Journal of Geosciences, 68 (2023), 249–259

DOI: 10.3190/jgeosci.378

Original paper

Navrotskyite, K2Na10(UO2)3(SO4)9·2H2O, a new sodium and potassium
uranyl-sulfate mineral from the Blue Lizard mine, Red Canyon, White
Canyon District, San Juan County, Utah
Travis A. OLDS1*, Anthony R. KAMPF2, Samuel N. PERRY3, Xiaofeng GUO4, Joe MARTY5,
Timothy P. ROSE6, Peter C. BURNS3,7
Section of Minerals and Earth Sciences, Carnegie Museum of Natural History, 4400 Forbes Avenue, Pittsburgh, Pennsylvania 15213,
USA; oldst@carnegiemnh.org
2
Mineral Sciences Department, Natural History Museum of Los Angeles County, 900 Exposition Boulevard, Los Angeles, CA 90007, USA
3
Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN 46556, USA
4
Department of Chemistry, Washington State University, Pullman, WA 99163, USA
55199 East Silver Oak Road, Salt Lake City, UT 84108, USA
6
Nuclear and Chemical Sciences Division, Lawrence Livermore National Laboratory, Livermore, CA 94550, USA
7
Department of Chemistry, University of Notre Dame, Notre Dame, IN 46556, USA* Corresponding author
1Navrotskyite (IMA 2019-026), K2Na10(UO2)3(SO4)9·2H2O, is a new potassium-sodium-uranyl-sulfate mineral from theBlue Lizard mine, San Juan County, Utah, USA. The new mineral occurs on sandstone and asphaltite matrix in close
association with belakovskiite, blödite, bobcookite, changoite, fermiite, ferrinatrite, ilsemannite, ivsite, meisserite,
pseudomeisserite-(NH4), seaborgite and tamarugite. Navrotskyite is orthorhombic, space group Pbcm (#57), with unit
cell parameters a = 5.4456(13), b = 21.328(5), c = 33.439(8) Å, V = 3883.8(2) Å3 and Z = 4. Crystals are acicular tapered
needles up to about 1 mm in length, typically occurring as radial sprays and tightly intergrown aggregates resembling
fibre-optic bundles. Crystals are elongated on [100] and exhibit only the {012} prism form, resulting in diamond-shaped
cross-sections. The terminations are generally not well-formed, but broken crystals are truncated by good {100} cleavage. No twinning was observed. Navrotskyite is pale greenish yellow in color, has a white or very pale-yellow streak
and fluoresces neon yellow green under both long- and short-wave UV. It is transparent with vitreous to silky luster. The
mineral exhibits a splintery, uneven fracture and has a Mohs hardness of about 2. The calculated density based on theempirical formula is 3.46 g/cm3. The mineral is optically biaxial (–), with α = 1.520(2), β = 1.557(2) and γ = 1.565(2)(white light). The measured 2V is 48.2(5)° and the calculated 2V is 48.9°. Dispersion is imperceptible and no pleochroism
was observed. The optical orientation is X = a, Y = c, Z = b. The empirical formula is K2.06Na9.98U3.02S8.98O44H3.97 basedon 44 O apfu. The eight strongest powder X-ray diffraction lines are [dobs Å(I)(hkl)]: 5.28(100)(110), 3.050(44)(049,119), 10.70(43)(020), 3.845(36)(046,134,116), 3.225(30)(153), 3.533(29)(060,061,136), 2.822(29)(139) and 5.59(27)(006). The crystal structure of navrotskyite (R1 = 0.0289 for 4032 reflections with I > 2σI) contains infinite [(UO2)(SO4)3]4– chains that extend along [100] and that link to neighbouring chains via a complex network of K–O and Na–O
bonds. Related topologies based on the same UL3-type chain are also observed in the minerals fermiite, meisserite andpseudomeisserite-(NH4), all of which occur in the same general assemblage as navrotskyite.
Keywords: Navrotskyite, uranyl sulfate, uranium, crystal structure, chains, Raman
Received: 13 March 2022; accepted: 19 June 2023; handling editor: F. Laufek

1. Introduction
Sixty-two uranyl-sulfate minerals have been describedto date, recently overtaking the 53 known uranyl phosphates, making sulfates the most numerous subgroup of
uranyl minerals containing polyoxoanions. While uranyl
phosphates almost exclusively form structures based on
sheet topologies, uranyl-sulfate structures, in addition
to sheets of polyhedra (i.e. the zippeite group), tend tocontain isolated clusters and infinite chains of polyhedra(~40%) (Gurzhiy and Plášil 2019). This is especiallytrue of the uranyl sulfates found in the mines in Red
Canyon; most species occurring there contain structuralunits with cluster or chain topologies and this tendency
is likely related to how the minerals formed. The semiarid climate in Red Canyon includes periodic torrential
rains. Large mines, such as the Blue Lizard, have relatively consistent temperature throughout; however, theunique microclimate formed during oscillations of wet
and dry periods cause flooding and slow-to-develop, butlarge fluctuations in relative humidity underground. The
uranyl-sulfate minerals have formed as efflorescent coatwww.jgeosci.org

