Maslennikov 2013 - Tellurium-Bearing Minerals in Zoned Sulfide Chimneys From Cu-Zn Massive Sulfide Urals

Miner Petrol (2013) 107:6799
DOI 10.1007/s00710-012-0230-x
ORIGINAL PAPER
Tellurium-bearing minerals in zoned sulfide chimneys

from Cu-Zn massive sulfide deposits of the Urals, Russia
V. V. Maslennikov & S. P. Maslennikova & R. R. Large &
L. V. Danyushevsky & R. J. Herrington & C. J. Stanley
Received: 21 June 2011 / Accepted: 18 October 2012 / Published online: 22 November 2012
# Springer-Verlag Wien 2012
Abstract Tellurium-bearing minerals are generally rare in

chimney material from mafic and bimodal felsic volcanic
hosted massive sulfide (VMS) deposits, but are abundant in
chimneys of the Urals VMS deposits located within Silurian
and Devonian bimodal mafic sequences. High physicochemical gradients during chimney growth result in a wide
range of telluride and sulfoarsenide assemblages including a
variety of Cu-Ag-Te-S and Ag-Pb-Bi-Te solid solution series and tellurium sulfosalts. A change in chimney types
from Fe-Cu to Cu-Zn-Fe to Zn-Cu is accompanied by gradual replacement of abundant Fe-, Co, Bi-, and Pb- tellurides
by Hg, Ag, Au-Ag telluride and galena-fahlore with
native gold assemblages. Decreasing amounts of pyrite,
both colloform and pseudomorphic after pyrrhotite, isocubanite ISS and chalcopyrite in the chimneys is coupled
with increasing amounts of sphalerite, quatz, barite or
talc contents. This trend represents a transition from lowto high sulphidation conditions, and it is observed across a
Editorial handling: L. Danyushevsky
V. V. Maslennikov (*)
Institute of Mineralogy, Ural Devision of RAS,
and the South Ural State University,
Miass, Chelyabinsk district, Russia
e-mail: mas@mineralogy.ru
S. P. Maslennikova
Institute of Mineralogy, Ural Division of RAS,
and the South Ural State University,
Miass, Chelyabinsk district, Russia
R. R. Large : L. V. Danyushevsky
CODES ARC Centre of Excellence in Ore Deposits and School
of Earth Sciences, University of Tasmania,
Hobart, Australia
R. J. Herrington : C. J. Stanley
Department of Mineralogy, Natural History Museum,
Cromwell Road,
London SW7 5BD, UK
range of the Urals deposits from bimodal mafic- to bimodal

felsic-hosted types: Yaman-Kasy Molodezhnoye
Uzelga Valentorskoye Oktyabrskoye Alexandrinskoye Tash-Tau Jusa.
Introduction
Tellurium-bearing mineralization is found associated with
many sulfide deposits, particularly in epithermal vein deposits of gold and silver (Afifi et al. 1988b; Ciobanu et al. 2006;
Cook et al. 2007a, b; Jaireth 1991). In general, telluriumbearing minerals are relatively uncommon in volcanichosted massive sulfide (VHMS or VMS) deposits (Afifi et
al. 1988b; McPhail 1995), with the notable exception of the
Urals, where tellurides and tellurium minerals are recorded
at a number of deposits (Shadlun 1942; Herrington et al.
1998; Prokin and Buslaev 1999; Moloshag et al. 2002;
Vikentyev 2006; Novoselov et al. 2006). Tellurium is scarce
in active seafloor hydrothermal systems, and tellurobismuthite is recorded rarely in sulfides from the modern oceans
(Iizasa et al. 1992).
In the Urals, tellurides are not present in all VMS deposits
(Prokin and Buslaev 1999; Vikentyev 2006). The causes of
this are poorly understood. A theory that tellurides form in
massive sulfide ores during recrystallization caused by late
(low-temperature) hydrothermal or metamorphic processes
(Vikentyev 2006; Eremin 1983) is in contradiction with
the discovery of rich telluride occurrences in some nonmetamorphosed VMS deposits (Shadlun 1942; Maslennikov
1999). In previous work (Herrington et al. 1998; Maslennikov
et al. 1997, 2009; Maslennikova and Maslennikov 2007), the
authors documented some tellurium-bearing phases in very
well preserved zoned vent chimney fragments from nonmetamorphosed Yaman-Kasy deposit. These results were
highly unusual, but more recently, numerous sulfide chimneys
from a number of unmetamorphosed VMS deposits of the
68
Urals have been discovered and are presented here. Diverse

tellurides are abundant in some chimneys but absent in others.
These conflicting data create numerous questions and require
an explanation. The problem can be resolved by research at
different scales including analysis of relevant genetic features
of host sequences, systematic textural and paragenetic studies
of different types of VMS deposits and chimneys, and their
rare mineral assemblages. Paragenetic models, compositional
analyses and ranges of tellurium-bearing minerals and the
physicochemical interpretation of chimney diversity in different types of VMS deposits are the main subjects of this paper.
Methods and samples studied

