Eur. J. Mineral., 33, 175–187, 2021
https://doi.org/10.5194/ejm-33-175-2021© Author(s) 2021. This work is distributed under
the Creative Commons Attribution 4.0 License.

Grimmite, NiCo2S4, a new thiospinel from Příbram,
Czech Republic
Pavel Škácha1,2 , Jiří Sejkora1 , Jakub Plášil3 , Zdeněk Dolníček1 , and Jana Ulmanová1
1 Department of Mineralogy and Petrology, National Museum, Cirkusová 1740,

193 00 Prague 9 – Horní Počernice, Czech Republic
2 Mining Museum Příbram, Hynka Kličky place 293, 261 01 Příbram VI, Czech Republic
3 Institute of Physics ASCR, v.v.i., Na Slovance 1999/2, 182 21 Prague 8, Czech Republic

Correspondence: Pavel Škácha (skachap@seznam.cz)
Received: 25 December 2020 – Revised: 2 March 2021 – Accepted: 8 March 2021 – Published: 19 April 2021

Abstract. The new mineral grimmite, NiCo2 S4 , was found in siderite–sphalerite gangue at the dump of shaft
no. 9, one of the mines in the abandoned Příbram uranium and base-metal district, central Bohemia, Czech
Republic. The new mineral occurs as rare idiomorphic to hypidiomorphic grains up to 200 µm × 70 µm in size
or veinlet aggregates. In reflected light, grimmite is creamy grey with a pinkish tint. Pleochroism, polarisingcolours and internal reflections were not observed. Reflectance values of grimmite in the air (R %) are 42.5
at 470 nm, 45.9 at 546 nm, 47.7 at 589 nm and 50.2 at 650 nm). The empirical formula for grimmite, basedon electron-microprobe analyses (n = 13), is Ni1.01 (Co1.99 Fe0.06 Pb0.01 Bi0.01 )62.07 S3.92 . The ideal formula is
NiCo2 S4 ; requires Ni 19.26, Co 38.67, and S 42.07; and totals 100.00 wt %. According to the single-crystal X-ray
diffraction data (Robs = 0.0489), grimmite is cubic, Fd–3m, a = 9.3933(9), with V = 828.81(14) Å3 and Z = 8.
The calculated density is 4.96 g cm−3 . The strongest reflections of the calculated powder X-ray diffraction pattern[d, Å (I)(hkl)] are 3.3210 (75) (220), 2.7116 (7) (222), 2.3483 (81) (400), 1.9174 (27) (422), 1.6605 (100) (440),
1.4852 (11) (620) and 1.3558 (15) (444). Grimmite is named after Johann Grimm (24 June or 24 July 1805 to
26 June 1874), the former director of the Příbram Mining College. The association of sulfides and sulfarsenides
was found with grimmite. Essentially non-zoned coarse-grained siderite encloses idiomorphic crystals and/or
aggregates of red sphalerite I and zoned skutterudite-group minerals. Skutterudites (skutterudite, niklskutterudite
and ferroskutterudite) are usually strongly corroded and replaced by younger phases. Relics of skutterudite arerimmed by nickeline and later on by gersdorffite with rare domains of glaucodot and arsenopyrite, whereas
completely leached parts of skutterudite crystals are filled up by quartz containing small isolated grains andaggregates of pyrite, sphalerite II, grimmite, galena, ullmannite, bismuthinite, parkerite and jaipurite, the latterbeing rarely enclosed in grimmite.

1

Introduction

The nomenclature of thiospinels between ideal polydymite,
NiNi2 S4 , and linnaeite, CoCo2 S4 , has been ambiguous fora long time. Although original siegenite from its type occurrence in the Siegen District, Westphalia, Germany (Dana,
1850), corresponds to CoNi2 S4 and usually siegenite analyses lie on the Ni-rich side of the Ni : Co = 1 : 1 point, along
the Co–Ni join (Biagioni and Pasero, 2014), some authors
used the name “siegenite” (Petruk et al., 1969; Imai et al.,1973) or “linnaeite” (Lee et al., 2002) for all compositions
between polydymite and linnaeite. Others used the unapproved name “nickellinnaeite” for composition close to the
NiCo2 S4 (Minčeva-Stefanova and Kostov, 1976; Wagner and
Cook, 1999). In the approved nomenclature of the spinel supergroup (Bosi et al., 2019), siegenite is unambiguously defined as a member with the formula CoNi2 S4 . Complementarily, the phase with the formula NiCo2 S4 (present grimmite) is mentioned as a possible new mineral by Hazen etal. (2017).

Published by Copernicus Publications on behalf of the European mineralogical societies DMG, SEM, SIMP & SFMC.

176

P. Škácha et al.: Grimmite, a new thiospinel from Příbram

Synthetically prepared thiospinel NiCo2 S4 was studied
by Bouchard et al. (1965), who described its unit-cell parameter (a = 9.384(2) Å) and electrical properties, and by
Knop et al. (1968), who described its crystal structure(a = 9.3872(7) Å) and magnetic properties. More recently,
synthetic NiCo2 S4 was intensively investigated for various
applications as anodes for lithium-ion batteries, as electroactive materials for micro-SCs and as a bifunctional electrocatalyst for oxygen reduction or evolution reactions (Gao and
Huang, 2017; Xia et al., 2015; Shen et al., 2015, and manyothers).
The new mineral and its name were approved by theCommission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA
2020-060). Grimmite is named after Johann Grimm (24 Juneor 24 July 1805–26 June 1874) born in Jáchymov, in thepresent Czech Republic. He studied at the Štiavnice Mining and Forest Academy in 1825–1830. Later he worked ina mining company in Příbram and he moved to Hungary in
1830, where he later became the main land mining measurer. In 1840 Grimm came back to Příbram to the position of the leading mining and mill administrator. He modernised the mining operations, installed the first steam engines and arranged the long-term stability of the company. In
1850, Grimm became, after Franz Xaver Zippe, the second
director of the Příbram Mining College, where he worked
until the end of his life. He wrote many books about mining technologies, geology, mining education, and Czech andHungarian ore districts (Makariová, 2017). The cotype material (two polished sections) is deposited in the mineralogicalcollection of the Department of Mineralogy and Petrologyof the National Museum, Prague, Czech Republic (catalogue
number P1P 49/2020), and in the mineralogical collection of
the Mining Museum Příbram, Příbram, Czech Republic (catalogue number 3/2020).