Travis A. Olds, Anthony R. Kampf, Samuel N. Perry, Xiaofeng Guo, Joe Marty, Timothy P. Rose, Peter C. Burns

Fig. 1 – Intergrown short prisms of navrotskyite with white ivsite. The
field of view is 0.84 mm across.

ings from groundwater seepage, and often these crusts
contain dozens of species in a small area. Blooms ofmineralization between wet and dry periods have likely
contributed to the observed diversity of minerals.
Navrotskyite is named for American physical chemist, geochemist and materials scientist Dr. Alexandra
Navrotsky (b. 1943). Her research interests have centred
about relating microscopic features of structure andbonding to macroscopic thermodynamic behaviour inminerals, ceramics and other complex materials. She has
published over 700 scientific papers and has received
numerous awards. In 2002, she was awarded the Benjamin Franklin Medal in Earth Science. In 2004, she waselected a Fellow of The Mineralogical Society (GreatBritain) and awarded the Urey Medal (the highest career

Tab. 1 Chemical composition of navrotskyite.
Constituent
Na2O
K 2O
UO3
SO3
H2O*
Total
* based on the structure

Theoretical
15.35
4.67
42.51
35.69
1.78
100.00

Mean
15.37
4.82
42.94
35.74
1.78
100.66Range
14.06–16.39
4.12–5.50
39.59–45.09
34.84–37.19–

Fig. 2 The Raman spectrum of navrotskyite taken with a 785 nm laser from 2000–60 cm –1.

250Stand. Dev.
0.87
0.55
2.16
0.96
–

Standard
albiteorthoclase
U metalanhydrite–

Navrotskyite, a new Blue Lizard mine mineral

Tab. 2 Powder X-ray data (d in Å) for navrotskyite. Only I ≥ 3 calculated lines are listed.
dcalc
10.6704
7.7163

Icalc
48
28

hkl
020
023

5.59

5.5860

33

100

5.28

12

4.90

5.27754.9489

26

4.78

Iobs

dobs

43

10.70

25

7.74

27

dcalc
2.18702.1741

Icalc
3
3

hkl
0 2 15190

2.16473

179

2.12292.0680

7
4

263
195

2.06093

0 4 15113

2.0325

12

249

122
130

2.02612.0165

8
4

196
266

2.00711.99353
5

0 8 11
0 10 6

Iobs

dobs

006

8

2.172

100
11

110
026

8

2.130

4.814419043

52.06194.7718144.65994.3246410192.0269

10

4.311

26

4.039

4.03303.8582

27
9

133
046

36

3.845

3.84293134

121.98691.98517

1 3 153.836232

116

2 0 12060
061

1.9454910
491.94983.55683.53690 8 12
1 7 1222029

1.91893
63.516091.9291
1.9263
1.91814

2 2 12

3.41963

136

1.90573280

3.389225063

1.90263281

3.35954150

1.89203

0 6 153.31323.2172
3.1182
3.0537

3
33
4
31

145
153
154
049

1.86991.86201.86051.8514

5
5
8
3

269
0 0 181 5 151 7 133.04273.00903.0002

20
5
3

119
138
066

1.83431.8036
1.78563
5
3

0 2 18286
1 11 42.98194147

1.755911

1 1 182.874

2.87908

156

1.7396

3

0 12 42.85523067

1.7377

7

333

2.822

2.821930

1391.73703

1 11 62.79302.72338
7

0 0 12200

1.72101.715663316
1 9 122.70202.69272.6676

4
3
6

3
5
4

336
353
2 4 152.6603

2 10 62.6520

29

3.533

27

3.385

30

3.225

44

3.050

6

3.002

8
29

12

23

8

22

21

2.715

2.657

2.582

2.483

2.384

5

1.893518

1.861291.8079101.770616

1.744315

1.71560 2 12
211
080

4
10

1.67761.65091.67791.65231.643412170

1.60774171

61.6086

6

339

4
4

220
173

1.58201.55774

2.63872.58794
71.59062 6 15
1 13 43069

1.54143
42.57215

1.55381.54481.53713

2 0 182.56812.4945

5
17

223
159

1.5293
1.52434
3

1 11 12359

2.46869

1 1 12

1.51834

3 1 122.44792.4018

6
6

206
176

1.49733

1 3 212.385962262.37049243

141.52487

1.4951251

Travis A. Olds, Anthony R. Kampf, Samuel N. Perry, Xiaofeng Guo, Joe Marty, Timothy P. Rose, Peter C. Burns

honour of the European Association of Geochemistry).
In 2006, she received the Harry H. Hess Medal of theAmerican Geophysical Union. In October 2009, she received the Roebling Medal, the highest honour awarded
by the Mineralogical Society of America.
The description is based on three cotype specimens (allmicromounts) deposited in the collections of the Natural
History Museum of Los Angeles County, 900 Exposition
Boulevard, Los Angeles, CA 90007, USA, catalogue numbers 73574, 73575 and 73576. The IMA-CNMNC approved
mineral abbreviation for navrotskyite is Nvr (Warr 2021).