A preliminary mineralogical study of the samples was followed by scanning electron microscopy (REMMA2M
SEM equipped with energy dispersive Xray detector and
JEOL JXA 733) at the Institute of Mineralogy, Russian
Academy of Sciences. Further mineral analyses were
obtained in several laboratories equipped with CAMEBAX
SX50 and JEOL-JXL-8600 (Natural History Museum,
London), Cameca SX-100 (University of Tasmania, Australia) and JEOL JXA 8900RL (Freiberg Mining Academy,
Germany). Analytical conditions were similar in the different laboratories. In all electron microprobe analyses, the
standard deviation of results is less than 0.1 %. Major and
minor elements were determined at 1525 kV accelerating
potential, 2035 nA beam current and acquisition time
between 10 and 20 s for Xray peak and background. The
effective probe size was between 1 and 2 m.. The following standards were used: SK (ZnS), AgL (Ag), SbL
(Sb2S3), CdL (CdS), TeL (Bi2Te3), TeLb (Ag2Te), SeK
(PbSe), BiL (Bi2Te3), PbL (PbS), CuK (CuFeS2), SK
(Bi2S3), AgL (Ag), SbL (Sb2S3), CdL (CdTe), SeK
(Bi2Se3), BiL (Bi2S3), HgMa (HgS) AsKa (GaAs), Cd La
(CdS), MnKa (Mn), CoKa (FeCoNi), TlMa (TlInS2). Detection limits were commonly within the following range
(wt%): S and Fe 0.06. Co 0.05, Ni 0.08, Cu 0.10, Zn
0.14, As 0.12, Ag 0.15, Sb 0.090.2, Te 0.120.29,
Hg 0.22, Au 0.18, Pb 0.190.34, Bi 0.180.26, Se
0.10.13, Sn 0.030.05, Hg 0.10.3, Tl 0.27, Sn 0.03,
Mn 0.04.
Quantitative analysis of chimney sulfides and tellurides
for a wide range of major and trace elements (Fe, Cu, Zn,
Co, Ni, Au, Ag, Bi, Pb, Tl, Cd, As, Te, Se, Mo, Sn, V, Ti,
and Mn) was carried out using LA-ICPMS. The instrumentation includes a New Wave 213 nm solid-state laser microprobe coupled to an Agilent 7500cs quadrupole ICPMS
housed at the CODES LA-ICPMS analytical facility, University of Tasmania.
The laser microprobe was equipped with an in-house small
volume (~ 2.5 cm3) ablation cell characterised by<1 s
V.V. Maslennikov et al.
response time and<2 s wash-out time. Ablation was performed in an atmosphere of pure He (0.7 l/min). The He
gas carrying the ablated aerosol was mixed with Ar (0.9 l/min)
immediately after the ablation cell and the mix is passed
through a pulse-homogenising device prior to direct introduction into the torch.
The ICPMS was optimised daily to maximise sensitivity on
mid- to high-mass isotopes (in the range 130240 a.m.u.).
Production of molecular oxide species (i.e., 232Th16O/232Th)
and doubly-charged ion species (i.e., 140Ce++/140Ce+) was
maintained at<0.2 %. Due to the low level of molecular oxide
and doubly charged ion production no correction was introduced to the analyte signal intensities for such potential interfering species. Each analysis was performed in the timeresolved mode which involves sequential peak hopping
through the mass spectrum.
For this study, the quantitative analyses were performed
by ablating spots ranging in size from 40 to 60 m. Laser
repetition rate was typically 5 Hz and laser beam energy at
the sample was maintained between 4 and 5 J/cm2. The
analysis time for each sample was 100 s, comprising a
30 s measurement of background (laser off) and a 70 s
analysis with laser-on. Acquisition time for all masses was
set to 0.02 s. Data reduction was undertaken according to
standard methods (Longerich et al. 1996). Fe was used as
the internal standard for quantification of pyrite and chalcopyrite and Zn was used as the internal standard for quantification of sphalerite. Concentrations of the internal standard
were calculated assuming stoichiometry. In cases when a
significant degree of fine-grained mineral intergrowth occurred within the ablated volume, values for the internal
standard concentration were adjusted such that the total of
major elements (Fe, Cu, Za and S, the latter calculated
assuming stoichiometry) is 100 %. An in-house Li-borate
fused glass of a pyrite/sphalerite mixture (Danyushevsky et
al. 2003, 2011) was used as the primary calibration standard.
The standard was analysed twice every one and a half hour
to account for the instrument drift, with a 100 m beam and
at 10 Hz. The LA-ICP-MS is used for detection of rare
mineral micro-inclusions in sulfides studied, and for analysis of trace elements in tellurides.
Geological setting and types of VMS deposits

Several reviews have described the geological setting and
geology of the VMS deposits in the Urals (Gusev et al.
2000; Herrington et al. 2002, 2005a, b; Kontar 2001; Kontar
and Libarova 1997; Koroteev et al. 1987; Maslennikov 1999,
2006; Prokin and Buslaev 1999; Puchkov 2010; Seravkin
2010; Zaykov 2006; Zonenshain et al. 1984).
The VMS-deposits formed in a range of tectonic settings
(Fig. 1). Those within the Silurian Sakmara zone (e.g.
Fig. 1 The locations of the Urals VMS deposits with documented

chimney occurrences
69
Yaman-Kasy) are ascribed to either a marginal sea (Zaykov

2006) or an island arc (Herrington et al. 2005b). The Tagil
and Magnitogorsk zones include a range of arc, back- and
intra-arc rifts (Herrington et al. 2005b; Zaykov 2006). In the
Sakmara and Tagil arcs, the VMS deposits are hosted in
Silurian age basalt-rhyolite complexes whilst those in the
Magnitogorsk zone are Devonian. The VMS deposits are
situated in extensional graben or half-graben rift valleys
not only in back-arc basins, but also in intra-arc rifted
basement (Maslennikov 1999). The intra-arc rifts contained
infrequently developed calderas (Seravkin 2010). Most of
VMS deposits are located within several stratigraphic levels
(Fig. 2).
Urals VMS deposits have been subdivided as into four
main types: Cyprus, Uralian, Besshi and Baymak (note that
names such as Kuroko-type and Altai-type have also
been used in the literature to describe the latter type),
depending on the geological and geodynamic conditions of
formation (Glasby et al. 2006; Gusev et al. 2000; Herrington
et al. 2002, 2005a; Prokin and Buslaev 1999; Seravkin
2010; Zaykov 2006). These types can be broadly compared
to the classification of Franklin et al. (2005) where Cyprus0
Mafic, Besshi0Pelitic-mafic, Uralian0Bimodal-mafic, and
Baymak0Bimodal-felsic. The Urals VMS deposits where
chimneys were identified are related to the Uralian or
Baymak types. The Uralian and Baymak type deposits
can be subdivided based on the distance between the ore
bodies and basalt basements (Table 1). The distances are
roughly correlated with general ore mineralogy and Te
contents in ore bodies and in the chimneys studied.
The chimneys in situ were found in the central part of
orebodies interpreted as the relics of hydrothermal sulfide
Fig. 2 The locations of chimney-bearing Urals VMS deposits in compiled stratigraphic columns
70
Table 1 Te contents in the bulk ore (Data from open reports of