deposits of this type. The hydrothermal U mineralisation of
Late Variscan age is related to a 1–2 km wide and almost
25 km long zone formed by a strongly tectonised series ofUpper Proterozoic rocks along with the contact with granitoids of the Early Carboniferous Central Bohemian Plutonic
Complex (Litochleb et al., 2003). The Příbram uranium andbase-metal district can be sub-divided into several ore deposits (also called ore nodes or clusters), among which themost important were Bytíz, Háje and Brod (Ettler et al.,2010). In addition to economic importance, this ore district isalso marked by incredible mineralogical diversity (about 200
species known so far), reflecting the occurrence of various
types of mineralisation, from the earliest gold-bearing veinsthrough the main uranium and base-metal veins with rich selenide mineralisation locally and also Ag, Ag–Sb, Sb or Asbonanzas to post-ore zeolite mineralisations. Grimmite wasfound there in an arsenide assemblage during a research programme focused on mineralogy and genesis of this ore district, especially selenide (Sejkora et al., 2017; Škácha et al.,2017a, b, 2018), and base-metal and Ag-bearing bonanzatype mineralisations (Sejkora et al., 2019, 2021; Škácha etal., 2019, 2020).
The Jerusalem deposit is located in the central part of thePříbram uranium and base-metal district. The main rocks in
the Jerusalem deposit are represented by shales, conglomerates, sandstones, siltstones and mudstones of the upper Proterozoic age in contact with Devonian–Carboniferous granodiorites (Janoušek et al., 2010). The only Jerusalem vein
system J1-J38 was mined in the Jerusalem deposit from thesurface till the depth of about 1400 m. The NW–SE- or N–Strending veins usually have steep to sheer dips. The most important uranium content was concentrated in 14 veins, whichcontain more than 100 t of uranium. The base-metal ores
were registered on about only 15 veins and silver-rich oreson the vein B117 (Komínek, 1995).
The new mineral was found in siderite gangue cementing brecciated greenish-black shale. Macroscopically, the ore
mineralisation is represented by abundant red sphalerite andaggregates of skutterudite-subgroup minerals up to 1 cm insize. These aggregates show very visible hydrothermal decomposition, which led to the formation of black porous centres.

2

Occurrence

One hand-sized specimen of grimmite has been found at
the mine dump of the shaft no. 9 – Jerusalem deposit nearPříbram. In the period 1951–1991, this mine was one of the
shafts open in the shallow parts (to the depth of about 600 m)of the deposit Jerusalem, which belongs to the uranium andbase-metal Příbram ore district, central Bohemia, Czech Republic (Komínek, 1995). The GPS coordinates of grimmite
occurrence are 49◦ 400 12.80600 N, 14◦ 10 48.10200 E.
The Příbram ore area (central Bohemia, Czech Republic)
is famous for its deposits of base metals as well as for uranium ores. It could be divided into two main ore districts: thebase-metal Březové Hory ore district and the complex uranium and base-metal Příbram district. The latter represents
the most considerable accumulation of vein-type hydrothermal U ores in the Czech Republic (with the production of
48.432 t of pure U metal) and is comparable to world-class
Eur. J. Mineral., 33, 175–187, 2021

3

Appearance and physical properties

Grimmite occurs as idiomorphic to hypidiomorphic grains
up to 200 µm × 70 µm (Fig. 1) or veinlet aggregates
500 µm × 30 µm in size. The mineral is grey with a pinkish
tint in colour with a metallic lustre. It is opaque in transmitted light. No cleavage was observed and the fracture is
uneven. The calculated density (Z = 8) for the empirical formula is 4.96 g cm−3 ; for the ideal formula, the density is
4.89 g cm−3 . Mohs hardness is assumed at 4 1/2–5 1/2 byanalogy with other members of the linnaeite subgroup. In
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P. Škácha et al.: Grimmite, a new thiospinel from Příbram

177

Table 1. Reflectance values (%) for grimmite.
Rλ (nm)Rλ (nm)

38.6
41.1
41.1
42.1
42.5
42.8
43.7
44.7
45.6
45.9

400
420
440
460
470
480
500
520
540
546

46.5
47.4
47.7
48.2
48.9
49.8
50.2
50.4
51.3
51.9

560
580
589
600
620
640
650
660
680
700
Figure 2. Reflectivity curve for grimmite from Příbram
(1) compared with published data for Fe-rich grimmite(2) from Outokumpu (Criddle and Stanley, 1993, p. 323,
Ni1.07 Co1.77 Fe0.21 S3.95 ; described as linnaeite nickelian);siegenite (3) from Heinrichssegen mine, Siegen (Criddle and Stanley, 1993, p. 509, Co1.18 Ni1.82 Fe0.01 S3.98 ); Fe-rich polydymite(4) from Dry Nickel mine (Criddle and Stanley, 1993, p. 448,
Ni2.88 Fe0.17 S3.94 ); and linnaeite (5 – Picot and Johan, 1982).

Figure 1. (a) Hypidiomorphic grains of grimmite (grey) closely associated with minerals of the skutterudite group (skutterudite andferroskutterudite) with a thin nickeline rim (all white). BSE photo:
the area of extracted fragment for single-crystal study is outlined inred; (b) reflected light photo, partly crossed polarisers.

reflected light, grimmite is creamy grey with a pinkish tint.
Pleochroism, anisotropy under crossed polars and internal reflections were not observed. Reflectance spectra were measured in air with a TIDAS MSP400 spectrophotometer attached to a Leica microscope (50× objective) using a WTiC
(Zeiss no. 370) standard, with a square sample measurement
field of ca. 8 µm. The results from the 400–700 nm range are
given in Table 1 and compared (Fig. 2) with published data
for selected members of the linnaeite subgroup (Criddle andStanley, 1993; Picot and Johan, 1982).