2. Occurrence
Navrotskyite occurs underground in the Blue Lizard
mine, Red Canyon, White Canyon District, San JuanCounty, Utah. The Blue Lizard mine (37°33'26"N
110°17'44"W) is situated on the northern ridge of Red
Canyon, roughly 1 km to the northeast of the Markey
mine and ~22 km southeast of Good Hope Bay on Lake
Powell. Detailed historical and geologic informationon the Blue Lizard mine is provided elsewhere (Kampf
et al. 2015), and is primarily derived from a report by
Chenoweth (1993). Access to the underground workings
is no longer possible, as the entrance was gated in 2021.
Abundant secondary uranium mineralization in Red
Canyon is associated with post-mining oxidation ofasphaltite-rich sandstone beds laced with uraninite, coffinite and sulfides in the damp underground environment.
Navrotskyite was found in an area rich in K-bearing
sulfates (metavoltine, voltaite, zincovoltaite), and wasnoted as a close associate with seaborgite, LiK2Na6(UO2)(SO4)5(SO3OH)(H2O) (Kampf et al. 2021) in several specimens. Potassium enrichment has so far not been observedin secondary uranyl mineralization elsewhere in the Blue
Lizard mine, nor in any of the nearby U deposits in Red
Canyon that we have investigated. It is likely that K and Li
are sourced from Li- and K-bearing clays in the sediments.
Other associated minerals include belakovskiite, blödite,bobcookite, changoite, fermiite, ferrinatrite, ilsemannite,
ivsite, meisserite, pseudomeisserite-(NH4) and tamarugite.

3. Physical and optical properties

Crystals are acicular or thin tapered needles up to about
1 mm in length, typically occurring in radial sprays or
as tightly intergrown aggregates resembling fibre-optic
bundles (Fig. 1). The terminations are generally not wellformed, but broken crystals are truncated by good {100}cleavage. Crystals exhibit the prism form {012}, resulting
in diamond-shaped cross-sections. No other forms wereobserved, nor was twinning observed. Navrotskyite is palegreenish yellow, has a white or very pale-yellow streak andfluoresces neon yellow green under both long- and shortwave ultraviolet illumination.
Tab. 3 Data collection and structure refinement details for navrotskyite.
Aggregates sometimes appear
Temperature
293(2) K
greenish blue due to underlyStructural Formula
K2Na10(UO2)3(SO4)9·2H2O
ing ferrinatrite and coatings ofSpace groupPbcm
an amorphous hydrated MoUnit cell dimensionsa = 5.4456(13) Åoxide presumed to correspondb = 21.328(5) Åto ilsemannite. It is transparentc = 33.439(8) Åwith vitreous to silky luster and3883.8(16) Å3Vthe mineral exhibits a brittle
2
Z
tenacity; long, thin crystals are–3
Density (for above formula)3.453 g cm
flexible with splintery, uneven–1
Absorption coefficient13.428 mm
fracture and a Mohs hardness of
3696
F(000)
about 2 based on scratch tests.
Crystal size
4 × 4 × 5 µm
The density could not be meaθ range
2.64 to 25.24°
sured because the mineral is soluIndex ranges–6 ≤ h ≤ 6, –26 ≤ k ≤ 26, –41 ≤ l ≤ 41
ble in H2O (and Clerici solution).
Reflections collected/unique44551/4032; Rint = 0.09
The calculated density based on
3837
Reflections with I > 2σI
the empirical formula and density
Completeness to θ = 25.24°
99.9%
Refinement method
Full-matrix least-squares on F2
calculated using the cell derived
Parameter/restraints
332/3
from PXRD data is 3.46 g/cm3
GoF
1.038
and 3.45 g/cm3 using the cell volFinal R indices [I > 4σI]
R1 = 0.0289, wR2 = 0.0452
ume derived from the single-crysR indices (all data)
R1 = 0.0509, wR2 = 0.0498
tal X-ray diffraction study. The
Largest diff. peak/hole+1.22/–1.24 e A–3
mineral is optically biaxial (–),
Rint = Σ|Fo2–Fo2(mean)|/Σ[Fo2]. GoF = S = {Σ[w(Fo2–Fc2)2]/(n–p)}1/2. R1 = Σ||Fo|–|Fc||/Σ|Fo|.
with α = 1.520(2), β = 1.557(2)wR2 = {Σ[w(Fo2–Fc2)2]/Σ[w(Fo2)2]}1/2; w = 1/[σ2(Fo2)+(aP)2+bP] where a is 0.0114, b is 14.2186
and γ = 1.565(2) (determined in2
2
and P is [2Fc +Max(Fo ,0)]/3.

