Mineralogical Magazine, April 2018, Vol. 82(2), pp. 401–411

Greenlizardite, (NH4)Na(UO2)2(SO4)2(OH)2·4H2O, a newmineral with phosphuranylite-type uranyl sulfate sheets fromRed Canyon, San Juan County, Utah, USA
ANTHONY R. KAMPF1,*, JAKUB PLÁŠIL2, BARBARA P. NASH3 AND JOE MARTY4
1

Mineral Sciences Department, Natural History Museum of Los Angeles County, 900 Exposition Boulevard, Los
Angeles, CA 90007, USA
2
Institute of Physics ASCR, v.v.i., Na Slovance 1999/2, 18221 Praha 8, Czech Republic
3
Department of Geology and Geophysics, University of Utah, Salt Lake City, Utah 84112, USA
45199 East Silver Oak Road, Salt Lake City, UT 84108, USA[Received 1 June 2017; Accepted 19 June 2017; Associate Editor: Stuart Mills]
ABSTR ACTThe new mineral greenlizardite (IMA2017-001), (NH4)Na(UO2)2(SO4)2(OH)2·4H2O, was found in theGreen Lizard mine, Red Canyon, San Juan County, Utah, USA, where it occurs as a secondary alteration
phase. It is associated with ammoniozippeite, boussingaultite and dickite. It forms as light green-yellow
blades up to ∼0.3 mm long. The mineral is vitreous and transparent with a white streak. It fluoresces
greenish blue in 405 nm light. Mohs hardness is ∼2. Crystals are brittle with irregular fracture and two
cleavages: perfect {001} and good {210}. Greenlizardite is easily soluble in room-temperature H2O. The
calculated density is 3.469 g cm–3. Optically, it is biaxial (+) with α = 1.559(1), β = 1.582(1) and γ = 1.608(1) (measured in white light). The measured 2V is 88(1)°; the calculated 2V is 87.8°. Dispersion is moderate,r < v. Pleochroism is X = very pale yellow green, Y = pale yellow green and Z = light yellow green; X < Y < Z.
The optical orientation is X ≈ c, Y ≈ a and Z ≈ b*. The Raman spectrum exhibits bands attributable toboth sulfate and uranyl groups. Electron probe microanalyses (with H2O based on the crystal structure) yielded(NH4)0.98Na1.00U1.96S2.04O18.00H10.02. Greenlizardite is triclinic, P1, a = 6.83617(17), b = 9.5127(3),c = 13.8979(10) Å, α = 98.636(7), β = 93.713(7), γ = 110.102(8)°, V = 832.49(8) Å3 and Z = 2. The crystal
structure (R1 = 2.39% for 2542 I > 2σI ) contains edge-sharing dimers of UO7 pentagonal bipyramids. The
dimers link by sharing corners with SO4 groups to form a [(UO2)2(SO4)2(OH)2]2– sheet based on thephosphuranylite anion topology. Zig-zag edge-sharing chains of NaO6 octahedra link adjacent[(UO2)2(SO4)2(OH)2]2– sheets, forming thick slabs. NH4 bonds to O atoms in adjacent slabs linking
them together. H2O groups occupy channels in the slabs and space between the slabs.
K E Y WO R D S : greenlizardite, new mineral, uranyl sulfate, crystal structure, Raman spectroscopy,
Green Lizard mine, Red Canyon, Utah, USA.
Introduction
OUR interest in the secondary mineralization in theuranium mines of Red Canyon in White canyon
district of south-eastern Utah (USA) began several
years ago at the Blue Lizard mine. That mine has
now proven to be a prolific source for new mineral*E-mail: akampf@nhm.org
https://doi.org/10.1180/minmag.2017.081.054

species, having already yielded 16, with several
others still under study. We have expanded ourefforts to several nearby mines including the Green
Lizard, Giveaway-Simplot and Markey mines. All
share similar geology and mineralogy, and somenew species are found at more than one mine. We
have provided a brief synopsis of the history of
uranium mining in the area in our descriptive paperon shumwayite, a new mineral found at both theGreen Lizard and Giveaway-Simplot mines(Kampf et al., 2017). Herein, we describe