Raw intensities were converted to the concentrations of elements using the automatic “PAP” (Pouchou and Pichoir,1985) matrix-correction procedure.
Analytical data for grimmite crystal used for single-crystal
study (n = 13) are given in Table 2; these data lead to the empirical formula Ni1.01 (Co1.99 Fe0.06 Pb0.01 Bi0.01 )62.07 S3.92
on the basis of 7 apfu. The ideal formula is NiCo2 S4 ,which requires Ni 19.26, Co 38.67 and S 42.07 and a total 100.00 wt %. The representative analyses for all grimmite
grains (125 point analyses) in cotype samples are given in Table 3. It clearly reveals CoFe−1 substitution with Fe contents
up to 0.88 apfu (Fig. 3); no Ni–Fe correlation was observed.
The extent of Ni vs. Co+Fe substitution (Fig. 4) is significantly smaller than in the case of Co–Fe. Minor contents ofother elements do not exceed 0.10 apfu (As 0.10, Bi 0.04, Cu,
Pb, Mn 0.02 and Sb, Se 0.01 apfu).

5
4

Crystallography

Chemical composition

Chemical analyses were performed using a Cameca SX 100
electron microprobe (National Museum, Prague) operatingin wavelength-dispersive mode (25 kV, 20 nA and 1 µm widebeam). The following standards and X-ray lines were used tominimise line overlaps: Ag (Ag Lα), Au (Au Mα), Bi2 Se3(Bi Mβ), CdTe (Cd Lα), Co (Co Kα), CuFeS2 (Cu Kα, S
Kα), FeS2 (Fe Kα), HgTe (Hg Mα), Mn (Mn Kα), Ni (NiKα), NiAs (As Lα), PbS (Pb Mα), PbSe (Se Lα), PbTe (TeLα), Sb2 S3 (Sb Lα), TlBrI (Tl Lα) and ZnS (Zn Kα). Peak
counting time is 20 s for each element and 10 s for each background (detection limit was in the range 0.05–0.20 wt %).
https://doi.org/10.5194/ejm-33-175-2021

The powder X-ray diffraction data of grimmite could not becollected due to paucity of material. The calculated (PowderCell 2.3; Kraus and Noltze, 1996) powder diffraction datausing the atom coordinates from our crystal structure study
are given in Table 4.
A
short
prismatic
fragmentofgrimmite,
28 µm × 9 µm × 7 µm in size, extracted from the polished section (Fig. 1, Table 2) analysed using an electron
microprobe, was mounted on glass fibre and examined witha Rigaku SuperNova single-crystal diffractometer equippedwith an Atlas S2 charge-coupled device (CCD) detector
and a microfocus Mo Kα source. The ω rotational scans
Eur. J. Mineral., 33, 175–187, 2021

178

P. Škácha et al.: Grimmite, a new thiospinel from Příbram

Table 2. Chemical data (wt %) for grimmite grain used for single-crystal X-ray study (n = 13).
Constituent

Mean

Range

Stand. dev. (σ )

Apfu

Fe
Mn
Pb
Ni
Co
Cu
Bi
As
S

1.16
0.03
0.46
19.27
38.23
0.08
0.62
0.09
41.05

0.95–1.53
0–0.140.24–0.92
18.62–20.59
36.39–39.36
0–0.210–1.300–0.5640.28–41.87

0.17
0.05
0.21
0.47
0.78
0.07
0.38
0.19
0.45

0.064
0.002
0.007
1.005
1.987
0.004
0.009
0.004
3.921

Total

100.99Apfu calculated on the basis of seven atoms.

Table 3. Representative analyses (wt %) for grimmite from Příbram.
1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

Fe
Pb
Ni
Co
Mn
Cu
Sb
Bi
As
Se
S

0.90
0.30
18.30
38.99
–
0.05
–
–
–
–
42.19

1.02
0.16
18.28
38.44
–
–
–
0.46
–
–
42.15

1.34
0.16
17.89
39.34
–
–
–
–
–
–
41.70

1.46
0.17
18.61
38.23
–
–
–
–
–
–
41.44

1.55
0.65
19.10
36.52
0.05
0.11
–
0.78
–
0.11
41.30

1.58
1.01
18.14
35.75
–
0.36
–
2.60
–
–
41.30

1.63
0.08
19.01
37.28
–
–
–
–
–
–
42.07

1.68
0.44
18.09
36.99
–
0.14
–
1.65
–
–
41.36

1.84
0.71
17.31
37.58
–
0.26
–
2.27
–
–
40.31

2.01
0.71
18.23
37.78
–
0.11
–
1.15
–
0.15
40.48

3.12
0.25
18.90
36.38
–
–
–
–
–
–
41.72

5.16
0.14
21.28
29.35
0.40
–
0.11
–
2.30
–
40.51

7.18
0.18
21.71
28.06
0.15
0.07
0.11
–
0.87
–
41.55

14.36
0.30
22.30
20.07
0.06
–
0.15
–
0.47
–
42.05

15.57
0.29
22.42
18.73
0.06
0.05
0.14
–
–
–
42.34

Total

100.73100.51100.4399.91

100.17100.74100.07100.35100.28100.62100.37

99.25

99.88

99.76

99.60

Fe
Pb
Ni
Co
Mn
Cu
Sb
Bi
As
Se
S

0.049
0.004
0.946
2.007
–
0.002
–
–
–
–
3.992

0.056
0.002
0.948
1.986
–
–
–
0.007
–
–
4.002

0.073
0.002
0.928
2.034
–
–
–
–
–
–
3.962

0.080
0.003
0.971
1.987
–
–
–
–
–
–
3.959

0.086
0.010
1.002
1.909
0.003
0.005
–
0.012
–
0.004
3.969

0.088
0.015
0.959
1.883
–
0.018
–
0.039
–
–
3.999

0.089
0.001
0.986
1.927
–
–
–
–
–
–
3.997

0.093
0.007
0.951
1.937
–
0.007
–
0.024
–
–
3.981

0.103
0.011
0.921
1.992
–
0.013
–
0.034
–
–
3.927

0.111
0.011
0.961
1.983
–
0.005
–
0.017
–
0.006
3.906

0.170
0.004
0.981
1.881
–
–
–
–
–
–
3.964

0.287
0.002
1.125
1.545
0.023
–
0.003
–
0.095
–
3.920

0.393
0.003
1.132
1.457
0.008
0.003
0.003
–
0.036
–
3.965

0.783
0.004
1.157
1.037
0.003
–
0.004
–
0.019
–
3.993

0.847
0.004
1.161
0.966
0.003
0.002
0.003
–
–
–
4.013

Coefficients of empirical formula were calculated on the basis 7 apfu.