252

Navrotskyite, a new Blue Lizard mine mineral

white light). The measured 2V is48.2(5)° and the calculated 2V is
48.9°. Dispersion is imperceptible
and no pleochroism was observed.
The optical orientation is X = a,
Y = c, Z = b. The GladstoneDale relationship was calculated;
1 – (KP/KC) = –0.003 (superior)based on the empirical formulaand –0.005 (superior) based on theideal formula, in both cases usingk(UO3) = 0.118 (Mandarino 1976).

4. Chemical composition
Chemical analyses (6 points on
2 crystals) were performed on
a JEOL JXA-8230 electron microprobe using Probe for EPMA
software (Tab. 1). The analyticalconditions used were 15 keV
accelerating voltage, 3 nA beam
current and a beam diameter of 10
μm. Raw X-ray intensities werecorrected for matrix effects withthe φρ(z) algorithm (Pouchou andPichoir, 1985). Time-dependent
intensity corrections were applied to Na, K and S. Because
insufficient material was available for a direct determinationof H 2O, it has been calculated
based upon the structure determination (U + S = 12 apfu, O =44 apfu). The empirical formula,calculated on the basis of 44 O
apfu, is K2.06Na9.98U3.02S8.98O44H3.97.
The ideal formula is
K2Na10(UO2)3(SO4)9·2H2O, which
requires Na2O 15.35, K2O 4.67,
UO3 42.51, SO3 35.69, H2O 1.78,
total 100 wt. %.

Tab. 4 Atom coordinates and displacement parameters (Å2) for navrotskyite.
Site
U1
U2
S1
S2
S3
S4
S5
K1
Na1
Na2
Na3
Na4
Na5
Na6
Na7*
O1
O2
O3
O4
O5
O6
O7
O8
O9
O10
O11
O12
O13
O14
O15
O16
O17
O18
O19
O20
O21
O22
O23
OW1
H1A
H1B

x/a
0.23183(6)0.26713(4)0.6950(3)0.1233(3)0.3025(3)0.3461(4)0.1488(3)0.8076(3)0.2327(7)0.6757(7)0.6496(5)0.7976(7)0.6566(5)0.7813(5)0.032(2)0.9616(8)0.6215(9)0.5747(8)0.5913(8)0.3739(8)0.0695(8)0.0810(8)0.9465(8)0.0765(10)0.5032(8)0.3595(9)0.2836(11)0.0789(12)0.4539(9)0.4251(10)0.3721(8)0.9336(8)0.1591(8)0.1245(8)0.5187(12)0.9436(11)0.5496(8)0.9808(8)0.7020(10)0.586(9)0.775(11)

