Comparative study of Bi-Te-Se-S mineralizations in Slovak Republic and Transcarpathian region of Ukraine. Part 2. Crystal chemistry and genesis of layered Bi-tellurides
Bismuth tellurides of layered structure (tetradymite group) are characteristic minerals of metasomatically altered neovolcanites of Slovakia and Ukrainian Transcarpathians. Tsumoite, pilsenite and joseite (A and B) are established in both regions, but the tetradymite is not found in Transcarpathians...
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Інститут геохімії, мінералогії та рудоутворення ім. М.П. Семененка НАН України
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irk-123456789-497402014-05-19T17:28:08Z Comparative study of Bi-Te-Se-S mineralizations in Slovak Republic and Transcarpathian region of Ukraine. Part 2. Crystal chemistry and genesis of layered Bi-tellurides Melnikov, V. Jeleň, S. Bondarenko, S. Balintová, T. Ozdín, D. Grinchenko, A. Мінералогія Bismuth tellurides of layered structure (tetradymite group) are characteristic minerals of metasomatically altered neovolcanites of Slovakia and Ukrainian Transcarpathians. Tsumoite, pilsenite and joseite (A and B) are established in both regions, but the tetradymite is not found in Transcarpathians. Two new minerals, telluronevskite and vihorlatite, are found in Slovakia. Phase Ві2Те (X-ray, microprobe) that forms epitaxial intergrowths with pilsenite is determined in Transcarpathians (Il'kivtsy). Se-joseite-В, Se-tsumoite, Te-bismuthite, phase ~ Ві2SeS (intermediate phase between nevskite and ingodite) and phase with stoichiometry of А3Х2 (A = Bi; Х = Te, Se, S) are determined in globules of native bismuth (Smerekiv Kamin') by microprobe analysis, but the number of anions Х varies from Bi3Te1.5S0.5 to Bi3TeSe0.5S0.5. The temperature of formation of layered bismuth tellurides is estimated within the interval 350—100 ºС. Телуриди бісмуту шаруватої структури (група тетрадиміту) — характерні мінерали метасоматично змінених неовулканітів Словаччини і Українського Закарпаття. Цумоїт, пильзеніт і жозеіт (А і В) відомі в обох регіонах, але тетрадиміт не знайдений в Закарпатті. У Словаччині відкриті два нових мінерали — телуроневскіт і вигорлатит. У Закарпатті (Ільківці) в епітаксичному зростанні з пільзенітом визначена фаза Ві2Те (рентген, електронний зонд), що утворює епітаксичні зростання з пільзенітом. У глобулах самородного бісмуту (Смереків Камінь) за допомогою електронно-зондового аналізу виявлені Se-жозеїт-В, Se-цумоїт, Те-бісмутиніт, фаза ~Ві2SeS (проміжна між невскітом й інгодитом) і фаза зі стехіометрією А3Х2 (А = Ві; Х = Te, Se, S), але кількість аніонів Х змінюється від Bi3Te1,5S0,5 до Bi3TeSe0,5S0,5. Температурний інтервал утворення шаруватих телуридів бісмуту — 350–100 ºС. Теллуриды висмута слоистой структуры (группа тетрадимита) — характерные минералы метасоматически измененных неовулканитов Словакии и Украинского Закарпатья. Цумоит, пильзенит и жозеит (А и В) установлены в обоих регионах, но тетрадимит в Закарпатье не найден. В Словакии открыты два новых минерала — теллуроневскит и выгорлатит. В Закарпатье (Ильковцы) определена фаза Ві2Те (рентген, электронный зонд), образующая эпитаксические сростки с пильзенитом. В глобулах самородного висмута (Смерекив Каминь) с помощью электронно-зондового анализа определены Se-жозеит-В, Se-цумоит, Те-висмутинит, фаза ~Ві2SeS (промежуточная между невскитом и ингодитом) и фаза со стехиометрией А3Х2 (А = Ві; Х = Te, Se, S), но количество анионов Х изменяется от Bi3Te1,5S0,5 до Bi3TeSe0,5S0,5. Температурный интервал образования слоистых теллуридов висмута — 350–100 ºС. 2010 Article Comparative study of Bi-Te-Se-S mineralizations in Slovak Republic and Transcarpathian region of Ukraine. Part 2. Crystal chemistry and genesis of layered Bi-tellurides / V. Melnikov, S. Jeleň, S. Bondarenko, T. Balintová, D. Ozdín, A. Grinchenko // Мінералогічний журнал. — 2010. — Т. 32, № 1. — С. 38-44. — Бібліогр.: 20 назв. — англ. 0204-3548 http://dspace.nbuv.gov.ua/handle/123456789/49740 549.328/.334(437.6 + 477) en Мінералогічний журнал Інститут геохімії, мінералогії та рудоутворення ім. М.П. Семененка НАН України |
| institution |
Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| collection |
DSpace DC |
| language |
English |
| topic |
Мінералогія Мінералогія |
| spellingShingle |
Мінералогія Мінералогія Melnikov, V. Jeleň, S. Bondarenko, S. Balintová, T. Ozdín, D. Grinchenko, A. Comparative study of Bi-Te-Se-S mineralizations in Slovak Republic and Transcarpathian region of Ukraine. Part 2. Crystal chemistry and genesis of layered Bi-tellurides Мінералогічний журнал |
| description |