(frame width of 1.0◦ , counting time 1500 s) were adopted
for the acquisition of the three-dimensional intensity data.
From the total of 1081 reflections, 1078 were taken as
independent (without averaging) and 735 considered uniqueobserved with I > 3σ (I ). Data reduction was performed
using CrysAlisPro Version 1.171.39.46 (Rigaku, 2019). The
data were corrected for Lorentz factor, polarisation effectand absorption (multi-scan, ABSPACK scaling algorithm;
Rigaku, 2019).
According to the single-crystal X-ray data, grimmite is
cubic, Fd-3m, a = 9.3933(9), with V = 828.81(14) Å3 andZ = 8. The crystal structure of grimmite has been refined by

Eur. J. Mineral., 33, 175–187, 2021

the software Jana2006 (Petříček et al., 2014) using the structure model for siegenite (Huang and Knop, 1971). The crystal data and the experimental details are given in Table 5, andatom coordinates, atomic displacement parameters and site
occupancies are given in Table 6. The interatomic distance(Å) in grimmite for M-S1 (6×) is 2.2635(10) and for T-S1
(4×) is 2.1866(10). Anisotropic displacement parameters arereported in the crystallographic information file that has been
deposited in the Supplement.
The unit cell of grimmite is similar to that reported forsiegenite by Huang and Knop (1971). The structure of grimmite differs from that of siegenite in the manner that Co oc-

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P. Škácha et al.: Grimmite, a new thiospinel from Příbram

179
Table 4. Calculated X-ray powder diffraction data for grimmite.

Figure 3. The Co vs. Fe (apfu) graph for all studied grimmite grainsfrom Příbram; SCXRD – grain used for single-crystal study.

Icalc

dcalc

h

k

l

5.4
74.7
5.4
7.2
80.7
5.8
26.7
3.7
100.0
0.9
10.6
0.7
2.7
15.1

5.4232
3.32102.83222.71162.3483
2.15501.9174
1.80771.6605
1.58781.4852
1.43251.41611.3558

1
2
3
2
4
3
4
5
4
5
6
5
6
4

1
2
1
2
0
3
2
1
4
3
2
3
2
4

1
0
1
2
0
1
2
1
0
1
0
3
2
4

Intensity and dhkl were calculated using
the software PowderCell2.3 (Kraus andNolze, 1996) on the basis of the structural
data given in Tables 5 and 6. Only
reflections with Irel. ≥ 0.7 are listed. The
seven strongest reflections are given in
bold.

Figure 4. The Ni vs. Co+Fe (apfu) graph for all studied grimmite
grains from Příbram; SCXRD – grain used for single-crystal study.

cupies Wyckoff site 16c instead of Ni. This is in accordancewith the EPMA data. The 8b site in grimmite is occupied by
Ni then. We are convinced that Co does not enter the 8b site
since the refined value obtained for the refinement with Niplaced solely at 8b returned a value near unity. The refinement involving the restricted (unvaried) occupancy of Co at
the tetrahedral site, reflected by the formula Co(NiCo)62 S4 ,also led to similar R values (Robs ∼ 5.5 %), but to a significantly worse goodness of fit (∼ 2.46 %), in comparison to
the final mode we accepted, GOF = 1.46.
6

Crystal chemistry and relationship with known (Co,Ni) thiospinels

Grimmite is the Co-dominant (16c site) and Ni-dominant(8b site) member of the spinel supergroup, thiospinel group,
linnaeite subgroup, Strunz class 2/D.01 and Dana class
2.10.1. A comparison of selected data for members of
this subgroup is given in Table 7. Grimmite NiCo2 S4 isclosely chemically related to linnaeite CoCo2 S4 , siegenite
https://doi.org/10.5194/ejm-33-175-2021

CoNi2 S4 and polydymite NiNi2 S4 (which is erroneously
stated on page 186 of paper spinel supergroup classification – Bossi et al., 2019 – as NiCo2 S4 ). The classification of spinel supergroup minerals is based on the chemical
data only (Bossi et al., 2019); therefore Ni–Co thiospinels(series Co3−x Nix S4 ) would be divided into the following four chemical ranges: 0.00 ≤ x ≤ 0.50, linnaeite, ideally CoCo2 S4 ; 0.50 ≤ x ≤ 1.50, grimmite, ideally NiCo2 S4 ;1.50 ≤ x ≤ 2.50, siegenite, ideally CoNi2 S4 ; and 2.50 ≤x ≤ 3.00, polydymite, ideally NiNi2 S4 .
Mineral phases with chemical composition corresponding
to grimmite (Fig. 5) were previously described in various deposits, e.g., from Langis mine, Canada (Petruk et al., 1969);
Nippo ore deposit, Japan (Imai et al., 1973); Muzho and
Bakura deposits, Bulgaria (Minčeva-Stefanova, 1975); Outokumpu, Finland (Criddle and Stanley, 1993); Elatsite deposit, Bulgaria (Dragov and Petrunov, 1998); or Rainbow hydrothermal field, Mid-Atlantic Ridge (Lee et al., 2002).
7

Associated minerals

In addition to macroscopically observed skutterudite andsphalerite, a detailed mineralogical study of grimmitebearing mineralisation also permitted the identification oflower amounts of nickeline, gersdorffite and probably glaucodot, whereas pyrite, arsenopyrite, galena, jaipurite, bismuthinite, ullmannite and parkerite are accessories. The
gangue is formed in particular by siderite, whereas calcite
and quartz are subordinate, and a silicate with composition
close to chlorite is accessory. Essentially non-zoned coarsegrained siderite encloses idiomorphic crystals and/or aggreEur. J. Mineral., 33, 175–187, 2021

