Journal of Geosciences, 60 (2015), 251–257

DOI: 10.3190/jgeosci.199

Original paper

Karpenkoite, Co3(V2O7)(OH)2·2H2O, a cobalt analogue of martyite
from the Little Eva mine, Grand County, Utah, USA
Anatoly V. Kasatkin1, Jakub Plášil2*, Igor V. Pekov3, Dmitry I. Belakovskiy1, Fabrizio
Nestola4, Jiří Čejka5, Marina F. Vigasina3, Federico Zorzi4, Brent thorne6
Fersman Mineralogical Museum of Russian Academy of Sciences, Leninsky Prospekt 18-2, 119071 Moscow, Russia
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
3
Faculty of Geology, Moscow State University, Vorobievy Gory, 119991 Moscow, Russia
4
Dipartimento di Geoscienze, Università di Padova, Via Gradenigo 6, I-35131, Padova, Italy
5
Department of Mineralogy and Petrology, National Museum, Cirkusová 1740, 193 00 Prague 9, Czech Republic
63898 S. Newport Circle, Bountiful, UT 84010, USA* Corresponding author
1
2

Karpenkoite (IMA 2014-092), ideally Co3(V2O7)(OH)2·2H2O, is a new divanadate mineral species, the cobalt analogueof martyite, found at the Little Eva mine, Grand County, Utah, USA. It occurs on sandstone matrix in close association
with martyite, quartz, gypsum, baryte, roscoelite and an unidentified Al vanadate. Karpenkoite is a secondary mineralformed during the post-mining oxidation of corvusite and montroseite in a moist environment at ambient temperatures.
The new mineral occurs as lamellar crystals, coarsely hexagonal or irregular in shape, typically curved. The crystals formrose-like clusters or globular aggregates up to 0.2 mm across. Karpenkoite is orange with pale yellow-orange streak. It
is transparent with a vitreous luster. The mineral is brittle, with laminated fracture and perfect cleavage on {001}. The
calculated density is 3.415 g cm–3. The mineral is optically uniaxial (+), with ω = 1.827(8) and ε = 1.843(8). The chemical composition of karpenkoite (wt. %, electron-microprobe data) is: MgO 0.05, CaO 0.26, MnO 1.39, CoO 33.22, NiO
2.02, CuO 0.28, ZnO 12.66, V2O5 38.70, H2O (calc.) 11.61, total 100.19. The empirical formula, calculated on the basisof 11 O apfu, is (Co2.06Zn0.72Ni0.13Mn0.09Ca0.02Cu0.02Mg0.01)Σ3.05V1.98O7(OH)2·2H2O. The Raman spectrum demonstrates
symmetric stretching and bending vibrations of V5+O3 units and the O–H stretching and bending vibrations of the H2O
molecules. The new mineral is trigonal, the most probable space group is P3̄m1 (by analogy with its Zn analogue martyite),a = 6.016(4), c = 7.234(6) Å, V = 226.7(2) Å3 and Z = 1. The strongest powder X-ray diffraction lines are [dobs,Å(I)(hkl)]:
7.15(100)(001), 5.19(18)(010), 4.20(25)(101,011), 3.59(21)(002), 2.95(54)(012,102), 2.77(21)(111), 2.60(36)(200), and2.44(33)(201,021). The new mineral is named in honor of the Russian mineralogist Vladimir Yu. Karpenko (b. 1965),
an expert on the mineralogy of vanadium.
Keywords: karpenkoite, new mineral, cobalt divanadate, powder diffraction, Little Eva mine, Utah
Received: 25 August, 2015; accepted: 20 November, 2015; handling editor: F. Laufek
The online version of this article (doi: 10.3190/jgeosci.199) contains supplementary electronic material.