Copyright © Mineralogical Society of Great Britain and Ireland 2018

ANTHONY R. KAMPF ET AL.

greenlizardite, the second new mineral from theGreen Lizard mine.
Greenlizardite is named for the locality, theGreen Lizard mine. The new mineral and its
name were approved by the Commission on New
Minerals, Nomenclature and Classification of
the International Mineralogical Association(IMA2017-001). The description is based on one
holotype and one cotype specimen, which aredeposited in the collections of the Natural History
Museum of Los Angeles County, 900 Exposition
Boulevard, Los Angeles, CA 90007, USA, catalogue numbers 66558 and 66559, respectively.

of the Blue Lizard mine. The geology is similar tothat of the Blue Lizard mine (Kampf et al., 2015a;
Chenoweth, 1993). The Green Lizard mine is also a
cotype locality for shumwayite (Kampf et al., 2017).
Mineralized channels are in the Shinarump
member of the Chinle Formation. The Shinarump
member consists of medium- to coarse-grainedsandstone, conglomeratic sandstone beds and thicksiltstone lenses. Ore minerals were deposited as
replacements of wood and other organic material
and as disseminations in the enclosing sandstone.
Since the mine closed, oxidation of primary oresin the humid underground environment has produced a variety of secondary minerals, mainly
sulfates, as efflorescent crusts on the surfaces ofmine walls.
Greenlizardite is a rare mineral, found inassociation with ammoniozippeite, boussingaultite,dickite and a potentially new Mg uranyl sulfate
mineral, currently under study. Other secondary
minerals found in the Green Lizard mine assemblage include beshtauite, calcite, gypsum, fermiite,
johannite, natrozippeite, oppenheimerite, plášilite,
rozenite, shumwayite, sulfur and wetherillite.

Occurrence
Greenlizardite was discovered on specimens
collected underground in the Green Lizard mine
(37°34’37.10”N, 110°17’52.80”W) in the White
Canyon mining district, San Juan County, Utah,
USA. The Green Lizard mine is near the head of Low
Canyon on the east side of Red Canyon, 2.1 km northPhysical and optical properties
Greenlizardite occurs as light green-yellow blades,
up to ∼0.3 mm long, forming irregular sprays(Fig. 1). Blades are flattened on {001}, elongated on[100] and exhibit the forms {100}, {010}, {010},{001}, {001}, {110}, {110}, {120} and {210}

FIG. 1. Greenlizardite with ammoniozippeite (left) inincandescent light (top) and 405 nm ultraviolet light(bottom). The field of view is 0.84 mm across.

FIG. 2. Crystal drawing of greenlizardite, clinographic
projection in nonstandard orientation.

402

GREENLIZARDITE, NEW URANYL SULFATE FROM RED CANYON, UTAH

FIG. 3. Raman spectrum of greenlizardite recorded using a 785 nm diode laser.

(Fig. 2). Twinning, probably by reflection on {001},
is observed under crossed polars. The mineral istransparent with a vitreous lustre and has a white
streak. It fluoresces greenish-blue when illuminatedby a 50 mW 405 nm blue-violet laser (Fig. 1). The
Mohs hardness is ∼2. Crystals are brittle withirregular fracture and two cleavages: perfect on{001} and good on {210}. The mineral is easily
soluble in room temperature H2O. The density could
not be measured because the mineral is soluble in
Clerici solution and there is insufficient material forphysical measurement. The calculated density
is 3.469 g cm–3 for the empirical formula and3.507 g cm–3 for the ideal formula.

Optically, greenlizardite is biaxial (+), with
α = 1.559(1), β = 1.582(1) and γ = 1.608(1), measured in white light. The 2V measured directly on aspindle stage is 88(1)°; the calculated 2V is 87.8°.
Dispersion is r < v, moderate. The mineral is weakly
pleochroic: X = very pale yellow green, Y = paleyellow green and Z = light yellow green; X < Y < Z.
The optical orientation is X ≈ c, Y ≈ a and Z ≈ b*.