Ministry of Base Metals, USSR) and chimneys (original data by ICPMS and LA-ICP-MS analytical techniques) from different types of the
Urals VMS deposits and chimneys (original data from Zaykov 2006;
Maslennikov 1999; Moloshag et al. 2002; Tessalina et al. 1998, 2008;
Vikentyev et al. 2000, 2004)
VMS Deposit
Types
Distance from
Mean Te in Mean Te in
basalt basement (m) ore (ppm) chimneys
(ppm)
General ore mineralogy
Yubileynoye
Cyprus to
Uaralian
30
40
Yaman-Kasy
Uralian
0100
325
1349
Molodezhnoye
Uralian
30120
82
1030
Uzelga-4
Uralian
40150
110
358
Oktyabrskoye
Uralian to
Baymak
200
30
166
Valentorskoye
Uralian to
Baymak
90300
28
196
Alexandrinskoye Baymak
310
39
28
Tash-Tau
150300
25
Saphyanovskoye Baymak or Altai >300
1
1
17
Jusa
0.1
Pyrite, chalcopyrite, sphalerite, marcasite, pyrrhotite,

arsenopyrite, magnetite, tennantite, hessite, and
electrum
Pyrite, marcasite, chalcopyrite, sphalerite, bornite,
marcasite, arsenopyrite, pyrrhotite, altaite,
tellurobismuthite, coloradoite, empres, site, galena,
site, hessite, tennantite, barite, hematite and magnetite,
galena, enargite, petzite, sttzite, lllingite, volynskite,
greenockite, digenite, cervelleite, benleonardite,
covellite, goldfieldite, sylvanite, frohbergite,
native tellurium, native gold, magnetite
Pyrite, chalcopyrite, sphalerite, bornite, marcasite,
arsenopyrite, pyrrhotite, altaite, tellurobismuthite,
coloradoite, empressite, hessite, tennantite, barite,
hematite, and magnetite, galena, enargite,
stromeyerite, arsenosulvanite, jalpaite, mackinstryite,
stannoidite, mowsonite, native gold
Pyrite, chalcopyrite, pyrrhotite, altaite,
tellurobismuthite, sylvanite, petzite, coloradoite,
shttzite, hessite, native tellurium, native gold,
tennantite, tetrahedrite, magnetite, arsenopyrite,
coloradoite, siderite,
Pyrite, chalcopyrite, bornite, digenite, sphalerite,
quartz, bornite, barite, hessite, altaite, tennantite,
tetrahedrite, native gold
Pyrite, chalcopyrite, bornite, hessite, tellurobismuthite,
sttzite, empressite or kochkarite, tennantite,
cervelleite, wittichenite, renierite, native gold
Pyrite, chalcopyrite, sphalerite, bornite, barite, galena,
tennantite, , hessite, diagenite, stromeyerite, renierite,
germanite, acantite, pyrseite, native gold and electrum
Pyrite, sphalerite, and chacopyrite, bornite, tennantite,
galena, hessite, cervellite, native gold, and electrum,
enargite, galena, digenite, stromeyerite, jalpaite,
germanite, calcite, barite
Pyrite, chalcopyrite, sphalerite, pyrrhotite, galena,
tennatite, tetrahedrite, glauckodot, tellurobismuthite,
hessite and unresolved Bi-telluride, enargite,
stannite, native gold, Pb-sulfosalts
Pyrite, chalcopyrite, sphalerite, galena, tennantite,
tetrahedrite, arsenopyrite, native gold
Baymak
Baymak to
Kuroko
>300
mounds degraded on the seafloor (Fig. 3). The central part of

the ore lens consists of compact pyrite-chalcopyrite ores
consequently flanked by sulfide breccias and sulfide
turbidites intercalating with ferruginous cherts or black
shales (Maslennikov 1999, 2006; Herrington et al. 2005b;
Buschmann and Maslennikov 2006; Maslennikov et al.
2009). The clastic ores and in-situ massive sulfides collected
from the apex of the sulfide mounds contain abundant fragments of well-preserved chimneys and occasional sulfidized
fauna (Little et al. 1997). The lens-like shape of the ore bodies
and the presence of clastic ore with vent fossils indicate that the
Urals VMS deposits were ancient analogues of black smoker
sulfide mounds (Shadlun 1991; Zaykov et al. 1995). The
discovery of black smoker chimney fragments confirmed this
hypothesis (Herrington et al. 1998; Maslennikov 1991, 1999,
2006; Maslennikov et al. 2009).
Typical features of the Uralian type VMS deposits are a)
common colloform and biomorphic textures of pyrite, relic
71
Fig. 3 The position of sulfide

chimneys in the ore bodies from
the Urals VMS deposits
phyrrhotite, pseudomorphs of pyrite and marcasite after initial

euhedral pyrrhotite, b) common occurrence of isocubanite
intermediate solid solutions (ISS) and c) low-sulfidation conditions of formation, indicated by the presence of altaite. In the
Baymak-type VMS deposits, colloform and biomorphic pyrite
occurrences are rare, whereas pyrrhotite and pseudomorphs
after pyrrhotite are absent. In the footwall of the Baymak-type
deposits, volcanics are commonly highly altered to quartzsericite and sometimes pyrophyllite assemblages with scattered pyrite, chalcopyrite, sphalerite and galena, which form
economically important ores. Abundant galena and fahlores
suggest moderate- to high-sulfidation condition for Baymaktype deposit formation.
Preservation of chimney material

In the Magnitogorsk and Sakmara zones, the VMS deposits
have been affected by low grade metamorphism, typically to
prehnite-pumpellite facies only. The good preservation of
primary colloform, sulfidized fauna and chimney textures of
the ores is due to this low degree of metamorphic overprint
(Herrington et al. 1998; Little et al. 1997; Maslennikov et al.
2009; Shadlun 1991; Zaykov 2006). Further north in the
Urals, the rocks of the Tagil arc are dominated by volcanic