Bismuth tellurides of layered structure (tetradymite group) are characteristic minerals of metasomatically altered neovolcanites of Slovakia and Ukrainian Transcarpathians. Tsumoite, pilsenite and joseite (A and B) are established in both regions, but the tetradymite is not found in Transcarpathians. Two new minerals, telluronevskite and vihorlatite, are found in Slovakia. Phase Ві2Те (X-ray, microprobe) that forms epitaxial intergrowths with pilsenite is determined in Transcarpathians (Il'kivtsy). Se-joseite-В, Se-tsumoite, Te-bismuthite, phase ~ Ві2SeS (intermediate phase between nevskite and ingodite) and phase with stoichiometry of А3Х2 (A = Bi; Х = Te, Se, S) are determined in globules of native bismuth (Smerekiv Kamin') by microprobe analysis, but the number of anions Х varies from Bi3Te1.5S0.5 to Bi3TeSe0.5S0.5. The temperature of formation of layered bismuth tellurides is estimated within the interval 350—100 ºС. |
| format |
Article |
| author |
Melnikov, V. Jeleň, S. Bondarenko, S. Balintová, T. Ozdín, D. Grinchenko, A. |
| author_facet |
Melnikov, V. Jeleň, S. Bondarenko, S. Balintová, T. Ozdín, D. Grinchenko, A. |
| author_sort |
Melnikov, V. |
| title |
Comparative study of Bi-Te-Se-S mineralizations in Slovak Republic and Transcarpathian region of Ukraine. Part 2. Crystal chemistry and genesis of layered Bi-tellurides |
| title_short |
Comparative study of Bi-Te-Se-S mineralizations in Slovak Republic and Transcarpathian region of Ukraine. Part 2. Crystal chemistry and genesis of layered Bi-tellurides |
| title_full |
Comparative study of Bi-Te-Se-S mineralizations in Slovak Republic and Transcarpathian region of Ukraine. Part 2. Crystal chemistry and genesis of layered Bi-tellurides |
| title_fullStr |
Comparative study of Bi-Te-Se-S mineralizations in Slovak Republic and Transcarpathian region of Ukraine. Part 2. Crystal chemistry and genesis of layered Bi-tellurides |
| title_full_unstemmed |
Comparative study of Bi-Te-Se-S mineralizations in Slovak Republic and Transcarpathian region of Ukraine. Part 2. Crystal chemistry and genesis of layered Bi-tellurides |
| title_sort |
comparative study of bi-te-se-s mineralizations in slovak republic and transcarpathian region of ukraine. part 2. crystal chemistry and genesis of layered bi-tellurides |
| publisher |
Інститут геохімії, мінералогії та рудоутворення ім. М.П. Семененка НАН України |
| publishDate |
2010 |
| topic_facet |
Мінералогія |
| url |
http://dspace.nbuv.gov.ua/handle/123456789/49740 |
| citation_txt |
Comparative study of Bi-Te-Se-S mineralizations in Slovak Republic and Transcarpathian region of Ukraine. Part 2. Crystal chemistry and genesis of layered Bi-tellurides / V. Melnikov, S. Jeleň, S. Bondarenko, T. Balintová, D. Ozdín, A. Grinchenko // Мінералогічний журнал. — 2010. — Т. 32, № 1. — С. 38-44. — Бібліогр.: 20 назв. — англ. |
| series |
Мінералогічний журнал |
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2025-07-04T10:59:42Z |
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2025-07-04T10:59:42Z |
| _version_ |
1836713805721108480 |
| fulltext |
The data of localisation of tellurides within the
territory of Slovakia and Transcarpathian region of
Ukraine and typical mineral associations found
here were discussed in the first part of the article
[13]. As layered tellurides of bismuth are established
both in Transcarpathian region of Ukraine and
Slovakia they can be taken as the object to do
comparative study of their crystallochemistry. Table
1 and 2 show crystallochemical formulas of bismuth
tellurides found in both these regions. We would
like to note, that chemical analyses are not given
for all minerals listed in [13] (Table 1). Therefore,
the data summarized in Table 1 do not completely
display all the crystallochemical features of bis-
muth tellurides of Slovakia. Predominant mineral
varieties are related to such structural types as
tetradymite (А
2
Х
3
), tsumoite (AX ) and pilsenite
(А
4
Х
3
). There are also some problematic species of
bismuth tellurides that have not been studied
enough yet. The same situation is observed with
tellurides of Transcarpathians which crystallo-
chemical formulas are listed in Table 2.
Tetradymite and tellurobismuthite. In spite of the
fact that tetradymite and tellurobismuthite are the
most widespread tellurides in Slovakia a number of
chemically characterised samples is limited to
several manifestations (Table 1). Their compositions
are close to stoichiometric, but tetradymite from
Smolník and Úhorná localities shows high sele-
nium content (0.26 Se on f. u.). Tetradymite from
Zupkov is the first finding of this mineral (A. Wehrle,
1831). The parameters of the trigonal unit cell
(a = 4.2496(7) — 4.2463(6) Å, c = 29.576(6) —
29.560(4) Ǻ, V = 462.6(1) — 461.6(1) Ǻ3) are in
accordance with calculated formula (Bi
1.97
×
×As
0.01)1.98
(Te
2.00
S
0.96
Se
0.06)1.02
[16]. Strangely
enough but tetradymite has not been found in
the Transcarpathian region of Ukraine till now.