Raman spectroscopy
Raman spectroscopy was conducted on a Horiba
XploRA PLUS. Pronounced fluorescence was

TABLE 1. Chemical composition (in wt.%) for greenlizardite.
Constituent

Mean

Range

Stand. Dev.

Probe standard

Ideal composition(NH4)2O
Na2O
Na2O (1 apfu)*
UO3
SO3
H2O**
Total*

2.75(2.34)
3.34
60.45
17.70
9.76
94.00

1.82–4.02
1.80–3.05

0.89
0.46

Cr2N (syn.)albite2.96

58.14–63.60
16.85–18.87

2.21
0.69

UO2 (syn.)celestine

3.52
65.06
18.21
10.24
99.99

* The low analysis total and lower than expected Na are attributed to the irregular surfaces of mounted crystals. The
Na2O wt.% corresponding to 1 Na apfu is used in the empirical formula.
** Based on the structure.

403

TABLE 2. Powder X-ray data (d in Å) for greenlizardite. Only calculated lines with I ≥ 2 are listed.
Iobs

dobs
13.59
6.80
6.33
6.06
5.75

24
8
13

5.52
4.65
4.53

32
7

4.41
4.044

404

17

3.966

13
25

3.684
3.481

56

3.404

4
6

3.257
3.186

60
26

3.126
3.073

34

2.988

f
f
f

f
f

f

2.940

f

19

2.709

f

18

2.661

6

2.602

6

2.545

18

f
f

13.6320
6.81606.34866.06955.77305.73745.51154.66454.54404.47884.42324.39044.04533.9712
3.93993.70933.68103.49503.41593.41093.40803.35893.26103.18633.17503.12993.1166
3.07723.01292.99072.97642.95312.92892.73452.72642.69982.66882.66292.64922.60552.56402.5345

Icalc
25
100
7
26
18
25
18
7
11
2
11
10
4
7
8
5
9
18
10
19
14
2
7
6
2
26
15
14
4
16
7
4
9
2
6
9
5
4
4
4
4
4

hkl
001
002

110

101
1
11

111
101
1
12
003

1
11
0
21
020
0
22
021

103
1
13

113
0
23
022

210
004

211
2
11

1
21

104

212

130

1
22
1
14
1
32
2
12

131
121

2 1 1005
210
2 3 1
2 1 2
2
13

231

1 2 4
0
25

Iobs

dobs

11

2.495

5

2.456

7

2.380

16

2.254

15

2.222

19

2.146

11

2.107

8

2.079613

2.049272.01939

1.969418

1.940026

1.9097

dcalc

f
f
f

f
f

f
f
f

f

f

2.50722.49782.49032.48012.47152.42262.38082.37232.27202.25762.25372.25162.23752.23272.22222.16482.1597
2.15392.14472.13892.13672.11562.09662.09392.07392.06732.05982.05082.04822.03422.0232
1.9773
1.9661
1.9474
1.9356
1.92751.91981.91561.90841.90471.8975

Icalc

hkl

2
2
3
3
2
3
4
3
3
2
3
2
2
3
2
2
3
3
3
2
2
3
3
2
2
2
2
3
2
3
2
2
4
8
4
3
2
2
4
6
2

2 1 3
1 1 5
2 1 4024
1 3 4
1 3 3212
123006
3 1 1
3 2 02 3 3
3 2 1
0 4 12 4 1
3 2 2
2 2 3
2 4 1
1 1 6
3 0 1221
3 2 2
2 1 5
3 1 32 4 32 1 5106
3 2 3
2 3 4
1 2 6
3 0 32 3 5214007
3 1 1
1 3 5
3 1 20 2 7
1 4 2
3 4 0
1 5 1

Iobs

dobs

25

1.8817f

18

1.8553f

6

1.8341101.806212

1.78298

1.7283141.701613

1.6766

7

1.645912

1.591216

1.56718

1.52138
7
61.5022
1.4772
1.4546

f
f
f
f
f

f

f
f

dcalc

Icalc

hkl

1.8836
1.88151.87841.87371.8683
1.8572
1.8557
1.8473
1.83861.8123
1.7996
1.7891
1.78381.76151.7373
1.72691.7054
1.69301.6793
1.67371.64911.6473
1.63461.6302
1.5972
1.5955
1.5893
1.58791.57561.56561.56501.55991.5414
1.52661.51471.50251.48451.4475