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P. Škácha et al.: Grimmite, a new thiospinel from Příbram

Table 5. Summary of data collection conditions and refinement parameters for grimmite.
Chemical formula sum
Crystal system
Space group
Unit-cell parameters: a [Å]Unit-cell volume [Å3 ]Z
Calculated density [g cm−3 ]Crystal size [mm]Diffractometer
Temperature [K]Radiation, wavelength [Å]θ range for data collection [◦ ]Limiting Miller indicesAxis, frame width (◦ ), 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
Structure refinement
No. of param., restraints, constraints
R, wR (obs)
R, wR (all)
GOF obs/all
Weighting scheme, weights
Largest diffraction peak and hole (e− /Å3 )Ni0.991 Co1.931 S4
cubic
Fd–3m
9.3933(9)828.81(14)84.843 (for the formula from refinement)
0.028 × 0.009 × 0.007
Rigaku SuperNova with Atlas S2 CCD
286
Mo Kα , 0.71073 (50 kV, 30 mA)
3.76–27.30
h = −10 → 10, k = −11 → 11, l = −11 → 11
ω, 1.0, 1500
1081
1078
735, [I > 3σ (I )]14.03; multi-scan
0.784/1
97.00, 0.066
Full-matrix least squares on F 2
9, 0, 00.0539, 0.1746
0.0749, 0.1881
1.46/1.30
σ, w = 1/(σ 2 (I ) + 0.0081000002I 2 )1.43, −0.94

Table 6. Atom positions and equivalent displacement parameters (Å2 ) for grimmite.
Atom

Occupancy

x/a

y/b

z/c

Ueq

Co1
Ni2
S2

0.984(10)0.88(10)0.5
0.625
0.49058(12)

0.75
0.625
0.75942(12)

0.25
0.625
0.49058(12)0.0082(3)0.0110(3)0.0108(5)gates of red sphalerite I and zoned skutterudite-group minerals. Skutterudites are usually strongly corroded and replaced by younger phases (Fig. 6a). Relics of skutterudite arerimmed by nickeline (Fig. 6b) and later on by gersdorffite
with rare domains of glaucodot and arsenopyrite (Fig. 6c),whereas completely leached parts of skutterudite crystals arefilled up by quartz containing small isolated grains and aggregates of pyrite, sphalerite II, grimmite, galena, ullmannite, bismuthinite, parkerite and jaipurite, the latter being
rarely enclosed in grimmite (Fig. 6d). The youngest hypogene phase is veinlets and small nests (especially replacing
siderite or quartz) of chemically homogeneous calcite. In one
case skutterudite enclosed a short monomineral veinlet composed of a chemically heterogeneous porous Ni–Fe–Mg–Al
silicate with a composition close to chlorite. The supergene
alterations of the studied sample (weathering in dump material) are manifested by further corrosion of skutterudite, par-Eur. J. Mineral., 33, 175–187, 2021

tial leaching of carbonates and crystallisation of secondary
Zn–Mn–Ni–Co–Fe arsenates.
Sphalerite I has low Fe (up to 0.002 apfu) and significant Cd (up to 0.04 apfu), whereas sphalerite II incorporates Ni and Co up to 0.01 apfu and Cd only up to
0.005 apfu. Arsenopyrite contains minor Co (0.004 apfu) andSb (0.007 apfu); bismuthinite 0.10 apfu Ni and 0.02 apfu Sb;
and pyrite minor contents of Ni, Sb and As up to 0.003–
0.004 apfu.
Chemical composition of skutterudite-group mineral
ranges from skutterudite through nickelskutterudite to ferroskutterudite. Ferroskutterudite, very rare in the world, isthe most abundant arsenide in the studied mineral association. At the cation site, it also contains, in addition to prevailing Fe (0.37–0.50 apfu), significant contents of Ni andCo, up to 0.48 and 0.36 apfu, respectively (Table 8). HighFe contents (Fig. 7) were also found in nickelskutterudite

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P. Škácha et al.: Grimmite, a new thiospinel from Příbram

181

Table 7. Members of the thiospinel group and linnaeite subgroup. Minerals are listed according to the increasing atomic number of the main
cation.
Chem. formula
Joegoldsteinite
Daubréelite
Kalininite
Greigite
Linnaeite
Grimmite
Violarite
Siegenite
Polydymite
InditeCadmoindite
Cuprorhodsite
Xingzhongite (Q)MnCr2 S4
FeCr2 S4
ZnCr2 S4
FeFe2 S4
CoCo2 S4
NiCo2 S4FeNi2 S4
CoNi2 S4
NiNi2 S4
FeIn2 S4
CdIn2 S4
(Cu0.5 Fe0.5 )Rh2 S4
PbIr2 S4

Ref.

Space g.

a [Å]

(11)
(8)
(12)
(9)
(4)
(1)
(2)
(2, 3)(2)(10)(5)(6, 7)(7, 13)

Fd3m
Fd–3m
Fd3m
Fd3m
Fd–3m
Fd–3m
Fd–3m
Fd–3m
Fd–3m
Fd3m
Fd3m
Fd3m
?

10.11
9.966
9.997(1)9.876(2)9.44
9.3933(9)9.458
9.408–9.442
9.471
10.62(1)10.81(2)9.88(1)
9.970(1) This paper. (2) Riley (1980). (3) Huang and Knop (1971). (4) Buerger and Robinson (1955).
(5) Chaplygin et al. (2004). (6) Rudashevsky et al. (1985). (7) Bossi et al. (2019). (8) Lundqvist (1943).
(9) Skinner et al. (1964). (10) Genkin and Murav’eva (1963). (11) Isa et al. (2016). (12) Reznickij etal. (1985). (13) Yu et al. (1974); Q – questionable mineral (Bossi et al., 2019).

