2002) The Chemical Bond in Inorganic Chemistry. The Bond Valence Model. Oxford University Press,
Oxford, pp 1–288
Brown ID, Altermatt D (1985) Bond-valence parameters
obtained from a systematic analysis of the inorganic
crystal structure database. Acta Cryst B41: 244–248
Brugger J, Meisser N, Burns PC (2003) Contribution to
the mineralogy of acid drainage of uranium minerals:
marecottite and the zippeite-group. Amer Miner 88:
676–685
Brugger J, Wallwork KS, Meisser N, Pring A, OndrušP, Čejka J (2006) Pseudojohannite from Jáchymov,
Musonoï, and La Creusaz: a new member of the zippeitegroup. Amer Miner 91: 929–936
Burns PC, Hayden LA (2002) A uranyl sulfate cluster
in Na10[(UO2)(SO4)4](SO4)2·3H2O. Acta Cryst C58:
i121–i123
Burns PC, Ewing RC, Hawthorne FC (1997) The crystal
chemistry of hexavalent uranium: polyhedron geometries, bond-valence parameters, and polymerization ofpolyhedra. Canad Mineral 35: 1551–1570Čejka J (1999) Infrared spectroscopy and thermal analysisof the uranyl minerals. In: Burns PC, Ewing RC (eds)
Uranium: Mineralogy, Geochemistry and the Environment. Mineralogical Society of America and Geochemical Society Reviews in Mineralogy and Geochemistry
38: pp 521–622
Fernandes HM, Veiga LHS, Franklin MR, Prado VCS,
Taddei JF (1995) Environmental impact assessment of
uranium mining and milling facilities; a study case at thePocos de Caldas uranium mining and milling site, Brazil.
In: Allan RJ, Salomons W (eds) Heavy Metal Aspectsof Mining Pollution and its Remediation. Elsevier, Amsterdam, pp 161–173
Finch RJ, Murakami T (1999) Systematics and paragenesis ofuranium minerals. In: Burns PC, Ewing RC (eds) Uranium:
Mineralogy, Geochemistry and the Environment. Mineralogical Society of America and Geochemical Society
Reviews in Mineralogy and Geochemistry 38: pp 91–179
Grevel KD, Majzlan J (2011) Internally consistent thermodynamic data for metal divalent sulphate hydrates.
Chem Geol 286: 301–306
Hawthorne FC (2012) A bond-topological approach totheoretical mineralogy: crystal structure, chemicalcomposition and chemical reactions. Phys Chem Miner
39: 841–874

Bluelizardite, a new uranyl sulfate mineral

H awthorne FC, S chindler M (2008) Understanding
the weakly bonded constituents in oxysalt minerals.
Z Kristallogr 223: 41–68
Hayden LA, Burns PC (2002a) The sharing of an edge
between a uranyl pentagonal bipyramid and sulfate tetrahedron in the structure of KNa5[(UO2)(SO4)4](H2O).
Canad Mineral 40: 211–216
Hayden LA, Burns PC (2002b) A novel uranyl sulfate
cluster in the structure of Na6(UO2)(SO4)4(H2O)2. J Solid
State Chem 163: 313–318
Johnson DB (2003) Chemical and microbiological characteristics of mineral spoils and drainage waters atabandoned coal and metal mines. Water Air Soil Pollut:
Focus 3: 47– 66
Johnson DB, Hallberg KB (2005) Acid mine drainage remediation options: a review. Sci Total Environ 338: 3–14
Kampf AR, Plášil J, Kasatkin AV, Marty J (2013) Belakovskiite, IMA 2013-075. CNMNC Newsletter 18,
December 2013, page 3252. Mineral Mag 77: 3249–3258
Kasatkin AV, Nestola F, Plášil J, Marty J, Belakovskiy
DI, Agakhanov AA, Mills SJ, Pedron D, Lanza A,
Favaro M, Bianchin S, Lykova IS, Goliáš V, Birch
WD (2013) Manganoblödite, Na2Mn(SO4)2·4H2O, andcobaltoblödite, Na2Co(SO4)2·4H2O: two new membersof the blödite group from the Blue Lizard mine, San JuanCounty, Utah, USA. Mineral Mag 77: 367–383
Krivovichev SV, Burns PC (2001) Crystal chemistryof uranyl molybdates. III. New structural themesin Na 6[(UO 2) 2O(MoO 4) 4], Na 6[(UO 2)(MoO 4) 4] andK6[(UO2)2O(MoO4)4]. Canad Mineral 39: 197–206
Krivovichev SV, Burns PC (2003) Crystal chemistry of uranyl molybdates. VIII. Crystal structures of Na3Tl3[(UO2)(MoO4)4], Na13–xTl3+x[(UO2)(MoO4)3]4(H2O)6+x (x = 0.1),
Na3Tl5[(UO2)(MoO4)3]2(H2O)3 and Na2[(UO2)(MoO4)2](H2O)4. Canad Mineral 41: 707–719
Krivovichev SV, Plášil J (2013) Mineralogy and Crystallography of Uranium. In: Burns PC, Sigmon GE (eds)
Uranium: From Cradle to Grave. Mineralogical Association of Canada Short Courses 43: pp 15–119
Libowitzky E (1999) Correlation of O–H stretching frequencies and O–H…O hydrogen bond lengths in minerals.
Monatsh Chem 130: 1047–1059
Majzlan J (2010) Advances and gaps in the knowledge ofthermodynamics and crystallography of acid mine drainage sulfate minerals. Chimia 64: 699–704
Malcherek T, Schlüter J (2007) Cu3MgCl2(OH)6 and thebond-valence parameters of the OH–Cl bond. Acta Cryst
B63: 157–160
Mikhailov YuN, Gorbunova YuE, Kokh LA, Kuznetsov
VG, Grevtseva TG, Sokol SK, Ellert GV (1977) Synthesis and crystal structure of potassium trisulfatouranylate K4(UO2(SO4)3). Koord Khim 3: 508–513
Ondruš P, Veselovský F, Hloušek J, Skála R, Vavřín I,Frýda J, Čejka J, Gabašová A (1997) Secondary miner-