3
3
3
3
2
4
3
3
3
3
2
2
2
2
2
3
3
2
4
4
2
3
2
2
2
2
2
2
2
2
3
2
2
2
3
2
2
2

125
026
140

150

3
13
3
42
311
3
24
1
53

342

1
44

3
14
0
51
1
37

152
142

420
0
54
4
21
1
55
1
18
2
17


128

344
3
45

402


241

3
16

2
43
2
62

424

137

154
127
009

327
3
61
3
63

ANTHONY R. KAMPF ET AL.

24
100
12
36
62

dcalc

GREENLIZARDITE, NEW URANYL SULFATE FROM RED CANYON, UTAH

observed using a 532 nm diode laser; consequently,
a 785 nm diode laser was utilized. The spectrum
was recorded from 3000 to 50 cm–1; however, only
the portion from 1600 to 50 cm–1 is shown in Fig. 3
because no features were observed between 3000
and 1600 cm–1.
Quite intense Raman bands at 1225 cm–1 and at
1097, 1086 (sh) and 1068 cm–1 are attributed to split
triply degenerate ν3 antisymmetric stretching vibrations of the SO4 tetrahedra. The number of split
bands is in line with the presence of two symmetrically non-equivalent SO4 tetrahedra in the structure of greenlizardite (cf. bluelizardite or synthetic
klaprothite, Plášil et al., 2016). Bands at 1031 and1027 (sh) cm–1, having the highest intensity within
the region of SO4 stretching modes, are assigned tothe ν1 symmetric stretching vibrations of SO4
tetrahedra. A weak, two-component band at 938
and 933 cm–1 is assigned to the ν3 antisymmetricstretching vibration of the uranyl ion, UO2 2+; a verystrong band at 837 cm–1 is assigned to the ν1symmetric U–O stretching vibration of the UO2 2+.
The inferred U–O bond lengths (after Bartlett andCooney, 1989) in the uranyl ion of ∼1.77 Å (fromν1) and 1.76 (from ν3) are in line with those derived
from the present X-ray study.
Weak Raman bands at 635 and 618 cm–1 are
attributed to the ν4 (δ) triply degenerated antisymmetric stretching vibrations of SO4 tetrahedra.
Weak Raman bands 469, 450 and 435 (sh) cm–1
are related to the split ν2 (δ) doubly degeneratebending vibrations of the SO4.
The band at 355 cm–1 and possibly also that at
297 cm–1 can be attributed to Na–O stretchingvibrations (cf. Kampf et al., 2015b,c; Plášil et al.,2010, 2016; Volkovich et al., 1998). The twocomponent strong Raman band at 234 and 194 cm–1,
with shoulders at 258 cm–1 and 177 cm–1 is mostprobably related to the ν2 (δ) doubly degeneratebending vibration of the UO2+
2 and U–Oeq–ligand
stretching modes (cf. Bullock and Parret, 1970;
Ohwada, 1976; Brittain et al., 1985; Plášil et al.,2010). Weak bands at the lowest energies can be
assigned to unclassified lattice modes, most probably
skeletal vibrations of the whole sheets of polyhedra.

TABLE 3. Data collection and structure refinement
details for greenlizardite.
Diffractometer