units strongly metamorphosed from greenschist to granulite
facies. The Tagil arc, which contains magnetite-rich ferruginous sediments, is generally metamorphosed to greenschist
facies. Chimney fragments were not found in the Tagil arc,
Dombarovsk and Orsk areas, where the VMS deposits are
metamorphosed to epidote-amphibolite facies. Two exceptions to this are the recovery of sulfide chimneys from the
Valentorskoye and Saphyanovskoye deposits. The latter only
shows zeolite facies metamorphism (Grabezhev et al. 2001),
and a similar of metamorphic grade is also assumed for the
Valentorskoye deposit. These deposits are located in tectonically preserved fragments of less-metamorphosed terrains.
Recovery of chimney material is thus restricted to specimens from less metamorphosed VMS deposits, which are
comparable in textural features to modern black and gray
smokers (Herrington et al. 1998). In the core of the sulfide
mounds, chimneys are variably recrystallized to granular
pyrite. The most diverse and well-preserved fragments of
sulfide chimneys are instead found within ore breccias. In
sulfide turbidites, the primary colloform and sooty pyrite
fragments of the chimneys were replaced by diagenetic
chalcopyrite, granular pyrite and cryptocrystalline hematite due to seafloor oxidation (Saphina and Maslennikov 2008)
72
Results
Mineral zonation of chimneys studied
Previous papers have described three Urals chimney fragments where there was clear evidence for high-temperature
fluid flow through the axial zone, passing to a temperaturezoned chimney wall (Herrington et al. 1998; Maslennikov
1999). These authors recognized the presence of three broad
mineralogical zones developed in response to the interaction
of high-temperature vent fluid with seawater.
Chimneys can be broadly divided into three radial
zones described here from the outer wall, formerly in
contact with seawater, to the inner axial hydrothermal
flow cavity: A - external zone typified by pyrite,
marcasite and/or sphalerite; B - internal zone typified
by the presence of chalcopyrite, and C - lining of the
axial zone normally infilled by sphalerite, quartz or
barite. Each of these zones may be subdivided into
several subzones in each sample, depending on the
presence of other minerals.
Our new work based on more than 200 well-preserved
chimney/conduit fragments also shows that we can broadly
classify the chimney into 3 types based on mineralogy
(Figs. 4 and 5):
Type 1: chalcopyrite-pyrite to quartz-pyrite-chalcopyrite;
Type 2: chalcopyrite-pyrite (marcasite)-sphalerite to quartzsphalerite-pyrite-chalcopyrite barite;
Type 3: chalcopyrite-sphalerite to barite-sphalerite-chalcopyrite;
The types form a general range with an increase of
sphalerite abundance from type 1 to type 3. In each type,
the mineralogical variations lead to a decrease in chalcopyrite accompanied by an increase in either quartz + pyrite
(type 1 in Fig. 4ad), or sphalerite + quartz (type 2 in
Figs. 4eh and 5ac), or sphalerite + quartz + barite (type
3 in Fig. 5dh). Each type or subtype of these chimneys
exhibits specific mineralogical zonation, loosely adhering to
the broad A, B, C zones classification indicated above.
Mineralogical and textural proxies of the zonation can be
found in the segments of chimney walls (Figs. 6, 7, 8). Each
type of the chimneys contains different rare mineral assemblages (Table 2).
Type 1 chimneys
Numerous fragments of chalcopyrite-pyrite chimneys are
present in the Yubileinoye deposit, but the most complete range from chalcopyrite-pyrite to quartz-pyritechalcopyrite chimneys was found in the Yaman-Kasy
deposit. Other type 1 chimney fragments occur in the
lower part of the Saphyanovskoye ore body, and rarely
Fig. 4 Type 1 (ad) and Types 23 (eh) chimneys specimens from

Yaman-Kasy deposit. Type 1 chimneys: a chalcopyrite-pyrite, b
chalcopyrite-pyrite-marcasite-sphalerite, c marcasite-chalcopyritepyrite-quartz, d quartz-pyrite-chalcopyrite. Type 2 and 3 chimneys:
e chalcopyrite-pyrite-sphalerite; f chalcopyrite-sphalerite-pyritemarcasite, g sphalerite-chalcopyrite-marcasite, h quartz-sphaleritebarite-pyrite-chalcopyrite. a, b, c chimney structural zones (see text
for details). Scale is 1 cm
at the Molodezhnoye, Uzelga-4 and Valentorskoye

deposits. The largest piece of a chimney recovered
measures some 4 cm in diameter and is 12 cm long.
Another typical fragment was found in the sulfide breccia layer on the southern flank of the massive sulfide
lens, measuring some 3-5 cm in diameter, about 4-8 cm
long, and is very strikingly zoned. In cross-section, all
fragments have a simple 23 fold zonation with the
development of A, B and C zones.
Zone A In the chimneys from the Yaman-Kasy deposit, the
outermost zone is composed of laminated and botryoidal
colloform pyrite and the orientation suggests a centrifugal
growth of the botryoidal pyrite (Figs. 6a and 7ac).
Fig. 5 Type 2 (ac) and Type 3 (dh) chimneys from the Uselga (a),
Molodezhnoye (b), Saphyanovskoye (c, d), Valentorskoye (e, f), and
Alexandrinskoye (g, h) VMS deposits. a chalcopyrite-pyritesphalerite-quartz, b chalcopyrite-pyrite-sphalerite, c chalcopyritequartz-pyrite-marcasite, d sphalerite-pyrite-chalcopyrite, e
chalcopyrite-sphalerite-quartz, f quartz-sphalerite-pyrite-chalcopyrite; g sphalerite-chalcopyrite-barite, h sphalerite-chalcopyrite. a,
b, c chimney structural zones (see text for details)
Colloform pyrite grades to a vuggy, fine to medium

grained pyrite towards the central part of zone A (subzone A2). The outer layers in the chimneys from the
Saphyanovskoye deposit are made up of botryoidal,
framboidal and dendritic pyrite partly replaced by chalcopyrite (Fig. 7df). In subzone A2 (Fig. 7a, c, f), there
are rare disseminated tabular-hexagonal crystals of either
nonstochiometric cryptocrystalline pyrite or fine-grained
marcasite, replacing an initial subhedral pyrrhotite
phase. This texture has been also described in modern
chimneys (Peter and Scott 1988; Marchig and Rsch
1988; Paradis et al. 1988), in ores of the Uralian type
deposits (Maslennikova and Maslennikov 2007), and in the
ancient chimney fragments (Maslennikov et al. 2009). The
pseudomorphs contain relic inclusions of pyrrhotite and display incomplete cleavages in the pyrite, characteristic of former pyrrhotite crystals (Zhabin and Samsonova 1975). Pyrite
73
Fig. 6 The most important microfabrics of the chimneys studied:

Yaman-Kasy (af), Oktyabrskoye (g) and Alexandrinskoye (h) deposits.
Reflected light a reniform colloform pyrite from the outer wall; b
marcasite pseudomorphs after tabular pyrrhotite crystals in the central
part of the outer wall; c subhedral and euhedral pyrite at the boundary
with the chalcopyrite wall; d drusy chalcopyrite with isocubanite lattice;
e kidney-shaped chalcopyrite segregations within sphalerite frame, and
disseminated lllingite in the transition zone between the wall and the
channel; f marcasite pseudomorphs after tabular pyrrhotite crystals in
the sphalerite cement of the channel; g sphalerite with disseminated
chalcopyrite of the outer wall at the contact with crustified chalcopyrite of the wall; h graphic intergrowth of chalcopyrite and sphalerite
in the channel
net veining and porous textures are typical of pyrite pseudomorphs after pyrrhotite crystals (Zierenberg et al. 1993). Chalcopyrite abundance increases towards the inner rim of zone A
(subzone A3), where idiomorphic coarse-grained pyrite is the
main phase. Euhedral pyrite can contain inclusions of
pyrrhotite. Sphalerite and marcasite are rare to absent in
subzone A3 of chalcopyrite-pyrite chimneys but are abundant
in quartz-rich varieties. The boundary between zones A and B
is distinctive, marked by the disappearance of the granular
aggregates of pyrite.
74

Table 2 Accessory minerals in the chimneys from the Urals VMS
deposits
Minerals
Types of VMS deposits

Uralian
Baymak
Yb Y S M U V O A TT
Fig. 7 Wall zonation of type 1 chimneys from the Urals VMS deposits
Zone B The interior of the chimneys is formed by rhythmic

layers of coarse-grained bladed drusy chalcopyrite (Fig. 7).
In chalcopyrite-pyrite chimneys, the outer part (subzone B1),
close to the boundary with zone A, contains cubic crystals of
pyrite only (Yubileynoye, Yaman-Kasy deposits) and is devoid of accessory minerals (Fig. 4a). Sulphoarsenides or/and
Pyrrhotite Fe9S8
+
Co- and Te-rich lllingite
(Fe0.8Co0.2)(As1.5Te0.4S0.1)
Cobaltite CoAsS
Arsenopyrite FeAsS
Glaucodot (Fe,Co)AsS
Frohbergite (Fe, Co)Te2
Altaite PbTe
Tellurobismuthite Bi2Te3
Sylvanite AgAuTe4
Petzite AuAg3Te2
Coloradoite HgTe
Sttzite Ag5Te3 or -phase Ag1.88Te
Hessite Ag2Te
+
EmpressiteAgTe
Volynskite AgBiTe2
Native tellurium Te
TeO + Te or Te.H2O
Native gold Au0.8Ag0.2
CuAg-sulfotellurides
(CuAgHg)-sulfosalts
Tennantite
Cu10(Zn,Fe)2(As,Sb,Te)4S13
Tetrahedrite
Cu10(Zn,Fe)2(Sb,As,Te)4S13
Goldfieldite Cu10Te4S13
Greenockite CdS
Bornite Cu5FeS4
Galena PbS
Copper sulfides CuSCu2S
Magnetite FeOFe2O3
Hematite F2O3
+ +
+
+
+ +
+
+
+
+
+ +
+
+
+
+
+ + +
+
+
+
+
+
+
+
+
+
+ + + +
+
+
+ + +
+
+ +
+
+
+ + + + +
+
+
+
+
+
+
+ +
+
+
+ + + +
+ +
+
+
+ + + +
+
+
Deposits: Yb Yubileynoye, Y Yaman-Kasy, V Valentorskoye, M

Molodezhnoye, U Uzelga, O Oktyabrskoye, S Saphyanovskoye, A
Alexandrinskoye, TT Tash-Tau
Fig. 8 Wall zonation of type 2 chimneys from the Urals VMS deposits. For legend see Fig. 7
tellurides occur in chalcopyrite-pyrite-quartz transitional

members of the series.
In the Saphyanovskoye deposit, glaucodot occurs in such
chimneys whilst in the Valentorskoye deposit, the chimneys
contain Pb-rich tellurobismuthite. Chalcopyrite-pyrite-quartz
chimneys from the Molodezhnoye deposit contain altaite. In
the Yaman-Kasy deposit, the quartz-chalcopyrite-pyrite
chimneys contain disseminated frohbergite, altaite, Sb-rich
tellurobismuthite, sylvanite, sttzite and coloradoite which is
partly replaced by As, Cu, Ag-sulfosalts (e.g., (Cu,Ag)3AsS4)

related to the enargite group. In quartz-pyrite-chalcopyrite
end-members, tetrahedrite, tennantite and native gold
are common minerals. In the subzone B2, the coarsegrained chalcopyrite crystals rarely contain pyrite and
accessory mineral assemblages. These are commonly
found in subhedral chalcopyrite crystals of subzone B3.
Zone C This axial conduit zone is poorly developed in the
chalcopyrite-pyrite chimneys. The position of the axial conduit is marked by subhedral marcasite and pyrite or framboidal pyrite (Fig. 7). The open channels located in the
centre of the chalcopyrite-pyrite-quartz and quartz-pyrite
chalcopyrite chimneys are subsequently infilled with subhedral pyrite, marcasite and quartz. In quartz-rich conduits,
tetrahedrite, tennantite, digenite, and bornite occur in association with relics of chalcopyrite.
Type 2 chimneys
The chimneys range from chalcopyrite-pyrite-sphalerite
chimneys to quartz-sphalerite-pyrite-chalcopyrite barite
varieties and are most abundant in the Uralian type of the
VMS deposits (Yaman-Kasy, Uzelga-4, Molodezhnoye, and
the lower level of Saphyanovskoye). Chimneys 210 cm in
diameter and 515 cm long were recovered. Three zones
and several subzones are present in this chimney type
(Figs. 4c, d and 8).
Zone A This zone shares features with type 1 chimneys. In
chalcopyrite-pyrite-sphalerite chimneys, the outermost subzone A1 is dominated by laminated and botryoidal colloform pyrite with interstitial quartz and marcasite (Fig. 8).
However, in some chimneys from the Baymak type deposits
(e.g., Valentorskoye) aggregates of recrystallized dendritic
pyrite are predominant (Fig. 8g, h). The fine-grained pyrite
is often quite porous and may be replaced and overgrown by
coarse marcasite. In the middle part (subzone A2), granular
aggregates of pyrite and marcasite enclose very rare pseudomorphs after subhedral pyrrhotite (Figs. 6b and 8a, b, c,
e). Tetrahedral crystals of chalcopyrite, iron-free sphalerite
and sparry marcasite successively form an epitaxial incrustation on relics of fine-grained colloform pyrite. The cores
of some sphalerite crystals contain emulsion-like chalcopyrite forming chalcopyrite disease described in sphalerite
from modern black smoker chimneys (Herrington et al.
1998; Shadlun 1991). The amount of colloform pyrite and
its pseudomorphs after pyrrhotite decline with the increase
in sphalerite at the outer wall of the chimneys. The outer
wall of the sphalerite-rich end-members of this range contains mainly globular colloform, framboidal or/and dendritic
pyrite disseminated in sphalerite and cryptocrystalline quartz
(Maslennikov et al. 2009). Colloform pyrite is partly replaced
75
by anhedral sphalerite, chalcopyrite or quartz in the innermost