1. Introduction
Natural divanadates, i.e., minerals with the [V 2O 7] 4–
group as the species-defining anion, are not numerous.
To date, only seven such minerals are known. Amongthem, four species are H-bearing, namely volborthite,
Cu 3(V 2O 7)(OH) 2(H 2O) 2 (Volborth and Hess 1838), fianelite, Mn2V(V,As)O7(H2O)2 (Brugger and Berlepsch
1996), martyite, Zn 3(V 2O 7)(OH) 2(H 2O) 2 (Kampf andSteele 2008), and engelhauptite, KCu 3(V 2O 7)(OH) 2Cl(Pekov et al. 2015), and three are anhydrous: chervetite,
Pb2V2O7 (Bariand et al. 1963), ziesite, β-Cu2V2O7 (Hughes
and Birnie 1980), and blossite, α-Cu2V2O7 (Robinson etal. 1987). All of them, except voborthite, are very rare.
Here we present the mineralogical description of a new
divanadate mineral karpenkoite (pronounced ‘kar pen

koʊ ait’; Cyrillic – карпенкоит), Co3(V2O7)(OH)2(H2O)2,
the cobalt analogue of martyite, named in honor of theprominent Russian mineralogist Vladimir Yur’evich
Karpenko (born 1965), who works as scientific researcher
at the Fersman Mineralogical Museum of the Russian
Academy of Sciences in Moscow. Vladimir Karpenko isespecially known for his contribution to the mineralogyof vanadium (Karpenko 1993; Karpenko et al. 2004,
2005, 2009, 2011).
The new mineral and its name have been approvedby the IMA Commission on New Minerals, Nomenclature and Classification (IMA2014-092). The holotype
specimen is deposited in the systematic collection of
the Fersman Mineralogical Museum of the Russian
Academy of Sciences, Moscow, under catalogue number
94997.
www.jgeosci.org

Anatoly V. Kasatkin, Jakub Plášil, Igor V. Pekov, Dmitry I. Belakovskiy, Fabrizio Nestola, Jiří Čejka, Marina F. Vigasina, Federico Zorzi, Brent Thorne

2. Occurrence
Specimens containing karpenkoite were collected underground by one of the authors (BT) at the Little Eva
mine, Yellow Cat District, Grand County, Utah, USA(38°50'17"N, 109°31'35"W) in September 1999. This
mine belongs to a group of deposits that were worked
intensively for uranium and vanadium from the 1940’s to
the 1970’s. The ore ranged in grade from a fraction of apercent to 10 % V2O5 and up to 0.4 % U3O8 (Stokes andMobley 1954). Mineralization was developed in the Salt
Wash member of the Jurassic Morrison Formation. The
Salt Wash member forms the lower part of the Morrison
Fm. and consists of about equal proportions of gray,lenticular, cross-bedded sandstone, and gray and red mudstone with a few limestone and chert beds. Stokes andMobley (1954) particularly underlined that the conglomeratic sandstone is vanadium-bearing in several places.
The sandstone forms either a stratum composed of asingle lenticular bed (from ~0.3 to ~6 m thick) or strata
composed of many lenticular beds which may have a total
thickness of more than ~24 m. Typically, the Salt Wash
member includes a basal sandstone unit, one or moreintermediate sandstone units, and a top sandstone unit.
Strata between the sandstone units consist of dominantly
greyish and reddish mudstones and claystones with minor
sand lenses. Sandstone accounts for c. 58 % by volume,
mudstone 41 % and limestone 1 %. The ore deposits in
the Salt Wash member are generally tabular bodies thatappear to be localized in the thicker parts of sandstonelenses. Within a mineralized layer, high-grade concentrations of uranium and vanadium minerals occur in bodies
or pods commonly associated with carbonaceous material(Newman 1962).
Mining operations at the Little Eva mine, which were
stopped in 1979, exposed primary and secondary vana-Fig. 1 Clusters and globular aggregates of orange karpenkoite crystals
overgrowing sandstone. Image 1 mm wide.