Rigaku R-Axis Rapid II

X-ray radiation/power MoKα (λ = 0.71075 Å)/50 kV,
40 mA
Temperature
293(2) K
Structural formula(NH4)Na(UO2)2(SO4)2(OH)2·4H2OSpace groupP1
Unit-cell dimensions a = 6.83617(17) Åb = 9.5127(3) Åc = 13.8979(10) Å
α = 98.636(7)°β = 93.713(7)°γ = 110.102(8)°V
832.49(8) Å3
Z2
Density (for above
3.492 g cm–3
formula)Absorption coef.
19.794 mm–1
F(000)
776
Crystal size (μm)
100 × 20 × 2
θ range
3.20 to 25.03°
Index ranges−6 ≤ h ≤ 8, –11 ≤ k ≤ 11, –16 ≤l ≤ 16
Refl. collected/unique 11,856/2926; Rint = 0.037
Refl. with I > 2σI
2542
Completeness to99.7%
θ = 25.03°
Refinement method
Full-matrix least-squares on F 2Parameter/restraints
217/0
Goof
1.070
Final R indices [I >R1 = 0.0239, wR2 = 0.0491
2σI]
R indices (all data)
R1 = 0.0301, wR2 = 0.0511
Largest diff. peak/hole +1.24/–0.99 e A–3
Rint = Σ|Fo2–Fo2(mean)|/Σ[Fo2]. Goof = S = {Σ[w(Fo2–F2c )2]/(n–p)}1/2. R1 = Σ||Fo|–|Fc||/Σ|Fo|. wR2 = {Σ[w(Fo2–F2c )2]/Σ
[w(Fo2)2]}1/2; w = 1/[σ2(Fo2)+(aP)2+bP] where a is 0.0151,
b is 5.461 and P is [2F2c +Max(Fo2,0)]/3.

Composition
Chemical analyses (6 points on 4 crystals) were
performed at the University of Utah on a Cameca
SX-50 electron microprobe with four wavelength
dispersive spectrometers and using Probe for
EPMA software. Analytical conditions were405

15 kV accelerating voltage, 10 nA beam current
and a beam diameter of 5 µm. Counting times were
30 s on peak and 30 s on background for eachelement. Raw X-ray intensities were corrected for
matrix effects with a PAP algorithm (Pouchou andPichoir, 1991). A time-dependent intensity correction was applied to Na; the N intensity was time
independent. Na and N exhibited significant
variability, and a negative relationship was apparent. Greenlizardite was very challenging to analyse.
It was not possible to obtain a good polish and someTABLE 4. Atom coordinates and displacement parameters (Å2) for greenlizardite.
y/b