Sulphur bearing tellurobismuthite from Sauliak
shows significant amount of lead (0.54 Pb p. f. u.)
(Table 2).
Tsumoite and similar minerals. Tsumoite from
Smolnik and Úhorná contains about 0.16 Cu on
UDC 549.328/.334(437.6 + 477)
V. Melnikov, S. Jeleň, S. Bondarenko,
T. Balintová, D. Ozdín, A. Grinchenko
COMPARATIVE STUDY OF Bi-Te-Se-S
MINERALIZATIONS IN SLOVAK REPUBLIC
AND TRANSCARPATHIAN REGION OF UKRAINE.
PART 2. CRYSTAL CHEMISTRY AND GENESIS
OF LAYERED Bi-TELLURIDES
Bismuth tellurides of layered structure (tetradymite group) are characteristic minerals of metasomatically altered
neovolcanites of Slovakia and Ukrainian Transcarpathians. Tsumoite, pilsenite and joseite (A and B) are established in both
regions, but the tetradymite is not found in Transcarpathians. Two new minerals, telluronevskite and vihorlatite, are found in
Slovakia. Phase Ві
2
Те (X-ray, microprobe) that forms epitaxial intergrowths with pilsenite is determined in Transcarpathians
(Il'kivtsy). Se-joseite-В, Se-tsumoite, Te-bismuthite, phase ~ Ві
2
SeS (intermediate phase between nevskite and ingodite)
and phase with stoichiometry of А
3
Х
2
(A = Bi; Х = Te, Se, S) are determined in globules of native bismuth (Smerekiv
Kamin') by microprobe analysis, but the number of anions Х varies from Bi
3
Te
1.5
S
0.5
to Bi
3
TeSe
0.5
S
0.5
. The temperature of
formation of layered bismuth tellurides is estimated within the interval 350—100 ºС.
E-mail: alexgrin@univ.kiev.ua
МІНЕРАЛОГІЧНИЙ ЖУРНАЛ
MINERALOGICAL JOURNAL
(UKRAINE)
© V. Melnikov, S. Jeleň, S. Bondarenko,
T. Balintová, D. Ozdín, A. Grinchenko, 2010
38 ISSN 0204-3548. Mineral. Journ. (Ukraine). 2010. 32, No 1
39ISSN 0204-3548. Мінерал. журн. 2010. 32, № 1
COMPARATIVE STUDY OF Bi-Te- Se-S MINERALIZATIONS IN SLOVAK REPUBLIC
f. u. As the replacement of large Bi by transitive
elements (Ni, Co, Fe, Cu) is rather limited, high
contents of copper seem strangely enough. Telluro-
nevskite is the new bismuth telluride found in
Slovakia [15]. Formula Bi
3
TeS
2
represents stoi-
chiometrically idealized composition, but ratio Bi :
(Te + Se + S) = 1 : 1 indicates its relation to minerals
of tsumoite subgroup. The ratio of Te : (Se + S) ≈
≈ 1 : 2 is rather similar to nevskite than to tsumoite.
Vihorlatite Bi
21.90
Se
17.40
Te
4.10
S
1.60
shows stable
chemical composition with low contents of Sb, Au
and Ag [17]. Based on the ratio of Bi : (Te + Se +
+ S) ≈ 1 : 1 vihorlatite is much closer to nevskite,
which formula can be represented as Bi (Te
0.19
×
×Se
0.79
S
0.07)1.05
(AX type of structure). However
more structural investigations to substantiate this
assumption are necessary.
In the Transcarpathian region of Ukraine the
composition of tsumoites is different for three
different types of metasomatites (Table 2). Tsumoite
from quartz-turmaline metasomatites of tract
Podulky contains small amount of silver (up to 0.18
Ag p. f. u.) and insignificant admixtures of Pb and
Sb. Tsumoite from montmorillonite-hydromica
metasomatites of Il'kivtsy is characterized by
complete absence of any Se and S admixtures. But
one interesting feature typical of lamellar bismuth
tellurides is observed in this area. Very often the
plates of this mineral are comprised by pilsenite
and tsumoite, but single-phase plates were also
found here. In the area of Smerekіv Kamin'
tsumoite was found in bismuth globule separated
from montmorillonite. Tsumoite shows wide range
of tellurium, selenium and sulfur contents (in p. f.
u.): Te — 0.18—0.72, Se — 0.40—0.17, S — 0.37—
0.03. Thus, formally these minerals should be
named as seleno-sulfo-tsumoites, and phases with
the minimum contents of tellurium show their
similarity to sulfonevskite (Table 2).
Pilsenite, joseite and similar minerals. The
selenium bearing pilsenite from Hnúšťa location is
interesting to study due to its high arsenic contents
that reach 0.22 As p. f. u. (Table 1). Two joseites (A
and B) from Chyžne contain lead (0.16 p. f. u.) that
indicates to the isomorphism between Pb and Bi in
pilsenite structural type (А
4
Х
3
). Wide isomorphism
between S and Se is found in ikonulite-laitakarite
series (Smolník and Úhorná), but there are no data
available about tellurium contents in these minerals
(Table 1).