Figure 5. Determined range of Ni contents in grimmite. (1) Příbram
(this paper). (2) Příbram – grain used for SCXRD study (this paper). (3) Rainbow hydrothermal field, Mid-Atlantic Ridge (Lee etal., 2002). (4) Elatsite deposit, Bulgaria (Dragov and Petrunov,1998). (5) Outokumpu mining district, Finland (Criddle and Stanley, 1993). (6) Muzho and Bakura deposits, Bulgaria (MinčevaStefanova, 1975). (7) Nippo ore deposit, Japan (Imai et al., 1973).
(8) Langis mine, Canada (Petruk et al., 1969).

(up to 0.47 apfu, Ni 0.48–0.69 and Co up to 0.20 apfu) andin skutterudite (up to 0.44 apfu, Co 0.46–0.59 and Ni up to
0.27 apfu). Similar large Ni–Co–Fe substitution in skutterudite subgroup minerals is described, e.g. from Norilsk ore
field (Spiridonov and Gritsenko, 2007) or Dobšiná, Slovakia(Kiefer et al., 2017), and corresponds to the solid-solution
field of skutterudite experimentally determined by Roseboom (1962). At the anion site, all members of this subgroupcontain S in the range 0.13–0.35 apfu; such increased conhttps://doi.org/10.5194/ejm-33-175-2021

tents are unusual (Anthony et al., 1990; Spiridonov and Gritsenko, 2007; Spiridonov et al., 2007; Ahmed et al., 2009);
similar contents (up to 0.33 apfu S) are described only forsamples from Jáchymov (Ondruš et al., 2003).
The mineral chemistry of weakly anisotropic (to isotropic)
sulfarsenides (Ni,Fe,Co)AsS changes rapidly at the micrometre scale. There appear two groups of analyses (Table 9). The composition of the first (Ni-dominant) groupvaries from gersdorffite with minor Fe and Co contents toward the centre of the Ni–Co–Fe triangle (Fig. 8), and Ni
contents correlate positively with As (Fig. 9), as also foundby Kiefer et al. (2017) for samples from Dobšiná. The second
group is Fe- and Co-dominant members with a Fe : Co ratioaround 1 : 1 (Fig. 8); their compositions are close to that ofglaucodot with the ideal formula Co0.5 Fe0.5 AsS.
Nickeline is almost stoichiometric (Table 10) but with very
unusual increased Fe contents (0.11–0.16 apfu) and minor
Co up to 0.08 apfu. At the anion site, As is partly substituted by S (0.04–0.08 apfu) and Sb (up to 0.02 apfu). Its
empirical formula (mean of 21 analyses) on the basis of
2 apfu is (Ni0.81 Fe0.14 Co0.05 )61.00 (As0.93 S0.06 Sb0.01 )61.00 .
Very rare jaipurite (with only a few known occurrencesin the world) is close to stoichiometric (Co,Ni,Fe)S (Table 10). In addition to dominant Co, minor contents ofNi and Fe up to 0.18 and 0.08 apfu, respectively, were
found. Similar Ni and Fe contents in jaipurite were described by Gertsen et al. (1988). The empirical formula ofjaipurite (mean of 13 analyses) on the basis of 2 apfu is(Co0.83 Ni0.14 Fe0.06 )61.03 S0.97 . The ideal chemical formulafor parkerite is reported as Ni3 (Bi,Pb)2 S2 (Anthony et al.,1990), due to the existence of limited substitution BiPb−1
in the parkerite–shandite series (Fleet, 1973). Parkerite fromstudied mineral association corresponds to this stoichiome-

Eur. J. Mineral., 33, 175–187, 2021

182

P. Škácha et al.: Grimmite, a new thiospinel from Příbram

Figure 6. Mineral assemblage and textural features of the studied grimmite-bearing sample on BSE images. (a) Zoned skutterudite (Sku) withcertain zones selectively replaced by quartz (Qtz) with disseminated grimmite (Gr). Ca – calcite. (b) Corroded skutterudite (Sku) rimmed
by nickeline (Ni). (c) Zoned gersdorffite (Ger) with darker domains formed by arsenopyrite (Asp) and glaucodote (Glc) and a bright Asenriched S-poor growth zone. Ga – galena. (d) Skutterudite (Sku) cut by a grimmite (Gr) veinlet containing abundant xenomorphic inclusionsof jaipurite (J).

Table 8. Representative analyses (wt %) for members of the skutterudite subgroup from Příbram.
1

2

3

4

5

6

7

8

Fe
Ni
Co
Sb
Bi
As
S

7.87
6.30
7.82
2.01
0.14
73.66
3.67

9.32
7.10
4.67
1.23
0.00
74.93
2.55

9.47
9.84
1.65
1.96
0.00
75.24
2.01

10.10
8.44
2.28
1.59
0.00
75.65
1.82

9.14
10.36
2.05
1.00
0.00
77.42
1.60

9.61
10.27
2.30
0.85
0.00
76.17
1.74

6.85
2.01
12.92
1.43
0.17
72.58
4.14

5.82
4.54
10.94
1.74
0.00
73.22
3.59

Total

101.4799.90

100.1799.88

101.57100.94100.28

99.85

Fe
Ni
Co
6
Sb
Bi
As
S
6

0.377
0.287
0.355
1.019
0.044
0.002
2.629
0.306
2.981

0.458
0.332
0.218
1.008
0.028
–
2.745
0.218
2.991

0.468
0.463
0.077
1.009
0.044
–
2.774
0.173
2.991

0.501
0.399
0.107
1.007
0.036
–
2.799
0.157
2.993

0.446
0.481
0.095
1.023
0.022
–
2.819
0.136
2.977

0.470
0.478
0.107
1.055
0.019
–
2.778
0.148
2.945

0.330
0.092
0.590
1.011
0.032
0.002
2.605
0.347
2.986

0.283
0.210
0.505
0.999
0.039
–
2.658
0.305
3.001

Ferroskutterudite 1–4; nickelskutterudite 5–6; skutterudite 7–8. Coefficients of empirical formula were calculated on
the basis of 4 apfu.