part of the zone. Towards the inner part of the outer wall,
coarse-grained marcasite is replaced by euhedral pyrite
enclosed in a chalcopyrite and/or quartz matrix (Fig. 6c). A
galena-tennantite-tetrahedrite assemblage is common for subzones A2 and A3. In the Molodezhnoye deposit, veinlets of
altaite were found in colloform pyrite of pyrite-chalcopyritesphalerite chimneys.
Zone B This zone can be divided into two or three parts
(Fig. 8). The first part (subzone B1) consists of mediumgrained massive or laminated chalcopyrite. Some of the chalcopyrite layers intercalate with thin interlayers of sphalerite
and/or quartz. Subhedral pyrite, marcasite and accessory minerals are common in this subzone. Subzone B2 is composed of
coarse-grained bladed inclusion-free chalcopyrite. This subzone is usually broader in the chalcopyrite-pyrite-sphalerite
members of this chimney type but is commonly absent in the
quartz-sphalerite-pyrite-chalcopyrite barite end-members.
Subzone B3 comprises spear-shaped crystals of chalcopyrite
with inclusions of disseminated pyrite and accessory minerals.
In the B1 and B3 subzones, relicts of tartan isocubanite structures are occasionally observed (Fig. 6d), as was previously
described at Yaman-Kasy (Herrington et al. 1998; Shadlun
1991). Some chimneys from the Molodeznoye, Yaman-Kasy
and Saphyanovskoye deposits contain inclusions of pyrite
pseudomorphs over euhedral pyrrhotite crystals.
In chalcopyrite-pyrite-sphalerite chimneys from the
Yaman-Kasy deposit, subzones B1 and B3 contain tellurobismuthite, occasional altaite, frohbergite and sylvanite.
Abundant and diverse rare mineral assemblages are common in sphalerite-chalcopyrite-pyrite varieties of the
chimneys. Also present are successive overgrowths of cobaltite, altaite, sylvanite, sttzite, volynskite, native tellurium, unresolved black-brown oxide-rich tellurium phases,
and galena. Petzite, empressite, coloradoite and tellurian
lllingite are present occasionally. Tellurobismuthite and
frohbergite are rare, confined to the boundaries with subzone B2. In some chimneys, Ag-sulphotellurides or finegrained unresolved Ag-Te-S micrographic phases are found.
A later assemblage comprises native tellurium and gold,
covellite, galena and a newly identified Cu, Pb, Ag, Fe
arsenic-tellurium sulphosalt phase with an approximate formula (Cu, Pb, Hg, Ag,Fe)3 (As,Te)S4. Galena and other
sulphosalts occur together in the outermost part of subzone
B1 and the innermost part of subzone B3. These sulphosalts
replace sulphoarsenides, tellurides, and galena. Mineral diversity declines in the barite-rich end member of type 2
chimneys. These quartz-sphalerite-pyrite-chalcopyrite
barite end-members of the chimney range contain mostly
very small grains of hessite, native gold, galena, volynskite,
and tennantite, which are confined to the boundaries between chalcopyrite and sphalerite. Altaite, arsenopyrite, and
76
native gold were found in association with hessite, galena

and tennantite in zone B of chalcopyrite-sphalerite-pyrite type
chimneys from the Molodezhnoye deposit. Chalcopyritepyrite-sphalerite-quartz barite chimneys from the Uzelga-4
deposit contain disseminated coloradoite, and very small
grains of tellurobismuthite and gold-rich silver telluride
(probably hessite). In the Saphyanovskoye deposit, small
grains of tellurobismuthite and hessite in association with
glaucodot and arsenopyrite have been found. Sulphoarsenides
are replaced by tennantite and tetrahedrite. Tellurides and
arsenides have been replaced by a native gold galena tennantite association in sphalerite-pyrite-chalcopyrite
chimneys, found at the upper level of the Saphyanovskoye
deposit. At the boundary with zone C, lllingite occurs in
chalcopyrite, sphalerite and quartz (Fig. 6e).
Zone C The conduits of chalcopyrite-pyrite-sphalerite
chimneys are successively in-filled by pyrite, marcasite, sphalerite and occasional quartz (Fig. 8). Quartz-sphalerite-pyritechalcopyrite barite chimneys are characterized by an
increased amount of galena, quartz and euhedral barite.
Sphalerite shows extensive chalcopyrite disease and also a
texture consistent with being a pseudomorph after wurtzite
(Herrington et al. 1998). Pseudomorphs of marcasite or pyrite
after pyrrhotite are also present in this zone (Fig. 6f). In the
chimneys from the Yaman-Kasy deposit, goldfieldite occurs
in association with a quartz-marcasite assemblage. In the
chimneys of all other deposits, sphalerite-galena-tennantite
assemblages are more common.
In chalcopyrite-pyrite-sphalerite chimneys, the Co- and
Fe-sulfoarsenides and Fe, Co, Bi, Pb-tellurides are replaced
successively by native gold and hessite, and then galenasulfosalts assemblages with generally increasing contents of
sphalerite, quartz and barite. The quartz-sphalerite-pyritechalcopyrite barite end-members of this chimney type
resemble the type 3 chimneys.
Type 3 chimneys
This chimney type ranges from chalcopyrite-sphalerite to
quartz-sphalerite -chalcopyrite barite varieties. The main
differences from the previous types are the absence of
marcasite and pyrite pseudomorphs after pyrrhotite. Pyrite
occurs as minor inclusions of euhedral, subhedral pyrite.
Colloform varieties of pyrite are very rare.
Fragments of type 3 chimneys have been collected from
the Alexandrinskoye, Tash-Tau, Jusa , Oktyabrskoye, Valentorskoye and Talganskoye deposits. The chimneys are
commonly 2-4 cm in diameter and up to 8 cm in length,
with the largest fragment measuring 10 cm in diameter and
16 cm in length. Mineralogical zones defined from the
exterior to the interior in this type of chimneys are described
below and shown on Fig. 9
Fig. 9 Wall zonation of type 3 chimneys from the Urals VMS deposits. Chimneys (d) to (f) are intermediate between Types 2 and 3. For
legend see Fig. 7
Zone A The outer wall of this zone comprises predominant