In Transcarpathians layered tellurides of pilsenite
subgroup are represented by pilsenite and joseites
(Table 2). The whole absence of any admixtures of
S and Se is typical for pilsenite, as well as for
tsumoite from metasomatites of Podulky and
Il'kivtsy areas.
Bismuth globules from Smerekiv Kamin' do not
contain pilsenite (Table 2), but selenium bearing
joseite is usually found in them (Fig. 1). Joseite-A
shows selenium content ranging from 0.1 to 0.83 of
AmXn Mineral Formula Location
A
2
X
3
Tetradymite
(Bi
1.82
Sb
0.13
Cu
0.06)2.01 (Te
1.96
Se
0.04
S
0.99)2.99
Katarínska Huta
(Bi
1.84
Sb
0.05
Cu
0.05
Pb
0.04)2.00 (Te
1.78
Se
0.26
S
0.84)2.88
Smolník and Úhorná
(Bi
1.97
As
0.01)1.98 (Te
2.00
S
0.96
Se
0.06)3.02 Župkov
Tellurobismuthite (Bi
2.01
Ag
0.07
Au
0.02
Cd
0.01)2.11 (Te
2.84
Se
0.03)2.87 Kokava nad Rimavicon
АХ
Tsumoite
(Bi
0.97
As
0.03
Pb
0.03
Fe
0.03
Cu
0.02)1.08 (Te
0.80
Se
0.14
S
0.02)0.96
Hnúšťa
(Bi
1.77
Cu
0.16
Pb
0.09)2.02 (Te
0.89
Se
0.72
S
0.37)1.98 Smolník and Úhorná
Telluronevskite (Bi
2.92
Pb
0.02
)
2.94 (Te
1.01
Se
1.73
S
0.32)3.06
≈ Bi
0.95 (Te
0.33
Se
0.57
S
0.11)1.01
Poruba pod
Vihorlatom, Remetske
HamreVihorlatite Bi
21.90 (Se
17.40
Te
4.10
S
1.60)23.1
A
4
X
3
Pilsenite (Bi
3.50
Sb
0.03
As
0.22
Au
0.01
Pb
0.07
Cu
0.13)4.04 (Te
2.72
Se
0.35
S
0.08)3.15 Hnúšťa
Joseite-A (Bi
4.11
Sb
0.01
Pb
0.16)4.28 (Te
1.29
S
1.41)2.70
Chyžne
Joseite-B (Bi
3.97
Sb
0.01
Pb
0.16)4.1498 (Te
1.55
Se
0.02
S
1.30)2.87
Ikunolite-laitakarite
A
4.00(S, Se)3.08
up to A
4.00 (Se, S)2.86
A = Bi (+Sb, Pb, Cu, Fe)
Smolník and Úhorná
A
7
X
3+x
Hedleite (Bi
6.15
Sb
0.69
Cu
0.16)7.00 (Te
2.49
Se
0.88
S
0.25)3.62
Smolník and Úhorná
Table 1. The crystallochemical characteristics of layered tellurides of bismuth of Slovakia
40 ISSN 0204-3548. Mineral. Journ. (Ukraine). 2010. 32, No 1
V. MELNIKOV, S. JELEŇ, S. BONDARENKO et al.
Se p. f. u. Joseite-B is characterized by steady values
of selenium content (0.5—0.6 Se p. f. u.), with ratio
Se/S ≈ 1. The compositions of joseites indicate
that, despite fluctuations of sulphur/selenium ratio
there is a tendency to maintain values of Te : (Se +
+ S) ratio close to 1 : 2 for joseite-A and to 2 : 1 for
joseite-B.