Eur. J. Mineral., 33, 175–187, 2021

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P. Škácha et al.: Grimmite, a new thiospinel from Příbram

183

Table 9. Representative analyses (wt %) for Ni–Fe–Co sulfarsenides from Příbram.
1

2

3

4

5

6

7

8

9

10

11

12

Fe
Pb
Ni
Co
Sb
Bi
As
S

8.45
0.00
13.72
13.38
0.26
0.00
48.47
17.27

9.63
0.00
14.04
11.80
0.26
0.00
48.68
17.10

12.79
0.10
15.21
7.24
0.47
0.00
49.26
17.16

7.99
0.00
17.22
9.72
0.32
0.00
50.88
15.57

4.50
0.00
26.13
2.85
1.49
0.00
55.40
11.47

3.70
0.00
26.25
2.86
1.02
0.00
58.04
10.00

18.24
0.00
0.12
15.13
0.27
0.00
49.73
16.40

22.74
0.00
0.23
10.72
1.01
0.00
49.52
16.17

15.07
0.00
3.02
15.54
0.42
0.00
49.78
15.87

17.08
0.25
3.04
11.88
1.13
0.15
58.14
9.17

14.97
0.00
3.50
15.98
0.49
0.00
51.16
15.63

10.78
0.00
11.36
13.68
0.26
0.00
47.03
18.48

Total

101.55101.51102.23101.70101.84101.8799.89

100.3999.70

100.84101.73101.59

Fe
Pb
Ni
Co
6
Sb
Bi
As
S
6

0.252
–
0.390
0.378
1.020
0.004
–
1.078
0.898
1.980

0.288
–
0.399
0.334
1.021
0.004
–
1.085
0.890
1.979

0.380
0.001
0.430
0.204
1.015
0.006
–
1.091
0.888
1.985

0.243
–
0.497
0.280
1.020
0.004
–
1.151
0.823
1.979

0.144
–
0.793
0.086
1.023
0.022
–
1.318
0.637
1.977

0.120
–
0.810
0.088
1.017
0.015
–
1.403
0.565
1.983

0.555
–
0.003
0.437
0.995
0.004
–
1.129
0.870
2.002

0.691
–
0.007
0.309
1.006
0.014
–
1.122
0.856
1.992

0.463
–
0.088
0.453
1.004
0.006
–
1.140
0.850
1.996

0.562
0.002
0.095
0.370
1.030
0.017
0.001
1.426
0.526
1.970

0.454
–
0.101
0.459
1.013
0.007
–
1.155
0.825
1.987

0.317
–
0.318
0.382
1.017
0.004
–
1.032
0.947
1.983

Gersdorffite 1–6; Fe- and Co-dominant members (glaucodot?) 7–12. Coefficients of the empirical formula were calculated on the basis of 3 apfu.

Figure 7. Chemical composition (at. units) for members of theskutterudite subgroup from the grimmite-bearing association fromPříbram.

try (Table 10), but it does not contain any Pb; similar Pbfree parkerite was described by Petruk et al. (1969), Grovesand Hall (1978), and Sejkora et al. (2009, 2020). Its empirical formula (mean of two analyses) on the basis of 7 apfu is(Ni2.90 Co0.03 Fe0.02 )62.95 (Bi1.99 Sb0.01 )62.00 S2.05 . Extraordinary Bi-rich ullmannite (Table 10) has an empirical formula
https://doi.org/10.5194/ejm-33-175-2021

Figure 8. Ternary plot Fe–Ni–Co (at. unit) for sulfarsenides fromgrimmite-bearing association from Příbram.

of (Ni0.95 Co0.01 )60.96 (Sb0.68 Bi0.33 )61.01 S1.02 on the basis of
3 apfu.
Siderite shows rather uniform chemical composition(Sid63−74 Rdc13−20 Mag10−20 Cal1−3 ). Calcite is Mn-rich(Cal85−91 Rdc6−11 Sid1−3 Mag1−3 ), in part with slightly
elevated content of Ni (up to 0.7 mol. % NiCO3 ). Chemical composition of Ni–Fe–Mg–Al silicate with elevated conEur. J. Mineral., 33, 175–187, 2021

184

P. Škácha et al.: Grimmite, a new thiospinel from Příbram

Table 10. Representative analyses (wt %) for nickeline, jaipurite, parkerite and ullmannite from Příbram.
Nickeline

Jaipurite

Parkerite

Ullmannite

Fe
Pb
Ni
Co
Sb
Bi
As
S

6.48
0.00
34.60
1.87
1.28
0.00
54.37
1.32

6.27
0.00
35.87
1.96
0.56
0.00
53.98
1.06

5.65
0.00
37.12
1.49
0.77
0.11
54.45
1.23

4.62
0.10
37.22
2.66
1.08
0.00
52.84
1.51

2.87
0.17
11.73
48.40
0.00
0.00
0.20
37.24

5.12
0.23
9.57
51.95
0.00
0.28
0.00
33.33

3.28
0.18
8.56
54.33
0.00
0.00
0.00
34.58

3.06
0.16
7.38
57.29
0.00
0.00
0.00
33.19

0.14
0.00
25.59
0.25
0.18
62.64
0.00
9.91

0.00
0.00
22.52
0.20
33.41
27.39
0.36
13.11

Total

99.92

99.70

100.82100.03100.61100.48100.93101.08

98.71

96.99

Fe
Pb
Ni
Co
Sb
Bi
As
S
Base

0.153
–
0.778
0.042
0.014
–
0.958
0.054
2

0.148
–
0.807
0.044
0.006
–
0.951
0.044
2

0.132
–
0.826
0.033
0.008
0.001
0.950
0.050
2

0.109
0.001
0.832
0.059
0.012
–
0.926
0.062
2

0.046
0.001
0.179
0.734
–
–
0.002
1.038
2

0.084
0.001
0.150
0.809
–
0.001
–
0.954
2

0.053
0.001
0.132
0.836
–
–
–
0.978
2

0.050
0.001
0.115
0.888
–
–
–
0.946
2

0.017
–
2.898
0.028
0.010
1.993
–
2.055
7

–
–
0.954
0.008
0.683
0.326
0.012
1.017
3

Coefficients of empirical formula were calculated on the given base.

Figure 9. The Ni/(Ni+Co+Fe) vs. As (apfu) graph for sulfarsenides from the grimmite-bearing association from Příbram.

tents of Sb and Zn (up to 0.4 wt % and 1.6 wt % of Sb2 O3
and ZnO, respectively) roughly corresponds to Ni-rich Fechlorite (chamosite), but its chemical composition was probably partly disturbed (Si excess, low analytical totals) by acidsolutions due to weathering.