252

dium mineralization. Karpenkoite and closely associated martyite were formed as a result of the supergene
oxidation of the primary vanadium minerals corvusite
and montroseite in a moist environment at ambient temperatures.
Karpenkoite is a very rare mineral. It was foundon sandstone blocks in close association with its zincanalogue martyite, quartz, abundant gypsum, baryte,roscoelite, and an unidentified Al vanadate. Other supergene minerals identified at the site include andersonite,
ansermetite, calciodelrioite (Kampf et al. 2012), calcite,
carnotite, cobaltomenite, dickthomssenite, ferroselite,
huemulite, hughesite, lasalite, melanovanadite, metarossite, nashite (Kampf et al. 2013), native selenium, natrozippeite, nestolaite (Kasatkin et al. 2014), orschallite,
pascoite, rossite, schröckingerite, sherwoodite, tyuyamunite and also secondary uraninite.

3. General appearance, physical properties
and optical data
Karpenkoite forms orange lamellar crystals up to 0.05
mm across (usually much smaller), coarsely hexagonalor irregular in shape, typically curved. The crystals growin groups, rose-like clusters or globular aggregates up
to 0.2 mm across (Figs 1–2). These aggregates occur ininterstices and small cavities between quartz grains in themineralized sandstone (Fig. 3).
Karpenkoite is transparent, with a pale yellow-orange
streak and vitreous luster. It is non-fluorescent underultraviolet irradiation or when exposed to cathode rays.
The mineral is brittle, with laminated fracture and perfect cleavage on {001}. The Mohs hardness could not bemeasured because of tiny size of crystals and openwork
character of aggregates; it is probably about 3, by anal-Fig. 2 A typical rose-like cluster of lamellar karpenkoite crystals; SEM(SE) image.

Karpenkoite, a new divanadate mineral from Utah

tween the calculated value for H2O and the deficiency inthe total of the averaged electron microprobe analysis(Tab. 1) supports the correctness of this assumption.
The empirical formula of karpenkoite, calculated on
the basis of 11 O apfu, is (Co2.06Zn0.72Ni0.13Mn0.09Ca0.02
Cu0.02Mg0.01)Σ3.05V1.98O7(OH)2·2H2O. The idealized formula
Co3(V2O7)(OH)2·2H2O requires CoO 48.81, V2O5 39.45,
H2O 11.74, total 100 wt. %.

5. Raman spectroscopy

Fig. 3 Bunches and globular aggregates of divergent lamellar andacicular-looking crystals (white) of karpenkoite overgrowing the grainsof quartz (gray) in the mineralized sandstone. A SEM (BSE) image
0.33 mm wide.

ogy with martyite. Karpenkoite is insoluble in H2O but
easily soluble in cold diluted HCl or HNO3. Its density
was not measured due to the paucity of pure material.
The calculated density based on the empirical formulais 3.415 g cm–3.
The new mineral is optically uniaxial (+), with ω= 1.827(8) and ε = 1.843(8) (measured at 589 nm). In
transmitted light, karpenkoite is reddish-brown and nonpleochroic.
The Gladstone-Dale compatibility index 1 – (Kp/Kc) is
0.053 that is rated as good (calculated for the empiricalformula).

4. Chemical composition

Our Raman studies included the collection of the spectraof karpenkoite and, for comparison, its zinc analogue
martyite, Zn3(V2O7)(OH)2(H2O)2. The sample of the latter (from the collection of Anatoly Kasatkin; confirmed
by electron microprobe and powder X-ray diffraction)
originates from the mineral’s type locality, the Blue Cap
mine, San Juan Co., Utah.
The Raman spectra of both minerals were obtainedusing an EnSpectr R532 spectrometer (Department ofMineralogy, Moscow State University) utilizing a green
laser (532 nm) at room temperature. The output power ofthe laser beam was about 4 mW. Spectra were processedby the EnSpectr expert mode program in the range 100
to 4000 cm–1 with the use of a 1800 mm–1 holographic
diffraction grating and a spectral resolution of 5–8 cm –1.
The diameter of the focal spot on each sample was about
15 μm. The spectra were obtained for polycrystalline aggregates of both minerals.
The Raman spectra of karpenkoite and martyite arequite similar (Electronic Supplement). Tentative assignment of Raman bands of these minerals was done
following Schwendt and Joniaková (1975), Nakamoto(1986), Hardcastle and Wachs (1991), Obbade et al.
(2004) and Frost et al. (2011). The broad band with amaximum in the region 3450–3530 cm–1 corresponds to
O–H stretching vibrations. The relatively weak, broadband with maximum at 1660–1670 cm –1 is assigned to