Insufficiently distinguished phases. Some tellu-
rides enriched in bismuth (Bi > X = Te, Se, S)
which composition is close to stoichiometry of
Bi
6
X
5
, Bi
3
Х
2
, Bi
2
Х or Bi
7
X
3
should be related to this
group. Baksanite (Bi
6
Te
2
S
3) was established at
Chyžné location (Table 1). This sulfotelluride is
enriched by Bi and its structural formula can be
rewritten as (Bi
2
TeS) (Bi
4
TeS
2). Thus the baksanite
AmXn Mineral Formula Location
А
2
Х
3
Tellurobismuthite (Bi
1.53
Pb
0.54)2.07(Те
2.51
S
0.42)2.93
Sauliak
Bismuthite Bi
2.06(Te
0.51
Se
0.04
S
2.39)2.94
Smerekiv Kamin’
AX
Nevskite-ingodite Bi
1.05(Te
0.18
Se
0.40
S
0.37)0.95
Se-tsumoite
Bi
1.07(Te
0.51
Se
0.26
S
0.16)0.93
Bi
1.09(Te
0.54
Se
0.22
S
0.16)0.92
Bi
1.08(Te
0.72
Se
0.17
S
0.03)0.92
Tsumoite
(Bi
0.920
Ag
0.05)0.97
Te
1.034
Podulky
(Bi
0.850
Ag
0.18
)
1.03
Te
0.970
Bi
0.96
Te
1.04
Il’kivtsy
Bi
3.00
Te
0.92
A
4
X
3
Joseite-А
Bi
4.01
(Te
0.86
Se
0.10
S
2.03)3.00
Smerekiv Kamin’
Bi
4.04
(Te
0.85
Se
0.22
S
1.86)2.93
Bi
4.00
(Te
1.01
Se
0.21
S
1.78)3.00
Bi
4.09
(Te
1.30
Se
0.83
S
0.78)2.91
Joseite-B
Bi
4.04
(Te
1.81
Se
0.57
S
0.58)2.96
Bi
4.05
(Te
1.75
Se
0.55
S
0.65)2.95
Pilsenite
(Bi
3.80
Ag
0.10)3.90
Te
3.06 Podulky
Bi
3.96
(Te
2.91
(Se, S)
0.15)3.06 Il’kivtsy
A
3
X
2
Phase Bi
3
Te
2
Bi
2.98
(Te
0.84
Se
0.55
S
0.63)2.02
Smerekiv Kamin’
Bi
2.93
(Te
1.20
Se
0.11
S
0.67)2.07
Bi
2.99
(Te
1.51
S
0.50)2.01
Bi
3.02
(Te
1.47
S
0.50)1.97
A
2
X Phase Bi
2
Te
Bi
1.92
(Te
0.51
S
0.57)1.08
Bi
2
Te Il’kivtsy
Table 2. Crystallochemical characteristic of layered Bi-tellurides of Transcarpathian region of Ukraine
Fig. 1. Globule of bismuth (white) with margin
of phase Bi
4.04
Te
1.81
Se
0.57
S
0.58
(grey). Smerekiv
Kamin'
N o t e s. The samples were analyzed with microprobe JXA-8200 in Analytical centre of NAS of Ukraine.
41ISSN 0204-3548. Мінерал. журн. 2010. 32, № 1
COMPARATIVE STUDY OF Bi-Te- Se-S MINERALIZATIONS IN SLOVAK REPUBLIC
structure represents the interlaying of ingodite
(Bi
2
TeS) and joseite-A (Bi
4
TeS
2) blocks [14]. The
presentation of structure of sulfotellurides as
sequence of simple structural blocks (as example
Bi
2
Te
3
and Bi
2) is useful for interpretation of their
interrelation [11, 12]. Taking into consideration
the fact, that ingodite has structure similar to
tsumoite, and joseite does of pilsenite, the sequence
of blocks in baksanite is possible to be represented
as: 2 Bi
2
X
3
⋅ Bi
2
⋅ Bi
2
X
3
⋅ Bi
2
= 2Bi
2
(Te
0.5
S
0.5)3
×
×Bi
2
⋅ Bi
2
(Te
0.33
S
0.66)3
⋅ Bi
2
. Having designated
blocks as in [12], Bi
2
X
3
= m and Bi
2
= n, we will
receive the formula for baksanite as 5m + 4n. If S be
substituted by Te we will receive composition of
hypothetical bismuth telluride, Bi
6
Te
5
. This for-
mula can be expressed as Bi
3
Te
2 + x (x = 0.5).
Tellurides of such composition are established in
bismuth globules of occurrences from Smerekiv
Kamin' [11].
However, as it is easy to see that the proportion
of different blocks may be slightly changed. That
disproportion may be a reason of the deviation of
the telluride composition from stoichiometry.
Microprobe analyses of the Bi-tellurides often
show the existence of the phase composition of
which close to Bi
2
Te. The following phase of Bi
2
Te
is distinctly fixed on X-ray pattern of pilsenite from
Il'kivtsy area (Fig. 2, а, b). This phase forms thin
intergrowths in pilsenite, with orientation along
plane (0001) that is common for these phases
(mixed-layering in Bi-tellurides [10]). Its compo-
sition was estimated on parameter with c ≈ 18 Å.
Moreover, phase ~Bi
4
TeS was found in globules of
bismuth from the Smerkiv Kamin' (Table 2). In
addition, mineral Bi
2
Te is described in the Ergeliach
deposit (The Indigirka river, Siberia) in association
with tellurobismuthite and native bismuth [3]. It is
worth to note that the phase Bi
2
Te does not nece-
ssary to be matched with hedleyite (Bi
7
Te
3), which
composition and parameters are considerably diffe-
rent [19]. The reality of the structure of the phase
Bi
2
Te was justified by HREM investigation [2].
The phase Bi
3
Te
2
has been and still remains as a
subject of discussions since such composition was
assumed for "vehrlite" [4, 6, 7]. The possibility of
existence of compounds as Bi
3
X
2
(X = Te, S) has
been shown in some papers [4, 5, 10]. Natural
phases with idealized composition Bi
3(Te
1.33
S
0.67)2
(mineral-K) and Bi
3(Te
0.5
S
1.5)2
(mineral-P) were
described in the paper by A. Godovikov et al. [4, 5].