5. Raman Spectroscopy
Raman spectroscopy was conducted on a Horiba XploRA PLUS. The spectrum recorded from 2000 to 60 cm–1
using a 785 nm laser is given in Fig. 2. A broad bandwith low intensity centred near 1370 cm –1 is attributed
to combination bands. The split ν3 (SO4)2– antisymmetricstretching vibrations occur as weak bands at 1196, 1184,
1169, 1153 and 1119 cm–1. A complex set of medium andy/b0.82129(2)0.70323(2)0.34189(7)0.67776(7)0.85138(7)0.98870(11)0.53797(7)0.93900(8)0.250.68312(17)0.47365(12)0.07201(16)0.59104(12)0.86602(16)0.5144(5)0.3351(2)0.4060(2)0.2982(2)0.3257(2)0.6590(2)0.7404(2)0.6802(2)0.6323(2)0.8708(3)0.8909(2)0.7852(2)0.8572(2)0.9917(3)0.0181(2)0.9214(3)0.5372(2)0.5286(2)0.4886(2)0.5996(2)0.7837(3)0.8587(3)0.6723(2)0.7310(2)0.5527(2)0.565(3)0.583(2)z/c
0.25
0.41392(2)0.48078(4)0.30985(5)0.36007(5)0.250.40134(5)0.31790(5)0.5
0.25
0.41573(8)0.250.33911(8)0.42471(9)0.5001(5)0.48109(14)0.47093(14)0.45186(13)0.52071(12)0.30037(13)0.29238(13)0.35327(13)0.29354(13)0.37849(19)0.37413(15)0.36980(13)0.31651(13)0.25
0.28551(14)0.25
0.37753(14)0.37615(14)0.43214(13)0.42260(13)
0.25
0.25
0.39708(13)0.43161(13)0.46665(16)0.4809(18)0.4572(19)Ueq
0.00886(8)0.00941(6)0.0100(3)0.0092(3)0.0123(3)0.0127(5)0.0103(3)0.0309(4)0.0235(8)0.0214(9)0.0215(6)0.0204(9)0.0195(6)0.0393(8)0.037(3)0.0189(11)0.0218(11)0.0172(10)0.0135(10)0.0162(11)0.0163(10)0.0158(10)0.0165(10)0.0428(16)0.0216(12)0.0226(12)0.0366(14)0.0266(19)0.0239(12)0.0128(14)0.0177(11)0.0206(11)0.0170(10)0.0158(10)0.0250(17)0.0158(15)0.0167(10)0.0169(10)0.0252(11)0.02(2)0.02(2)strong intensity bands at 1036 (1050 sh), 1026, 1016,
1010, 993 and 975 cm–1 are assigned to the ν1(SO4)2–
symmetric stretching vibrations. The weak band at 917
cm–1 is related to the ν3 (UO2)2+ antisymmetric stretching vibration, which is normally absent; however slight
distortions lead to its activity here. The ν 1 (UO 2) 2+
symmetric stretching vibration is present as two very
intense bands at 866 and 847 cm–1, corresponding to thetwo symmetrically independent U sites in navrotskyite.
Using the empirical relationship developed by Bartlett
and Cooney (1989), we have calculated the approximate
uranyl oxygen (U–Oyl) bond lengths from the positions
253

Travis A. Olds, Anthony R. Kampf, Samuel N. Perry, Xiaofeng Guo, Joe Marty, Timothy P. Rose, Peter C. Burns

Tab. 5 Anisotropic displacement parameters (Å2) for navrotskyite.
U1
U2
S1
S2
S3
S4
S5
K1
Na1
Na2
Na3
Na4
Na5
Na6
Na7
O1
O2
O3
O4
O5
O6
O7
O8
O9
O10
O11
O12
O13
O14
O15
O16
O17
O18
O19
O20
O21
O22
O23
OW1

U11
0.01081(17)0.01236(12)0.0139(8)0.0113(7)0.0177(9)0.0140(12)0.0113(8)0.0324(10)0.018(2)0.018(2)0.0280(15)0.020(2)0.0151(14)0.0183(16)0.023(6)0.011(2)0.037(3)0.017(2)0.019(2)0.012(2)0.019(2)0.023(3)0.017(2)0.022(3)0.022(3)0.048(3)0.081(4)0.015(4)0.028(3)0.010(3)0.014(2)0.018(3)0.028(3)0.022(3)0.019(4)0.010(3)0.013(2)0.014(2)0.025(3)U220.00731(14)0.00897(11)0.0099(7)0.0111(8)0.0114(7)0.0089(12)0.0098(8)0.0364(9)0.0224(18)0.027(2)0.0171(14)0.0124(18)0.0229(15)0.071(2)0.067(10)0.025(3)0.010(2)0.022(2)0.015(2)0.024(3)0.015(3)0.019(2)0.020(3)0.055(4)0.016(3)0.009(3)0.018(2)0.014(4)0.020(3)0.010(3)0.019(3)0.018(3)0.011(2)0.012(2)0.013(4)0.013(3)0.020(3)0.021(3)0.022(3)U33
0.00845(15)0.00691(10)0.0064(7)0.0053(8)0.0080(7)0.0151(13)0.0099(8)0.0239(9)0.030(2)0.019(2)0.0194(15)0.029(2)0.0204(15)0.0286(17)0.020(3)0.021(3)0.019(3)0.013(2)0.006(2)0.013(3)0.015(2)0.006(2)0.013(3)0.052(4)0.027(3)0.011(3)0.010(2)0.051(5)0.023(3)0.018(4)0.020(3)0.026(3)0.011(2)0.014(3)0.043(5)0.025(4)0.018(3)0.016(2)0.029(3)of the ν1(UO2)2+ bands, which give 1.76 and 1.75 Å. The
calculated values are in good agreement with average
U–Oyl bond lengths from the X-ray data: U1, 1.759(4)Å, and U2, 1.768(4) Å.
Several weak overlapping bands between 651 and610 cm–1 are attributed to the split, triply degenerate ν4(δ) (SO4)2– bending vibrations, and those at 470 and 455
cm–1 to the split doubly degenerate ν2 (δ) (SO4)2– bending
vibrations. We base the remaining assignments for the
low wavenumber region on those provided by Plášil etal. (2010). The bands at 269 and 253 cm–1 are assigned
to split ν2 (δ) (UO2)2+ modes and one at 232 cm–1 to U–
Oeq–S modes. The weak bands at 190 and 131 cm–1 are
attributable to U–Oeq–U bending modes, and the remain254