z/c

Ueq

U 11

U 22

U 33

U 23

U 13

U 12

0.1545(11)0.2764(4)0.13909(4)0.37132(4)0.5653(3)0.9452(3)0.5528(9)0.7745(8)0.4104(7)0.5235(8)0.9615(9)0.7370(7)0.1024(8)0.9814(8)0.0994(8)0.1834(8)0.3130(8)0.4386(8)0.4468(7)0.0742(7)0.6569(14)0.7706(11)0.3001(12)0.7681(10)0.3668(7)0.0559(3)0.22166(3)0.65068(3)0.06488(19)0.82295(19)0.0678(6)0.1623(6)0.1195(6)0.9077(5)0.8819(6)0.7066(5)0.7516(6)0.9476(5)0.2112(6)0.2309(6)0.5935(6)0.7112(6)0.4297(5)0.4489(5)0.8585(10)0.1127(8)0.6217(8)0.4831(8)0.9677(5)0.4990(2)0.27410(2)0.27563(2)0.29872(13)0.29716(13)0.4025(4)0.2812(4)0.2539(4)0.2467(4)0.4013(4)0.2599(4)0.2780(4)0.2404(4)0.1458(4)0.4025(4)0.1468(4)0.4043(4)0.2810(4)0.2970(4)0.0431(6)0.9455(5)0.8743(5)0.4353(5)0.0288(16)0.0250(7)0.01180(8)0.01173(8)0.0140(4)0.0140(4)0.0297(13)0.0292(13)0.0225(12)0.0199(11)0.0301(13)0.0216(12)0.0308(14)0.0204(12)0.0224(12)0.0214(12)0.0217(12)0.0214(12)0.0173(11)0.0224(12)0.076(3)0.0550(19)0.0549(19)0.0471(17)0.041(4)0.0223(16)0.00982(14)0.00974(14)0.0103(8)0.0081(8)0.039(3)0.015(3)0.016(3)0.020(3)0.031(3)0.012(3)0.020(3)0.019(3)0.029(3)0.024(3)0.027(3)0.022(3)0.012(2)0.011(2)0.093(6)0.044(4)0.081(5)0.045(4)0.020(4)0.0296(18)0.00848(14)0.00748(14)0.0100(8)0.0100(8)0.036(3)0.016(3)0.018(3)0.010(2)0.031(3)0.011(3)0.018(3)0.009(3)0.019(3)0.016(3)0.019(3)0.017(3)0.010(2)0.010(3)0.085(6)0.063(5)0.059(5)0.067(5)0.016(3)0.0229(17)0.01759(15)0.01776(15)0.0230(10)0.0249(10)0.020(3)0.056(4)0.038(3)0.031(3)0.021(3)0.038(3)0.060(4)0.032(3)0.020(3)0.023(3)0.019(3)0.022(3)0.031(3)0.047(4)0.073(6)0.049(4)0.041(4)0.034(4)0.001(3)0.0041(14)0.00406(11)0.00249(10)0.0040(7)0.0055(7)0.006(3)0.008(3)0.006(2)0.006(2)0.002(3)0.003(2)0.012(3)0.006(2)0.006(2)0.003(2)0.003(2)0.002(2)0.006(2)0.008(2)0.034(5)0.017(4)0.019(4)0.008(3)−0.001(3)0.0003(13)0.00245(10)0.00207(10)0.0043(7)0.0042(7)0.003(2)0.010(3)0.003(2)0.010(2)0.004(2)0.003(2)0.007(3)0.003(2)0.003(2)0.001(2)0.001(2)0.003(2)0.008(2)0.008(2)0.029(5)0.000(3)0.017(4)0.002(3)0.002(3)0.0099(14)0.00308(11)0.00268(11)0.0046(7)0.0032(7)0.019(3)0.002(2)0.013(2)0.004(2)0.003(3)−0.001(2)0.012(2)0.003(2)0.007(2)0.005(2)0.008(2)0.003(2)0.005(2)0.003(2)0.048(5)0.008(4)0.039(4)0.026(4)ANTHONY R. KAMPF ET AL.

406

NH4
Na
U1
U2
S1
S2
O1
O2
O3
O4
O5
O6
O7
O8
O9
O10
O11
O12
OH1
OH2
OW1
OW2
OW3
OW4

x/a

GREENLIZARDITE, NEW URANYL SULFATE FROM RED CANYON, UTAH

beam damage was noted. The low analysis total andlower than expected Na are attributed to theirregular
surfacesof mounted crystals.
Preliminary analyses on unpolished crystal faces
using an Oxford SEMEDX200EDS on a Hitachi
S-3000N SEM employing internal standards,
while only semi-quantitative, were consistent withstoichiometric Na atom per formula unit (apfu).
Because insufficient material is available for a
direct determination of H2O, it has been calculated
based upon the structure determination. Analytical
data are given in Table 1.
The empirical formula calculated on the basis of
18 O apfu is (NH4)0.98Na1.00U1.96S2.04O18.00H10.02.
The
ideal
formulais(NH4)Na(UO2)2(SO4)2(OH)2·4H2O. The Gladstone-Dalecompatibility index 1 – (KP/KC) is –0.016 basedon the empirical formula and –0.008 based on theideal formula, in both cases in the range of superior
compatibility (Mandarino, 2007).

microdiffractometer,withmonochromatized
MoKα radiation (λ = 0.71075 Å). A Gandolfi-likemotion on the j 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.). The powder data presented
in Table 2 show good agreement with the patterncalculated from the crystal-structure determination.
The single-crystal reflection data were collectedusing the same diffractometer and with the sameradiation as noted above. The Rigaku CrystalClearsoftware package was used for processing the data,
including the application of both shape-based andempirical absorption corrections, the latter using themulti-scan method with ABSCOR (Higashi, 2001).
The structure was solved using SIR2011 (Burla et al,2012). SHELXL-2013 (Sheldrick, 2015) was used
for the refinement of the structure. DifferenceFourier syntheses suggested possible positions forsome of the H atoms; however, their reliability was
not judged sufficiently high to report. Consequently,
they have not been included in the refined structure.
The proposed hydrogen-bonding scheme is based
upon bond geometries and bond-valence balance,
but must be considered highly conjectural. Data
collection and refinement details are given in
Table 3, atom coordinates and displacement