And finally, phase Bi
3(Te
1.5
S
0.5)2
was found in
globules from the Smerekiv Kamin' (Fig. 3;
Table 2). The main disadvantage of all investigations
Fig. 2. X-ray diffraction patterns of pilsenite samples
(Il'kivtsy) containing Bi
2
Te phase: a — intergrowth of
pilsenite Bi
4
Te
3
and phase Bi
2
Te along plane (0001) of
lamellar crystals. Diffraction pattern of plate oriented along
cleavage plane; b — diffraction pattern of more clear phase
Bi
2
Te; the weak reflections of pilsenite might be found
42 ISSN 0204-3548. Mineral. Journ. (Ukraine). 2010. 32, No 1
V. MELNIKOV, S. JELEŇ, S. BONDARENKO et al.
carried out at studying phase Bi
3
X2 is the whole
absence of reliable structural characteristics. It is
mainly caused by the submicroscopic size of grains.
Genesis. Detailed discussion of genesis of
tellurides was not the main aim of this paper.
However the preliminary analyses of the available
data allow us to make some conclusions. We note
that there is dependence between composition of
telluride and geochemical environment at which
this mineral was crystallized. It looks naturally,
because compositions of the mineral phases that
form mineral association should reflect association
of chemical elements at certain environment of
mi ne ralization. So, tellurides of silver, lead or bis-
muth can be formed only at the presence of these
elements in hydrothermal solution and at the same
time for their formation tellurium should be present
in this solution at certain concentration values. For
example, Beregovo gold deposit shows the presence
of bismuth sulphosalts and bismuthinite, but bis-
muth tellurides have not been found here till now [8].
In [13] (Table 1) have been indicated the
existence of three types of telluride mineralization
in Slovakia that corresponds to different degrees of
S, Se and Te fugacity.
1. Mineralization with the high fugacity of sulfur.
The characteristic minerals of this type are repre-
sented by bismuthinite (Bi
2
S
3
), ikunolite (Bi
4
S
3
),
tetradymite (Bi
2
Te
2
S), sulfo-skippenite (Bi
2
TeS
2
),
joseite (Bi
4
TeS
2
). Telluride occurrences are loca-
lized in Dubrava, Katarínska Huta, Kokava and
Rimavicou, Krokava, Rochovce, Banská Štiavnica
and Hodruša areas. All these occurrences do not
show any close association with volcanic processes.
2. Mineralization without manifestation of any
separate fugacity of sulfur, selenium or tellurium.
For this type telluride associations with different
relations S, Se and Te in their compositions are
observed: a) Layered structures are represented by
tetradymite, tsumoite, ikunolite (Bi
4
TeS
2
), pilse-
nite, laitakarite (Bi
4
Se
2
S), joséite-A, joséite-B and
Se-hedleyite (Bi
7
Te
2
Se), native bismuth; b) Some
other structures observed are bismuthinite, phase
(Bi,Sb,Cu)
3
S
4
(rakllidgeite type), gustavite (Bi
3
×
× PbAgS
6
), baksanite ((Bi,Pb)
6
Te
2
S
3
), gladite
(Bi
5
PbCuS
9
), hessite (Ag
2
Te).
The following occurrences were found in
Hnúšťa, Chyžné, Gemerská Poloma areas. For this
type any association with volcanic processes have
not been found.
3. Mineralization with high fugacity of tellurium.
For this type it is possible to distinguish two groups
of minerals: a) Layered tellurides of bismuth
represented by tetradymite (Bi
2
Te
2
S), tsumoite
(BiTe), pilsenite (Bi
4
Te
3
), joseite-B (Bi
4
Te
2
S),
ingodite (Bi (Te, Se)); b) Some other tellurides
found represented by hessite (Ag
2
Te), altaite (PbTe),
petzite (Ag
3
AuTe
2
), stutzite (Ag
5
Te
2
), silvanite
(AgAuTe
4
), cervelleite (Ag
4
TeS), weissite (Cu
3
Te
3
),
rickardite (Cu
3
Te
2
?). All these tellurides are
tellurides of Bi, Ag, Pb and Cu.
Telluride mineralization of this type is localised
in Jasenie, Kremnica, Zupkov, Banska Stiavnica
and Hodrusa, Zlata Bana, Bysta, Poruba pod
Vihorlatom and Remetske Hamre areas [13]. These
occurrences are found to be confined to neo-
volcanites.
It is also worth to note that manifestations of
tellurides with predominantly layered structures
(namely tellurides of tetradymite group) show close
association with secondary quartzite and argillizite
formations.
Some interesting interrelation between minerals
that form paragenetic association is observed in
bismuth globules sampled from the Smerekіv
Kamin' area. Besides native bismuth bismuth
sulfotellurides and tellurides, bismuthinite and
pyrite are found to be present in these globules. All
mineralogical phases found in globules show close
contact relation with native bismuth.