8

Remarks to the origin of grimmite-bearing
mineralisation

The economically most important uranium and base-metalmineralisation of the Příbram uranium ore district originatedduring four main mineralisation stages: (I) siderite–sulfidic;
Eur. J. Mineral., 33, 175–187, 2021

(II) calcite; (III) calcite–uraninite and (IV) calcite–sulfidic(Komínek, 1995). The oldest siderite–sulfidic stage (I) is developed in particular in the southern part of this ore districtbut on a smaller scale in comparison with the neighbouringBřezové Hory district. The younger calcite stages, characterised by notably lower temperatures, are more abundant;
calcite generations were used in distinguishing individual
mineralisation stages. For the calcite stage (II) pre-ore calcite
DK and calcite K1 are characteristic. In the calcite – uraninite
stage (III), carrying the main part of the economic uranium
mineralisation (uraninite, coffinite and U–bearing anthraxolite), are present calcite types K2–K4. The age of the uranium
mineralisation obtained by U–Pb radiometric age determination of two uraninite samples is middle Permian, 275 ± 4 and278 ± 4 Ma (Anderson, 1987). In the last calcite – sulfidic
stage (IV), post-ore calcite K5 appears and Ag, Ag–Sb, Sb
and As–Sb bonanza-type accumulations occur.
The paragenetic position, texture and/or chemical composition clearly suggest that siderite and skutterudite present
in mineralisation under this study undoubtedly belong to theoldest siderite–sulfide mineralisation stage. Further evolution, however, deviates from the published overall paragenetic scheme (see Žák and Dobeš, 1991; Komínek, 1995).
Skutterudite was initially partly dissolved and/or replaced bynickeline, then by gersdorffite and, finally, by quartz-hosted
sulfide paragenesis including grimmite and Bi-rich minerals.
This evidence implies a late paragenetic position of grimmite and its relation to younger hydrothermal processes possibly related to the same (i.e., siderite–sulfide) or some of
the younger mineralisation stages. Unfortunately, a more de-https://doi.org/10.5194/ejm-33-175-2021

P. Škácha et al.: Grimmite, a new thiospinel from Příbram
tailed specification of paragenetic position of the grimmitebearing mineralising event is not possible because of thespecific mineral association of the studied sample and difficulties correlating calcite from the dump sample with theabove-mentioned calcite generations, which were defined bymeans of field observations, textural features and bulk (wetchemical) composition (Cílek et al., 1984; Komínek, 1995).
The presence of grimmite in association with base-metalsulfides replacing older triarsenides indicates remobilisation
processes caused by hydrothermal fluids rich in reduced sulfur. Partial dissolution of earlier Ni–Co arsenides associatedwith remobilisation of Ni and Co was the likely source of Ni
and Co for the formation of grimmite and other Co–Ni enriched sulfides. Phenomena of ore dissolution, remobilisation
and replacement were widely detected in the ore veins of thePříbram uranium and base-metal ore district (Sejkora et al.,2019; Škácha et al., 2019; Sejkora et al., 2021). The elevatedcontent of Bi in the studied mineralisation, indicated by thepresence of the trace amount of bismuthinite, parkerite andBi-enriched ullmannite, can also be explained by remobilisation of Bi from earlier gold-bearing quartz veins containing
an accessory amount of Bi tellurides (Litochleb et al., 2005,
2006; Sejkora et al., 2019).
The studied mineralisation is characterised by a high activity of iron during the formation of arsenide mineralisation. This took place during crystallisation of triarsenides,
giving rise to dominating ferroskutterudite, an otherwise extremely rare mineral worldwide. Similarly, superimposed
nickeline incorporated iron in the highest reported concentrations worldwide, to our knowledge. However, explanationof reasons for such unusual iron enrichment cannot be basedon pure mineralogical study and need further investigation.

185
Supplement. The supplement related to this article is available online at: https://doi.org/10.5194/ejm-33-175-2021-supplement.

Author contributions. PŠ found the mineral, evaluated part of the
EPMA analyses and provided valuable information. JS, JP, ZD and
JU analysed the material (structure determinations were done by JP,
EPMA by ZD and JU; optical properties by JS). JS and ZD interpreted the results and wrote the paper, with help from PŠ and JP.

Competing interests. The authors declare that they have no conflictof interest.

Acknowledgements. The helpful comments of the anonymous
members of the Commission on New Minerals, Nomenclature andClassification I.M.A are greatly appreciated.

Financial support. The research was financially supported by the
project 19-16218S of the Czech Science Foundation for PavelŠkácha, Jiří Sejkora, Zdeněk Dolníček and Jana Ulmanová. We
acknowledge CzechNanoLab Research Infrastructure supported by
MEYS CR (LM2018110) for the financial support of the sample
measurements.

Review statement. This paper was edited by Sergey Krivovichev
and reviewed by Yves Moëlo and Ulf Hålenius.

References
9

Conclusions

Grimmite, NiCo2 S4 , a new thiospinel mineral, and its association were described from the Příbram uranium and basemetal district. Grimmite is the Co-dominant (16c site) andNi-dominant (8b site) member of the spinel supergroup. The
host association rich in Fe, Co and Ni includes the skutterudite group, sulfarsenides and arsenides. The presence ofgrimmite in association with base-metal sulfides replacing
older triarsenides indicates remobilisation processes causedby hydrothermal fluids rich in reduced sulfur. Partial dissolution of earlier Ni–Co arsenides associated with remobilisation of Ni and Co was the likely source of Ni and Co for theformation of grimmite and other Co–Ni-enriched sulfides.

Data availability. Crystallographic data for grimmite are available
in the Supplement.

https://doi.org/10.5194/ejm-33-175-2021

Ahmed, A. H., Arai, S., and Ikenne, M.: Mineralogy and paragenesis of the Co-Ni arsenide ores of Bou Azzer, Anti-Atlas, Morocco, Econ. Geol., 104, 249–266, 2009.
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