The chemical composition of karpenkoite (Tab. 1) was
determined using a JEOL Superprobe 733 scanning electron microscope (SEM) equipped with an INCA energydispersive X-ray spectrometer.
An operating voltage of 20 kV Tab. 1 Chemical composition of karpenkoite (wt. %)was used with a beam current Constituent
Mean (n = 12)
Range
SD
Probe standard
0.05
0.00–0.47
0.154
Olivineof 5 nA and a 1 μm beam diam- MgO
0.26
0.00–0.70
0.24
Cr-augite USNM**
eter. Contents of other elements CaO
1.39
0.00–3.53
1.28
Mn
with atomic number higher than MnO
33.22
23.05–45.23
8.08
Co
eight were found to be below CoO
2.02
0.98–3.85
0.91
Ni
the detection limits. The con- NiO
CuO
0.28
0.00–0.82
0.26
Cu
tent of H2O was not determined
ZnO
12.66
1.58–21.59
7.52
Zn2SiO4
directly due to the scarcity of
V 2O 538.70
37.48–39.92
0.68
Vpure material. It was calculated
11.61*
H2O calc.
by stoichiometry for the formula
Total
100.19based on 11 O apfu, by analogy
SD – standard deviation
with the isostructural mineral * calculated by stoichiometry
martyite. A good agreement be- ** Smithsonian National Museum of Natural History (Washington, D.C., USA)253

Anatoly V. Kasatkin, Jakub Plášil, Igor V. Pekov, Dmitry I. Belakovskiy, Fabrizio Nestola, Jiří Čejka, Marina F. Vigasina, Federico Zorzi, Brent Thorne

bending vibrations of H 2O molecules. Note that thisband is, however, rather broad for typical bands attributed to H–O–H bending modes. The broadening could
be explained by overlap with an overtone related to themost intense band of V5+–O stretching vibrations in theregion 800–860 cm–1. A very strong band centered at
823 cm–1 in the Raman spectrum of karpenkoite and thatat 844 cm–1 in the spectrum of martyite are undoubtedly due to symmetric stretching vibrations of V5+O3
units. Bands in the region 300–500 cm –1 are assigned
to V5+O3 bending vibrations and bands with frequencies
lower than 300 cm–1 may be related to lattice modes.
The lack of distinct bands in the regions 1000–1500
and 1700–3000 cm–1 indicates the absence of H3O+ andgroups with C–O, C–H, N–O, N–H and B–O bonds inkarpenkoite and martyite.
Tab. 2 Powder X-ray diffraction data of karpenkoite
Karpenkoite
dobs
Iobs
100
18