sphalerite with disseminated euhedral and subhedral pyrite
(Fig. 6g). Barite, quartz, galena and tennantite inclusions are
common for this zone. Rare colloform or framboidal pyrite
occurs only in the outermost subzone of the chimneys. Most
of the original colloform pyrite is replaced by chalcopyrite,
tennantite and galena.
Zone B This chalcopyrite-rich zone is formed by drusy
aggregates of chalcopyrite crystals, successively overgrown
by sphalerite (Fig. 6h). The chalcopyrite layers are intercalated with sphalerite. In chalcopyrite-sphalerite chimneys from
the Valentorskoye deposit, the chalcopyrite contains small
disseminated grains of Pb-rich tellurobismuthite, rare empressite and sttzite. In the central parts of this type, hessite and
native gold intergrowth occurs in association with chalcopyrite, pyrite, sphalerite and galena. In sphalerite-rich varieties
of these chimneys, galena and Te-rich tennantite are common
mineral inclusions. In the chimneys from the Oktyabrskoye
deposit, chalcopyrite contains rare inclusions of altaite, galena and euhedral pyrite. Chalcopyrite from other deposits is
devoid of accessory minerals. Some chimneys from the Alexandrinskoye deposit contain bornite inclusions in association
with euhedral pyrite.
Zone C The conduit zone consists of sphalerite, quartz and
barite. In the Oktyabrskoye deposit, sphalerite contains tellurobithmuthite, altaite, galena, and hessite inclusions in association with native gold. Galena-tennantite intergrowths in
association with native gold occur in sphalerite of the
chimneys, veinlets and conduits from both Alexandrinskoye
and Tash-Tau deposits (Maslennikova and Maslennikov 2007;
Zaykov 2006). Rare hessite in association with native gold has
been found in sphalerite chimneys from the Alexandrinskoye
deposit. Sphalerite-barite-chalcopyrite chimneys from the

Jusa deposit contain galena and tennantite only.
Composition of tellurium-bearing phases

Te-bearing sufides
We have used SEM and LA-ICP-MS techniques to investigate
the distribution of Te in the chimneys. The most detailed data
were collected by high-resolution LA-ICP-MS analyses of the
Yaman-Kasy deposit (Maslennikov et al. 2009). In this paper
we present average contents of Te in chalcopyrite, sphalerite
and pyrite in each main zone of the chimneys from other Urals
VHMS deposits (Table 3). A small number of bornite and
galena grains have also been analyzed by LA-ICP-MS.
Chalcopyrite (CuFeS2) Chalcopyrite is an important host
mineral for Te. The concentrations of Te in chalcopyrite of
the chimneys vary over several orders of magnitude between deposits: Yubileynoye (2560 ppm) Yaman-Kasy
(303200) Uzelga-4 (10250 ) Molodezhnoye (10
2050) Valentorskoye (5550) Octyabrskoye (440)
Alexandrinskoye (<145) Saphyanovskoye (130)
Tash-Tau (0.14) Jusa (<0.10.2) (Table 3). Higher concentrations and wider variations of Te contents are typical
for chalcopyrite in the chimneys from the bimodal mafic
class of VMS deposits. This chalcopyrite contains plentiful
micro-inclusions of tellurides resulting in the highest Te
contents. The lowest contents of Te occur in chalcopyrite
from the chimneys of the bimodal felsic class of VMS
deposits. Chalcopyrite in this class contains micro-inclusions
of Te-bearing tennantite only. In the Yubileynoye VMS deposit hosted in basalts, chalcopyrite has moderate contents of
Te due to nano-inclusions of silver tellurides which are observed in time-resolved LA-ICPMS analyses. Chalcopyrite
from zones B frequently displays the highest relative Te concentrations (Table 3).
Sphalerite (ZnS) Sphalerite contains significant, but lower
than chalcopyrite, concentrations of Te (Table 3). The variations of Te mean values differ between deposit types: Yubileynoye (323 ppm) Yaman-Kasy (201200) Uzelga-4
(2065) Molodezhnoye (20615) Valentorskoye (20
220) Oktyabrskoye (90365) Alexandrinskoye (0.1
16) Saphyanovskoye (0.55) Tash-Tau (0.047)
Jusa (0.10.3). Most of Te is contained in Te-rich tennantite
micro-inclusions, volynskite and hessite. Tellurobismuthite
and sylvanite micro-inclusions occur in sphalerite adjacent
to chalcopyrite.
Pyrite (FeS2) Despite the absence of detectable telluride
inclusions, pyrite displays elevated and variable concentration
77
of Te compared to chalcopyrite and sphalerite: Yubileynoye