X-ray crystallography and structurerefinement
The powder X-ray study was carried out using a
Rigaku R-Axis Rapid II curved imaging plate

TABLE 5. Selected bond distances (Å) for greenlizardite.
NH4–OW3
NH4–OW1
NH4–OW2
NH4–O11
NH4–O9
NH4–O6<NH4–O>

2.830(9)2.847(11)2.852(9)2.908(8)3.049(8)3.322(9)
2.968

Na–O1
Na–O5
Na–O5
Na–O1
Na–O10Na–O12<Na–O>

2.368(6)2.371(6)2.390(6)2.418(6)2.502(6)2.512(6)
2.427

U1–O9
U1–O10U1–OH1U1–OH2
U1–O2
U1–O3
U1–O8
<U1–OUr><U1–Oeq>1.768(5)1.774(5)2.325(4)2.333(5)2.371(5)2.385(5)2.411(5)
1.771
2.365

U2–O11
U2–O12U2–OH2U2–OH1
U2–O7
U2–O6
U2–O4
<U2–OUr><U2–Oeq>1.768(5)1.773(5)2.338(5)2.340(5)2.348(5)2.402(5)2.414(5)
1.771
2.368

S1–O1
S1–O2
S1–O3
S1–O4
<S1–O>

1.447(5)1.472(5)1.472(5)1.481(5)
1.471

S2–O5
S2–O7
S2–O6
S2–O8
<S2–O>

1.454(6)1.473(6)1.473(5)1.482(5)
1.468

407

Hydrogen bonds
OH1···OW4
OH2···OW4
OW1···OW2
OW1···OW3
OW2···O8
OW2···O9
OW3···OH1
OW3···OW1
OW4···O10
OW4···O12

2.824(8)2.996(8)3.039(11)3.228(12)3.266(9)3.26(2)2.941(9)3.228(12)3.169(9)3.199(8)ANTHONY R. KAMPF ET AL.

parameters in Table 4, selected bond distances inTable 5 and a bond-valence analysis in Table 6.

[(UO2)2(OH)2(SO4)2](H2O)8, (Mereiter, 1982),
deliensite, Fe(UO2)2(SO4)2(OH)2·7H2O, (Plášil
et al., 2012) and plášilite, Na(UO2)(SO4)(OH)·2H2O (Kampf et al., 2015a) are topologically
identical to that in greenlizardite; however, thesesheets are geometrical isomers, differing in theorientation of the SO4 groups (Fig. 4). In greenlizardite, within the same [(UO2)2(SO4)2(OH)2]2–
sheet, the corner of each SO4 group that is notshared with UO7 pentagonal bipyramids points inthe same direction.
In the structure of greenlizardite (Fig. 5), theNa bonds to two uranyl O atoms (one in each of
two adjacent sheets) and four sulfate O atoms(two in each of two adjacent sheets) yielding anapproximately octahedral coordination. NaO6
octahedra share edges to form zig-zag chains
along [100] and these chains link two adjacent[(UO2)2(SO4)2(OH)2]2– sheets forming a thickslab. This slab has channels along [100] that

Description of the crystal structure
The U sites in the structure of greenlizardite are
surrounded by seven O atoms forming a squat UO7pentagonal bipyramid. This is the most typicalcoordination for U6+, particularly in uranyl sulfates,
where the two short apical bonds of the bipyramid
constitute the UO2 uranyl group. In the structureof greenlizardite, pairs of pentagonal bipyramids
share a common edge, forming dimers. The dimers
are linked by sharing corners with SO4 groups,
yielding a [(UO2)2(SO4)2(OH)2]2– sheet parallelto (001) (Fig. 4). This sheet is based on thephosphuranylite anion topology (Burns, 2005),
with a ring symbol 61524232 (Krivovichev andBurns, 2007). The sheets in johannite, Cu