als of the Jáchymov (Joachimsthal) ore district. J Czech
Geol Soc 42: 3–76
Ondruš P, Veselovský F, Gabašová A, Drábek M, DobešP, Malý K, Hloušek J, Sejkora J (2003) Ore-forming
processes and mineral parageneses of the Jáchymov ore
district. J Czech Geol Soc 48: 157–192
Oszlányi G, Sütő A (2004) Ab initio structure solution bycharge flipping. Acta Cryst A60: 134–141
Oszlányi G, Sütő A (2008) The charge flipping algorithm.
Acta Cryst A64: 123–134
Palatinus L (2013) The charge flipping algorithm in crystallography. Acta Cryst B69: 1–16
Palatinus L, Chapuis G (2007) Superflip – a computer program for the solution of crystal structures by charge flipping in arbitrary dimensions. J Appl Cryst 40: 451–456
Palatinus L, van der Lee A (2008) Symmetry determination following structure solution in P1. J Appl Cryst 41:
975–984Petříček V, Dušek M, Palatinus L (2006) Jana2006. The
crystallographic computing system. Institute of Physics,
Prague, Czech Republic. Accessed on January 21, 2014,at http://jana.fzu.cz
Plášil J, Buixaderas E, Čejka J, Sejkora J, Jehlička J,
Novák M (2010) Raman spectroscopic study of the uranyl sulphate mineral zippeite: low wavenumber and U–Ostretching regions. Anal Bioanal Chem 397:2703–2715
Plášil J, Dušek M, Novák M, Čejka J, Císařová I, Škoda
R (2011a) Sejkoraite-(Y), a new member of the zippeite
group containing trivalent cations from Jáchymov (St.
Joachimsthal), Czech Republic: description and crystal
structure refinement. Amer Miner 96: 983–991
Plášil J, Mills SJ, Fejfarová K, Dušek M, Novák M, Škoda
R, Čejka J, Sejkora J (2011b) The crystal structure ofnatural zippeite, K1.85H+0.15[(UO2)4O2(SO4)2(OH)2](H2O)4,
from Jáchymov, Czech Republic. Canad Mineral 49:
1089–1103
Plášil J, Hloušek J, Veselovský F, Fejfarová K, Dušek M,Škoda R, Novák M, Čejka J, Sejkora J, Ondruš P (2012)
Adolfpateraite, K(UO2)(SO4)(OH)(H2O), a new uranylsulphate mineral from Jáchymov, Czech Republic. Amer
Miner 97: 447–454
Plášil J, Kampf AR, Kasatkin AV, Marty J, Škoda R, Silva
S, Čejka J (2013a) Meisserite, Na5(UO2)(SO4)3(SO3OH)(H2O), a new uranyl sulfate mineral from the Blue Lizard
mine, San Juan County, Utah, USA. Mineral Mag 77:
2975–2988
Plášil J, Fejfarová K, Škoda R, Dušek M, Marty J, Čejka
J (2013b) The crystal structure of magnesiozippeite,
Mg[(UO2)2O2(SO4)](H2O)3.5, from East Saddle Mine, San
Juan County, Utah (U.S.A.). Mineral Petrol 107: 211–219
Schindler M, Hawthorne FC (2001) A bond-valence approach to the structure, chemistry and paragenesis ofhydroxy-hydrated oxysalt minerals. III. Paragenesis ofborate minerals. Canad Mineral 39: 1257–1274
157

Jakub Plášil, Anthony R. Kampf, Anatoly V. Kasatkin, Joe Marty

Schindler M, Hawthorne FC (2004) A bond-valence approachto the uranyl-oxide hydroxy–hydrate minerals: chemicalcomposition and occurrence. Canad Mineral 42: 1601–1627
Schindler M, Hawthorne FC (2008) The stereochemistry
and chemical composition of interstitial complexes inuranyl–oxysalt minerals. Canad Mineral 46: 467–501

158

Schindler M, Hawthorne FC, Baur WH (2000) A crystal
chemical approach to the composition and occurrenceof vanadium minerals. Canad Mineral 38: 1443–1456
Schindler M, Huminicki DMC, Hawthorne FC (2006)
Sulfate minerals. I. Bond topology and chemical composition. Canad Mineral 44: 1403–1429