This fact indicates high bismuth abundance in
mineral-forming environment with high activity of
sulfur. It also results in the crystallization of bismuth
rich phases such as joseite, pilsenite, Bi
3
(Te, Se,
S)
2
and Bi
2
(Te, S) (Table 2). The fact of occurrence
of low-temperature association of Bi
2
Te phase and
bismuth rich tellurides were described in early
paper [3]. It is possible that there is direct relation
not only between amount of S and Se in structure
Fig. 3. Crystallisation of phase Bi
2.92
×
×(Te
0.93
Se
0.59
S
0.56)2.08
on boundary with
native bismuth. Stoichiometric formula is
Bi
6
Te
2
SeS (Smerekiv Kamin')'
43ISSN 0204-3548. Мінерал. журн. 2010. 32, № 1
COMPARATIVE STUDY OF Bi-Te- Se-S MINERALIZATIONS IN SLOVAK REPUBLIC
of bismuth tellurides but also between temperatures
of their formation. The similar conclusion might
be partly related to the values of bismuth content
found in telluride, notably the more high bismuth
content the more low temperature is.
The data on temperatures of telluride formation
are rather rare. And only few publications represent
data on composition of hydrothermal solutions.
Some results are obtained after carring out some
complex investigation of hydrothermal veins of the
Štiavnica-Hodruš ore district and discussed in
paper by Maťo [9]. The phase relations in the Au-
Ag-Te-(Se) and Bi-Te-S-(Se) systems compared
with data on the thermometry of fluid inclusion
indicate that: a — the temperature of the
precipitation of tellurides was commonly between
310—150 ºC; b — the fluid composition of solu-
tions corresponds to the systems of H
2
О — NaCl
and H
2
О — NaCl — KCl; c — the solution
concentration values vary from 0.7 to 3.9 equiv.
wt. % NaCl. Variable pressure (195—45 bars)
indicates continuous opening of the system and
transition from hydrostatic + litostatic to hydro-
dynamic conditions at shallow depths. Oxygen
isotopic data on quartz (–4.0 to 15.2 ‰) and
carbonates (+3.5 to 25.1 ‰), as well as the δD
values of chlorite and kaolinite indicate prog re s-
sively increasing percentage of meteoric waters
during the later mineralization stages (–52 to
–113 ‰). The values of the δ34S of sulphides
show that isotopic composition corresponds to
the δ34S of fluids, which were separated from
the uncontaminated granitic magmas, the δ34S
values of melt varied from –3 to +3 ‰ [9].
Temperatures of the formation stages of the
main mineral associations found in Saulak deposit
were determined with the help of studying of
gaseous-liquid inclusions and mineral paragene-
sises: 1 — gold-pyrite-quartz: 390—320 °С; 2 —
gold-sulfide-telluride: 270—200 °C; 3 — gold-
mica-carbonate: 220—160 °С [1]. Thus, lead and
silver tellurides were formed at middle tempera-
tures. Since the tellurobithmutite is commonly
found as separated from other tellurides, gold and
sulfides this fact allows us to assume, that its
crystalli za tion occurred at more low temperatures.
According to the data published in [18] the
homogenization of essentially gaseous inclusions
found in quartz sampled from quartz-turmaline
metasomatites occurred at temperatures more than
250 ºС. So it is possible to assume, that the tsumoite
crystallization temperature was also high. This facts
indicates possible tsumoite crystallization at the
stage of pre-metasomatic cracks formation and
its close association with pyrite and arsenopyrite.
These cracks played a role of conduits for the fluid
saturated with gases, that cause the processes of
metasomatic alteration. Thus, bismuth tellurides
are possible to be crystallized in the range from the
middle (350—300 ºС) to the lowest (150—100 ºС)
temperatures.
Conclusions. Tellurides and sulfotellurides of
layered structure are found widespread in locations
of gold associated with epithermal alteration
processes of volcanic rocks. Their composition
depends on environment conditions, first of all,
geochemical features, S and Te activity and cry-
stallization temperatures. The deviation from stoi-
chiometrical composition is typical of tellu ri des
and sulfotellurides that commonly cause the uncer-
tainty at their classifications. More detailed struc-
tural and chemical investigations are needed for
many mineral phases to be precisely distinguished.
Acknowledgements. This paper has been prepared
according to the project of international cooperation
between M.P. Semenenko Institute of Geochemistry,
Mineralogy and Ore Formation of the National
Academy of Sciences of Ukraine and Geological
Institute of Slovak Academy of Sciences. The title
of the project is "Comparative mine ra logical-geo-
che mical analysis of Au-Ag-Bi-Te-Se neovolcanic
mineralization of Ukraine and Slovakia (Carpathian
region)". This study was supported by of VEGA
grant UK/231/2009.
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2004. — 386 p. (in Russian).
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Amer. Miner. — 2009. — 94. — P. 517—534.
3. Gamyanin G.N., Leskova N.V., Vyal ′sov L.N., Laputina I.P. Bismuth tellurides — Bi
2
Te and BiTe — in deposits North-
East USSR // Proc. All-Union Miner. Soc. — 1980.— Pt. 109, No 2.— P. 230—235 (in Russian).
4. Godovikov A.A., Kochetkova, K.V., Lavrentyev, Y.G. Bismuth tellurides from the deposit Sokhondo // Ibid. — 1971. —
Pt. 109, No 3. — P. 257—265 (in Russian).
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Ibid. — 1971. — 100, No 4. — P. 417—428 (in Russian).
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Ukrainian).
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7. Lazarenko E.K., Lazarenko E.A., Baryshnikov E.К., Malygina O.A. Mineralogy of Transcarpathians. — Lvov : Publ.
House of Lvov. Univ., 1960. — 140 p. (in Russian).