TABLE 6. Bond-valence analysis for greenlizardite. Values are expressed in valence units.*
NH4

Na

U1

U2

S1

S2

Hydrogen bonds
Accepted

O1

0.20
0.18

O2
O3
O4
O5

0.50
0.49
0.46

1.98

1.50
1.50
1.47

2.00
1.99
1.93
1.96

1.57

O6
O7
O8
O9
O10
O11
O12
OH1
OH2
OW1

0.05

0.47
0.53

0.19

+0.10

OW2

0.18

+0.12

OW3

0.20

+0.10

0.15

1.50
1.50
1.46

0.46
1.80
1.78

0.16
0.14
0.55
0.55

1.80
1.78
0.54
0.54

+0.09
+0.10
+0.10
+0.10
+0.14

OW4
Σ

+0.18
+0.13
0.89

1.06

Donated

1.60

0.20
0.19

0.11

6.13

6.12

Σ

6.07

−0.18
−0.13
−0.12
–0.10
−0.10
–0.09
−0.14
–0.10
−0.10
–0.10

2.02
2.03
2.01
2.01
2.03
1.96
2.02
1.05
0.96
0.07
0.11
0.06
0.11

6.03

* NH+4 –O bond valence parameters from Garcia-Rodriguez et al. (2000); all other cation–O bond valence parameters from
Gagné and Hawthorne (2015); hydrogen-bond strengths based on O–O bond lengths from Ferraris and Ivaldi (1988).

408

GREENLIZARDITE, NEW URANYL SULFATE FROM RED CANYON, UTAH

FIG. 4. The uranyl sulfate sheets in greenlizardite, johannite, plášilite and deliensite. UO7 bipyramids are blue and SO4
tetrahedra are yellow. Note the differing orientations of SO4 tetrahedra.

contain isolated H2O groups (OW4). The NH4group and three H2O groups (OW1, OW2 andOW3) are located in the region between adjacentslabs. The NH4 bonds to each of the three interlayer
H2O groups (OW1, OW2 and OW3) and links
adjacent slabs together by bonding to two uranyl O
atoms (O9 and O11) in one slab and one of theequatorial O atoms (O6) of a UO7 bipyramid in
another slab (which is also part of the S2O4
tetrahedron). The NH4–O6 bond is quite long
(3.322 Å), which would be expected to result invery weak linkage between slabs; however, theNH4–O6 linkage is augmented by extensive409

hydrogen bonding from the interlayer H2O groups(OW1, OW2 and OW3).
The linkages between the sheets in the structureof greenlizardite are quite different than those in the
structures of johannite, deliensite and plášilite.
Most notably, there are two different intersheet
regions in greenlizardite, one containing edgesharing chains of NaO6 octahedra and the othercontaining irregular (NH4)O3(H2O)3 polyhedra andthey link the sheets together as described above.
The structures of johannite, deliensite and plášilite
all contain only one type of intersheet region. In
deliensite, an individual Fe2+O(H2O)5 octahedron

ANTHONY R. KAMPF ET AL.

FIG. 5. The structure of greenlizardite viewed down [100].
O atoms of isolated H2O groups are large white spheres.
NH4–O bonds are shown as sticks. Hydrogen bonds areshown as dashed lines. The unit-cell outline is in orange.

links to one uranyl O atom in one sheet and links tothe adjacent sheet only through hydrogen bonding.
In johannite, an individual Jahn-Teller distorted
CuO2(H2O)4 octahedron shares its apical O atoms
with uranyl O atoms in two adjacent sheets. In
plášilite, NaO2(H2O)4 octahedra form a cis edgesharing straight chain and each octahedron sharesone O atom with a uranyl group in one sheet andone O atom with a sulfate group in the adjacent
sheet.

Acknowledgements
The manuscript benefitted from constructive comments by reviewers Travis Olds and Andrew Locock.
This study was funded by the John Jago Trelawney
Endowment to the Mineral Sciences Department of
the Natural History Museum of Los Angeles County.
JP was supported through the project No. 17-09161Sof the Grant agency of the Czech Republic.

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