7.15
5.19

25

4.20

21

3.59

54

2.95

21
36

2.77
2.60

33

2.44

17

2.30

11

2.17

17

2.10

6
2

1.886
1.800

11

1.761

10

1.721

dcalc

Icalc**

4.228

8

3.617

3

7.234
5.210
4.228

100
16
9

2.971

22

2.971

27

2.777
2.605

14
30

2.451

29

2.451
2.313
2.188

2
9
3

2.188

1

2.114

13

2.114

1

1.881
1.808
1.770

3
4
9

1.770

8

1.729

7

1.729

7

1.566

2

1.566

2

1.504

18

Martyite*
Icalc
100
4
17
4
6
49
14
30
32
8
4
13
5
3
4
17
14
1

1

1.555

13

1.503

11

1.473

1.486

7

1.486

14

3
14
7
15

6. Powder X-ray diffraction data
Single-crystal X-ray diffraction studies of karpenkoite
could not be carried out because of the imperfection ofits single crystals, which are very thin and typically divergent lamellae. For these reasons a Gandolfi-like scans
were used to obtain powder diffraction data (Tab. 2) froman aggregate of randomly oriented crystals mounted ona glass fiber and scanned using an Agilent Technologies Supernova single-crystal diffractometer with a Mo
micro-focus X-ray tube (50 kV, 0.8 mA), which provides
a 140 μm focused brilliant beam. The diffracted X-rays
were collected using a Dectris Pilatus 200K detector. Raw
diffraction data were processed using CrysAlis software(Agilent Technologies 2014). The data were further
processed by the LeBail whole-pattern decompositionin Jana2006 software (Petříček
et al. 2006, 2014), using the
known structure model forthe isostructural mineral marh
k
l
dcalc
tyite. Refined values of the unit
7.179
0
0
1
cell parameters were corrected
5.267
0
1
0
4.247
1
0
1
for correlations after Bérar andLelann (1991), and are (for the
4.247
0
1
1
trigonal space group P¯3m1)
3.590
0
0
2
a = 6.016(4), c = 7.234(6) Å,
3.041
1
1
0
2.966
0
1
2
with V = 226.7(2) Å3 and Z = 1.
2.966

1

0

2

2.800
2.634

1
2

1
0

1
0

2.634

2

0

1

2.472
2.320
2.179

0
1
1

2
1
0

1
2
3

2.179

0

1

3

2.123

2

0

2

2.123

0

2

2

1.918
1.881
1.795
1.771

1
1
0
2

2
1
0
0

1
3
4
3

1.771

0

2

3

1.741

1

2

2

1.741

2

1

2

1.705
1.577

0
3

3
0

1
2

1.577

0

3

2

1.520
1.488
1.483

2
2
2

2
2
0

0
1
4

1.483

0

2

4

d values quoted in Å
Range: 3–30° 2θ, MoKα radiation*Kampf and Steele (2008)**Calculated based on the model of martyite structure with Co instead of Zn