U23

U13

0
–0.00011(9)0.0002(6)0.0002(7)0.0009(6)00.0003(6)0.0047(7)0.0050(16)00.0031(12)00.0075(12)0.0237(15)–0.004(7)–0.002(2)0.000(2)–0.001(2)0.0041(19)0.005(2)0.007(2)0.001(2)0.000(2)0.017(3)–0.003(2)0.0011(19)0.0030(19)0–0.011(2)00.003(2)–0.003(2)0.0053(19)–0.0013(19)000.001(2)–0.004(2)–0.003(2)0–0.00071(11)–0.0004(6)–0.0005(6)–0.0024(7)0–0.0001(6)0.0022(7)00–0.0022(13)00.0021(11)0.0001(14)–0.009(4)0.000(2)0.008(2)–0.0049(19)–0.0017(18)0.0029(19)0.001(2)–0.0020(19)–0.002(2)0.014(3)–0.007(2)–0.001(2)–0.017(3)0–0.002(2)00.006(2)–0.005(2)0.001(2)0.0064(19)000.0029(19)–0.001(2)0.008(3)U12–0.00041(15)–0.00093(11)0.0017(6)–0.0017(6)–0.0047(6)–0.0014(9)–0.0007(6)0.0080(8)00.0066(16)–0.0027(11)0.0007(16)0.0020(11)–0.0012(16)0.009(5)–0.001(2)0.008(2)0.003(2)–0.0005(19)0.003(2)0.0018(19)–0.004(2)–0.008(2)0.012(3)–0.009(2)–0.004(2)–0.014(3)0.004(3)–0.001(2)0.001(3)0.0032(19)–0.002(2)0.0020(19)–0.0036(19)–0.003(3)0.001(3)0.002(2)0.000(2)0.003(2)ing very weak bands at 87 and 64 cm–1 are unassigned
lattice modes corresponding to U atom displacements.
No modes belonging to K–O or Na–O stretching (~300
cm–1) were observed.

6. X-ray crystallography and structure
determination

6.1. Powder diffraction
X-ray powder diffraction data were recorded using a Rigaku R-Axis Rapid II curved imaging plate
microdiffracto­meter with monochromatized MoKα radia-

Navrotskyite, a new Blue Lizard mine mineralFig. 3 The crystal structure of navrotskyite viewed down a. The unit cell is indicated by dashed blue lines.

tion. A Gandolfi-like motion on the ϕ and ω axes was used
to randomize the sample. Observed d values and intensities were derived by profile fitting using JADE 2010 software (Materials Data, Inc.). Data are given in Tab. 2. Unit
cell parameters refined from the powder data using JADE
2010 with whole pattern fitting are a = 5.4466(8) Å,
b = 21.341(3) Å, c = 33.516(5) Å and V = 3895.8(10) Å3.

6.2. Single-crystal X-ray diffraction andstructure solution
A thin navrotskyite prism was chosen for the singlecrystal X-ray diffraction study. Data were collected using MoKα X-rays and an Apex II CCD-based detector
mounted to a Bruker Apex II three-circle diffractometer.
The Apex 3 software package was used for processing
collected diffraction data, including corrections for background, polarization and Lorentz effects. A multi-scansemi-empirical absorption correction was done using
SADABS, and an initial model in space group Pbcm wasderived by the intrinsic phasing method using SHELXT(Sheldrick 2015b). SHELXL-2016 (Sheldrick 2015a)
was used for the refinement of the structure. Difference
Fourier syntheses enabled location of H atom positions

associated with the single H2O group, Ow1, which wererefined with restraints of 0.84(3) Å on the O–H distancesand 1.34(3) Å for H–H distances. No restraints were used
for the H atom displacement parameters. Data collection
and refinement details are given in Tab. 3, atom coordinates and equivalent isotropic displacement parameters
are in Tab. 4, anisotropic displacement parameters are in
Tab. 5, selected bond distances are in Tab. 6 and a bondvalence analysis is given in Tab. 7.