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SSSR. — 1979. — 245, No 2. — P. 444—449 (in Russian).
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Slovakia // Understanding the genesis of ore deposits to meet the demands of the 21st cent., 12th IAGOD Quadren.
Symp. (21—24 aug. 2006) : Extended abstr. — M., 2006.
10. Melnikov V.S. A variation of Bi/Te ratio, polytytipism and mixed-layering in Bi-tellurides (Transcarpathians, Ukraine) //
32nd Intern. Geol. Congr., Florence : Abstr. vol. — 2004. — Pt. 1. — P. 275.
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Silver tellurides Deposits of the Golden Quadrilateral, South Apuseni Mts., Romania / Eds. N.J. Cook, C.L. Ciobanu. —
2004. — P. 214—216. — (IAGOD Guidebook. Ser. 12).
12. Melnikov V., Bondarenko S., Grinchenko A. Conditions of Bi-telluride formation in Vyghorlat-Huta volcanic ridge
(Transcarpathian region, Ukraine) // Geochemistry, mineralogy and petrology. Vol. 43. Au-Ag-Te-Se deposits. — Sofia,
2005. — P. 124—127. — (IGCP Project 486. 2005 Field Workshop, Kitten, Bulgaria).
13. Melnikov V., Jeleň S., Bondarenko S. et al. Comparative study of Bi-Te-Se-S mineralizations in Slovak Republic and
Transcarpathian region of Ukraine. Pt. 1. Localities, geological situation and mineral associations // Mineral. Journ.
(Ukraine). — 2009. — 31, No 4. — P. 38—48.
14. Pekov I.V., Zav'yalov E.N., Fedushchenko S.V. et al. Baksanite Bi
6
(Te
2
S
3
), a new mineral species from Tyrnyauz (Northern
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15. Řídkošil T., Skála R., Johan Z., Šrein V. Telluronevskite, Bi
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TeSe
2
, a new mineral // Eur. J. Miner. — 2001. — 13. —
P. 177—185.
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Miner. Slov. — 2004. — 36, No 3—4. — P. 303—315 (in Slovak).
17. Skála R., Ondruš P., Veselovský F. et al. Vihorlatite, Bi
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Se
17
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Mts., Slovakia // Eur. J. Miner. — 2007. — 19. — P. 255—265.
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P. 1439—1441 (in Russian).
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M.P. Semenenko Inst. of Geochemistry, Mineralogy and Ore Received 29.12.2009
Formation of the NAS of Ukraine, Kyiv, Ukraine
Geol. Inst. of Slovak Acad. of Sci., Bratislava, Slovak Rep.
Comenius Univ., Faculty of Natural Sci.,
Department of Mineralogy and Petrology, Bratislava, Slovak Rep.
Taras Shevchenko Kyiv Nat. Univ., Kyiv, Ukraine
РЕЗЮМЕ. Телуриди бісмуту шаруватої структури (група тетрадиміту) — характерні мінерали метасоматично змі-
нених неовулканітів Словаччини і Українського Закарпаття. Цумоїт, пильзеніт і жозеіт (А і В) відомі в обох регіо-
нах, але тетрадиміт не знайдений в Закарпатті. У Словаччині відкриті два нових мінерали — телуроневскіт і ви-
горлатит. У Закарпатті (Ільківці) в епітаксичному зростанні з пільзенітом визначена фаза Ві
2
Те (рентген,
електронний зонд), що утворює епітаксичні зростання з пільзенітом. У глобулах самородного бісмуту (Смереків
Камінь) за допомогою електронно-зондового аналізу виявлені Se-жозеїт-В, Se-цумоїт, Те-бісмутиніт, фаза ~Ві
2
SeS
(проміжна між невскітом й інгодитом) і фаза зі стехіометрією А
3
Х
2
(А = Ві; Х = Te, Se, S), але кількість аніонів Х
змінюється від Bi
3
Te
1,5
S
0,5
до Bi
3
TeSe
0,5
S
0,5
. Температурний інтервал утворення шаруватих телуридів бісмуту —
350–100 ºС.
РЕЗЮМЕ. Теллуриды висмута слоистой структуры (группа тетрадимита) — характерные минералы метасомати-
чески измененных неовулканитов Словакии и Украинского Закарпатья. Цумоит, пильзенит и жозеит (А и В)
установлены в обоих регионах, но тетрадимит в Закарпатье не найден. В Словакии открыты два новых минера-
ла — теллуроневскит и выгорлатит. В Закарпатье (Ильковцы) определена фаза Ві
2
Те (рентген, электронный зонд),
образующая эпитаксические сростки с пильзенитом. В глобулах самородного висмута (Смерекив Каминь) с по-
мощью электронно-зондового анализа определены Se-жозеит-В, Se-цумоит, Те-висмутинит, фаза ~Ві
2
SeS (про-
межуточная между невскитом и ингодитом) и фаза со стехиометрией А
3
Х
2
(А = Ві; Х = Te, Se, S), но количество
анионов Х изменяется от Bi
3
Te
1,5
S
0,5
до Bi
3
TeSe
0,5
S
0,5
. Температурный интервал образования слоистых теллуридов
висмута — 350–100 ºС.
|