254

7. Discussion
Despite of absence of singlecrystal X-ray diffraction data,
there is no doubt that karpenkoite Co3(V2O7)(OH)2·2H2O isthe cobalt analogue of martyite
Zn3(V2O7)(OH)2·2H2O (Kampf
and Steele 2008) and its synthetic analogue (Zavalii et al.
1997). Comparative characteristics of karpenkoite andmartyite are given in Tab. 3.
We based our conclusions regarding the isotypism of theseminerals primarily on the factthat the stereochemistry of Zn2+
and Co2+ in oxysalts is similar(effective ionic radii are 0.74
Å and 0.75 Å for [6]Zn 2+ and[6]
Co 2+ , respectively – Shannon 1976). In particular, thestoichiometry of both minerals is identical and their crystal morphology and physicalKarpenkoite, a new divanadate mineral from Utahproperties (including Raman Tab. 3 Comparative data for karpenkoite and martyite
spectra and optical data) are
MineralKarpenkoite
Martyite*very close. The most convinc- End-member formula
Zn3(V2O7)(OH)2 · 2H2O
Co3(V2O7)(OH)2 · 2H2O
ing argument is a very good Average divalent metal content
agreement between measured (for the holotype samples of
Co2.06Zn0.72Ni0.13Mn0.09Ca0.02Cu0.02Mg0.01
Zn2.66Co0.15Ca0.05
intensities of the reflections each mineral)
Trigonal
Trigonal
in the powder X-ray diffrac- Crystal system
Space group
P3̄m1
P3̄m1
tion pattern of karpenkoite and6.016(4)6.0818(4)a, Åcalculated intensities of reflec- c, Å
7.234(6)7.1793(10)tions for martyite (Tab. 2). A V, Å3
226.7(2)229.97(4)11comparison with hexagonal Z
engelhauptite and monoclinic
7.15(100)
7.211(100)volborthite (C2/m), structur- Strongest lines of the X-ray
4.20(25)
2.968(50)ally related to martyite (Kampf powder-diffraction pattern:
2.95(54)2.628(35)2.60(36)2.470(40)and Steele 2008; Pekov et al. d, Å (I, %)2.44(33)
1.485(25)2015), indicates much poorer correspondence. Based on
3500
3475
these similarities, we infer that
1670
1660
823
844
karpenkoite adopts the same Wavenumbers of main bands in
474
483
structure as martyite.
–1
the Raman spectrum, cm
443
440
Although crystals of karpen312
319
koite on the holotype specimen
253
258
exhibit considerable inhomoOrange
Yellow-orange to red-orange
geneity in their Co:Zn ratio, Color
all showed dominance of Co
Uniaxial (+)
Uniaxial (+)
over Zn in all analyzed points. Optical data
ω = 1.827(8)ω = 1.797(3)The cobalt-richest and zincε = 1.843(8)ε = 1.806(3)poorest point has the composi3.37 (meas.)tion (Co2.80Zn0.09Ni0.07Ca0.05Mn0.02 Density, g cm-3
3.416 (calc.)
3.375 (calc.)
Cu 0.02 ) Σ3.05 V 1.98 O 7(OH) 2·2H 2O,
Kampf and Steele (2008);
whereas the Co-poorest and Zn- References
This work
Raman data – this work
richest point has the composi*The
unit-cellparametersofthesynthetic
analogueofmartyiteare:a=6.05098(5)Å, c = 7.19498 Å,tion (Co1.46Zn1.15Mn0.21Ni0.20)Σ3.02
V = 228.15 Å3; Zavalii et al. (1997)
V 1.99O 7(OH) 2·2H 2O. On othersamples from the Little Eva
Acknowledgements. Reviewers Anthony R. Kampf,
mine studied by us, karpenkoite and martyite occur toUwe Kolitsch and handling editor František Laufek aregether forming a nearly continuous solid-solution series
thanked for their constructive comments on the manu(Fig. 4).
script. The authors are grateful to Atali A. Agakhanov
Note that the crystal structures of two copper divana(Fersman Museum, Moscow) for his help in the obtaining
date minerals, monoclinic (C2/m) volborthite Cu3(V2O7)
of chemical data and to Mark Rushton (USA) for provid(OH) 2·2H 2O (Lafontaine et al. 1990; Kashaev et al.
ing us additional samples of karpenkoite for studies. This
2008) and hexagonal engelhauptite KCu3(V2O7)(OH)2Cl
research was financially supported by the post-doctoral(Pekov et al. 2015), are topologically identical (withgrant of the GAČR no. 13-31276P to JP and by the longregard to the topology of the structural units) to thatterm project DKRVO 2015-02 of the Ministry of Cultureof martyite and, presumably, karpenkoite, but volborof the Czech Republic (National Museum 00023272) tothite and engelhauptite differ from one another in someJ. Č. The Raman spectroscopic study was financed by
crystal-chemical features. Volborthite adopts monoclinic
the Russian Foundation for Basic Research, grant no.
symmetry due to the significant Jahn–Teller distortion
14-05-00276-a.
of one of the two symmetrically non-equivalent CuO6
octahedra. Engelhauptite contains the contact ion pairs
Electronic supplementary material. Supplementary
K + –Cl – in channels of the framework [Cu 2+ 3 (V 2 O 7 )chemical analyses of karpenkoite and martyite, as well(OH) 2] 0 instead of H 2O molecules as in volborthite,as their Raman spectra are available online at the Journalmartyite and karpenkoite.
web site (http://dx.doi.org/10.3190/jgeosci.199).

255

Anatoly V. Kasatkin, Jakub Plášil, Igor V. Pekov, Dmitry I. Belakovskiy, Fabrizio Nestola, Jiří Čejka, Marina F. Vigasina, Federico Zorzi, Brent Thorne

Fig. 4 Ratios of species-defining M2+
cations in members of the karpenkoite–
martyite solid-solution series from the
Little Eva mine, Grand Co., Utah, USA.

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