6.3. Description of the crystal structure
The two symmetrically independent U6+ atoms in navrotskyite are coordinated by two multiply bonded apical‘yl’ oxygen atoms (Oyl) forming the approximately linear
uranyl cation (UO2)2+. The uranyl cations are coordinatedfive-fold equatorially by oxygen atoms of five different
SO4 groups, creating square bipyramids with Oyl atoms
at the opposing apical vertices of the polyhedron (Burns
2005; Lussier et al. 2016). The U1 polyhedron shares corners with two S2, two S3 and one S4 tetrahedron, while
U2 shares corners with two S1, one S2, one S3 and one
S5 tetrahedron. The S1, S2 and S3 tetrahedra link adjacent U1 and U2 polyhedra into infinite chains that extend
255

Travis A. Olds, Anthony R. Kampf, Samuel N. Perry, Xiaofeng Guo, Joe Marty, Timothy P. Rose, Peter C. Burns

Fig. 4 A comparison of the chain topologies
in navrotskyite, meisserite and fermiite.

along [100], producing a [(UO2)(SO4)3]4– structural unit.
The chains are also decorated by S4 and S5 tetrahedrathat link next-neighbor chains via a complex network of
K-O and Na-O polyhedra (Fig. 3).
The seven unique Na atom positions in navrotskyite
each exhibit irregular coordination geometries and form
between five to eight bonds with oxygen atoms of SO4
groups and Oyl atoms, serving to link together multiple[(UO2)(SO4)3]4– chains. Atoms Na1, Na2 and Na5 eachhave variable coordination numbers between six andeight and bond to oxygen atoms of SO4 groups and to
one Oyl atom each. Atoms Na3, Na4 and Na6 are sevenor eight-coordinated and bond solely with oxygen atomsof SO4 groups. Na7 forms a five-coordinated distorted
square pyramid with half occupancy that links two chains
together through the S1 and S5 tetrahedra attached toU2. The single unique K position is nine-coordinated256

and forms a dimeric arrangement with itself and binds
together multiple chains through SO4 tetrahedra (2 × S3,
2 × S4, S5) and O21, the Oyl atom of U1. The single
H2O group (Ow1, H1A, H1B) forms strong hydrogenbonds with oxygen atoms of two nearby SO4 groups, O2(Ow1–H1A···O2; 2.87 Å) and O19 (Ow1–H1B···O19;
2.91 Å) (Tab. 5).
Identical topologies based on the UL 3-type chain(Lussier et al. 2016) are also observed in the minerals
fermiite, Na4(UO2)(SO4)3(H2O)3 (Kampf et al. 2015) andmeisserite, Na5(UO2)(SO4)3(SO3OH)(H2O) (Plášil et al.
2013), and a related topology is found in pseudomeisserite-(NH4), (NH4)2Na4[(UO2)2(SO4)5](H2O)4 (Kampf etal. 2020), all of which occur in the same general assemblage as navrotskyite (Fig. 4). Pseudomeisserite-(NH 4)
contains a related UL3 chain fragment that constitutes
part of a more complex uranyl sulfate band. The chain

Navrotskyite, a new Blue Lizard mine mineral

Tab. 6 Selected bond distances (Å) for navrotskyite.
U1−O6
U1−O6
U1−O12
U1−O12
U1−O15
U1−O20U1−O21<U1−OUr><U1−OEq>

2.401(4)2.401(4)2.369(4)2.369(4)2.381(6)1.756(7)1.761(6)
1.759
2.384

U2−O3
U2−O4
U2−O7
U2−O11
U2−O19U2−O22U2−O23<U2−OUr><U2−OEq>

2.541(4)2.399(4)2.320(4)2.342(4)2.361(4)1.766(4)1.770(4)
1.768
2.393

K1−O9
K1−O10K1−O12
K1−O13
K1−O14
K1−O15
K1−O16
K1−O17
K1−O21<K1−O>

2.892(6)2.709(5)3.125(6)2.933(5)2.780(5)3.104(4)3.053(5)3.071(5)2.939(4)2.956

Na1−O1Na1−O1Na1−O3
Na1−O3
Na1−O4
Na1−O4
Na1−O23
Na1−O23<Na1−O>2.424(5)2.424(5)2.668(5)2.668(5)2.627(4)2.627(4)2.597(5)2.597(5)2.579

Hydrogen bonds
D–H··A
Ow1-H1A··O2
Ow1-H1B··O19

D–H
0.84(2)0.82(2)Na2−O5
Na2−O5
Na2−O6
Na2−O6
Na2−O8
Na2−O8
Na2−O20<Na2−O>

2.409(5)2.409(5)2.846(5)2.846(5)2.339(5)2.339(5)2.309(7)2.397

Na3−O2Na3−O9Na3−O10
Na3−O16
Na3−O17
Na3−O18
Na3−O18
Na3−Ow1<Na3−O>2.348(5)2.931(7)2.397(5)2.399(5)2.349(5)2.746(5)2.746(5)2.413(6)2.541

Na4−O5
Na4−O5
Na4−O8
Na4−O8
Na4−O13
Na4−O14
Na4−O14<Na4−O>2.674(5)2.674(5)2.391(5)2.391(5)2.298(7)2.497(6)2.497(6)2.489

Na5−O5Na5−O8
Na5−O14
Na5−O16
Na5−O17
Na5−O22<Na5−O>

2.480(5)2.364(5)2.449(5)2.317(5)2.363(5)2.665(5)2.440

Na6−O1Na6−O2
Na6−O3Na6−O9Na6−O10
Na6−O18
Na6−O23<Na6−O>2.439(5)2.816(6)2.584(5)2.232(7)2.332(6)2.646(6)3.086(6)2.591
H··A
2.06(3)2.25(4)

topologies in each phase differ in the relative orientation of SO4 tetrahedra and adjoining U-S-U polyhedra
exhibit torsion from planarity in the order (in degrees),
pseudomeisserite-(NH 4 ) (85.3/9.2) > navrotskyite(65.8/20.1/2.1) > meisserite (51.9/9.2) > fermiite(7.1/5.6). The torsion angle examined here is defined
between adjacent U atoms and the two connecting oxygen atoms of SO4 groups (U-O-O-U); with two such arrangements forming one link of the chain (Fig. 4). This
trend may be a response to increasing cation content or

Na7−O2
Na7−O18
Na7−O18
Na7−Ow1
Na7−Ow1<Na7−O>2.717(13)2.494(16)2.439(17)2.269(14)2.320(13)
2.448

S1−O1
S1−O2
S1−O3
S1−O4
<S1−O>

1.459(5)1.463(5)1.494(5)1.491(4)
1.477

S2−O5
S2−O6
S2−O7
S2−O8
<S2−O>

1.457(5)1.488(5)1.471(5)1.471(5)
1.472

S3−O9
S3−O10S3−O11S3−O12<S3−O>

1.437(6)1.458(5)1.482(5)1.466(5)1.461

S4−O13S4−O14S4−O14S4−O15<S4−O>

1.457(7)1.466(5)1.466(5)1.499(7)1.472

S5−O26S5−O45S5−O93S5−O61<S5−O>

1.454(5)1.457(5)1.474(5)1.500(5)
1.471

D··A
2.87(1)2.91(1)<DHA
163(7)
137(5)

cationic size, whereby bulky K+ and NH4+ cations induce
the highest distortions in the pseudomeisserite-(NH 4)
and navrotskyite chains.
Acknowledgements. We thank Dr. Nicolas Meisser forhis helpful comments that improved the manuscript.
A portion of this study was funded by the John Jago
Trelawney Endowment to the Mineral Sciences Department of the Natural History Museum of Los Angeles
County.
257

Travis A. Olds, Anthony R. Kampf, Samuel N. Perry, Xiaofeng Guo, Joe Marty, Timothy P. Rose, Peter C. Burns

Tab. 7 Bond valence analysis for navrotskyite. Values are expressed in valence units.*
U1
U2
K1
Na1
Na2
Na3
Na4
Na5
Na6
Na7
0.18
O1
0.17
×2 ↓
0.15
O2
0.21
0.07
×2 ↓
0.10
O3
0.35
0.12
×2 ↓
0.11
O4
0.47
×2 ↓
0.18
0.10
O5
0.15
×2 ↓
×2 ↓
0.47
0.06
O6
×2 ↓
×2
O7
0.56
0.22
0.19
O8
0.20
×2 ↓
×2 ↓
O9
0.12
0.05
0.28
O10
0.19
0.19
0.22
O11
0.53
O12
0.51 × 2 ↓
0.07
O13
0.11
0.24
0.15
O14
0.16
0.17
×2 ↓
0.07
O15
0.49
×2 →
O16
0.08
0.19
0.23
O17
0.08
0.21
0.20
0.08 ×2
0.16
O18
0.10
↓→
×2 ↓
O19
0.51
O20
1.85
0.23
0.11
O21
1.83
×2 →
O22
1.81
0.10
O23
1.79
0.12 ×2
0.04
0.24 ×2
Ow1
0.18
↓
Σcat
6.12
6.03
0.98
1.00
1.16
1.19
1.11
1.05
1.00
1.10

S1

S2

S3

S4

S5

H

1.55

Σanion
1.90

1.54

0.16

2.05

1.42

1.99

1.43

2.01
1.56

1.99

1.44

1.98

1.50

2.06

1.50

2.11
1.64
1.55
1.46
1.52
1.52

2.09
2.15
2.00
2.10
1.98

1.52

2.00

1.40

2.04
1.57
1.56

2.06
2.05

1.49
1.40

1.92
0.15

2.06
2.08
2.04

5.94

6.01

6.18

5.97

6.02

–0.15,
–0.16

1.91
1.95
0.11

*All cation–O bond valence parameters are from Gagné and Hawthorne (2015). Hydrogen-bond strengths are based on O–O bond lengths fromFerraris and Ivaldi (1988).

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