(10185 ppm) Yaman-Kasy (8021200) Uzelga-4
(1801190) Molodezhnoye (62010700) Valentorskoye (150540) Oktyabrskoye (100695) Alexandrinskoye (20160) Saphyanovskoye (555) Tash-Tau (20
120) Jusa (0.2) (Table 3). Tellurobismuthite nanoinclusions were found in euhedral pyrite (Maslennikov et al.
2009). In colloform pyrite, the time-resolved Te signal is
smooth, suggesting that it is homogenously distributed on
the scale of individual spot analyses (Large et al. 2009).
Although such data may be interpreted as an indication for
the lattice-bound substitution of Te in the colloform pyrite,
substitution of Te2- for S2- is restricted in sulfides compared to
Se2- due to a large difference in the ionic radius between
Te2- and S2-. Thus Te commonly forms its own minerals
(tellurides, sulfotellurides, and sulfosalts) under hydrothermal conditions (e.g. Ciobanu et al. 2006). A comparison
of the LA-ICPMS data with known stoichiometric compositions of tellurides suggests the presence of sylvanite and
hessite nano-inclusions. A correlation of Te with Bi, Ag and
Au suggests co-precipitation of tellurides and pyrite. Substitution of Te for As in tennantite micro-inclusions in pyrite may
explain the Te-As correlation (Maslennikov et al. 2009).
Galena (PbS) have moderate concentration of Te up to
70 ppm (Table 3).
Fe-, Co- tellurides, Te-bearig arsenides and sulphoarsenides
Frohbergite (FeTe2) occurs in chalcopyrite-pyrite chimney
type 1 from the Yaman-Kasy deposit in association with
tellurobismuthite, sylvanite and native tellurium, and commonly forms grains between 1-50 m (Fig. 10a). A cobaltrich variety (Fe0.7Co0.3)Te2 is found as fine grains (up to
7 m) in pyrite-marcasite-chalcopyrite-quartz chimney material associated with the altaite-tellurobismuthite-coloradoite
assemblage. The cobalt-rich frohbergite belongs to the
frohbergite-mattagamite series (Co content up to 5 wt. %;
Table 4), although its Co contents are clearly lower than in
typical mattagamite (Co0.54Fe0.37)Te2. Se contents (0.17-0.29
wt. %) of frohbergite also suggest the presence of ferroselite
(FeSe2) or hastite (CoSe2) endmembers, although hastite occurrence as a separate mineral phase was discredited by
Keutsch et al. (2009). Co-rich frohbergite has elevated contents of Sb (0.60.7 wt. %) due to possible isomorphic series
CoTe2CoSb2. LA-ICPMS analyses display high concentrations of Au, Ag and Mo in some grains of frohbergite
(Table 5).
Tellurian Co- and Te-rich lllingite (Fe 0.8 Co 0.2 )
(As1.5Te0.4S0.1)2. This mineral is found as very small rhombic
crystals (up to 10 m) within chalcopyrite, quartz and sphalerite at the boundary between zones B and C in the type 2
chimneys in the Yaman-Kasy deposit (Fig. 6e). High grades
of Co suggest a substitution series with safflorite (CoAs2)
0.2 (21)
28.8 (34)
530.0 (13)
167.1 (20)
78.1 (9)
2052.1 (13)
0.2 (12)
25.4 (7)
818.6 (2)
2.0 (5)
5.9 (3)
40.0 (2)
0.9 (5)
0.7 (3)
33.4 (3)
5.3 (4)
34.2 (2)
541.2 (6)
17.2 (1)
799.5 (3)
0.8 (2)
1.9 (2)
10 (8)
46.0 (8)
1.3 (3)
0.4 (1)
24.3 (6)
52.8 (2)
57.0 (6)
693.3 (1)
66.8 (2)
38.4 (6)
1541.6 (5)
405.5 (6)
78.4 (3)
1007.4 (1)
7.9 (1)
5.0 (4)
17.8 (6)
179.5 (18)
88.2 (7)
0.2 (2)
47.0 (8)
465.1 (4)
863.1 (7)
3603.2 (5)
838.0 (14)
3.2 (7)
232.4 (5)
223.5 (2)
18.2 (4)
46.0 (2)
17.9 (7)
16.5 (4)
218.6 (5)
2.8 (5)
0.6 (3)
0.5 (1)
24.3 (7)
0.4 (5)
14.6 (8)
73.2 (7)
19.6 (8)
54.5 (6)
51.9 (10)
(10)
(7)
(7)
(12)
(9)
(13)
(14)
(10)
(8)
(8)
(12)
(8)
(3)
(10)
(16)
(14)
(15)
(11)
0.0 (6)
32.1 (15)
1585.7 (22)
3194.5(8)
28837 (4)
73.3 (11)
34.3
5.0
3.9
0.1
1.5
41.2
25.7
18.4
138.7
1047.9
344.7
960.0
1.0
27.0
30.4
188.3
27.2
0.5
3.5 (10)
Chp
0.1 (2)
15.0 (4)
102.3 (3)
411.8 (1)
20.4 (4)
6.8 (2)
364.7 (2)
0.04 (1)
3.2 (11)
296.0 (5)
15.7 (5)
52.4 (8)
616.5 (4)
0.1 (1)
22.4 (6)
3.7 (3)
0.8 (4)
23.4 (5)
Sph
Number of analyses is shown in brackets. mineral is absent. Analyses were carried out at the University of Tasmania (Hobart, Australia)
Jusa
YamanKasy
Uzelga
Alexandrinskoye
Saphyanovskoye
Molodezhnoye
Valentorskoye
3
1
2
2
3
3
29.7 (12)
37.5 (10)
281.7 (7)
119.0 (9)
42.4 (5)
160.1 (6)
150.0 (9)
440.0 (7)
555.7 (8)
620.2 (14)
1651.0 (4)
34.3 (7)
5.9 (14)
21.2 (12)
1192.2 (16)
161.8 (3)
1
1
3
3
3
23
23
23
2
2
2
2
3
2
2
2
2
1
Oktyabrskoye
TashTau
59.1 (16)
Yubileynoye
Py
Sph
Py
Chp
B zone
A zone
Chimney type
Deposit
Table 3 Mean Te contents in sulfides from each zone of each chimney type (ppm)
7.7 (7)
26.0 (6)
3849.0 (6)
21587 (3)
1652.9 (4)
186.2(10)
103.0 (1)
22.4 (3)
90.9 (2)
166.6 (5)
127.2 (5)
148.8 (9)
10734 (5)
802.5 (3)
54.1 (1)
19.8 (1)
0.2 (1)
476.3 (8)
20.8 (3)
Py
C zone
1/0 (3)
6758.5 (13)
2748.5 (4)
63.2 (6)
22.0 (1)
3.6 (2)
0.1 (1)
0.4 (3)
367.1 (5)
11.6 (1)
240.2 (2)
2061.9 (1)
11.2 (1)
7.1 (2)
1.3 (3)
3.5 (5)
249.0 (6)
26.0 (2)
29.3 (6)
8.7 (2)
Chp
0.3 (1)
38.0 (20)
1205.2 (10)
11.5 (3)
10.0 (5)
92.7 (4)
6.6 (6)
6.7 (3)
22.3 (4)
38.6 (6)
412.4 (5)
360.4 (4)
154.3 (11)
4.5 (5)
3.3 (3)
4.8 (11)
64.2 (3)
24.7 (9)
16.2 (7)
4.0 (2)
Sph
78
79
%. The calculated formula is Co1.0(As0.7Te0.2)S1.1. Some of

the high grades of Te are, probably, caused by tellurides and
native tellurium micro-inclusions. Rare homogenous areas
within this mineral, as observed in back-scattered SEM
images, were used for analysis, revealing minor amounts
of Cu, Fe, Zn, and Sb (Table 6). Their small size prevents
any crystallographic studies to determine the structure of
this mineral. The mineral merits further investigations.
Te-containing glaucodot (Co 0.48 Fe 0.57 Cu 0.12 ) 1.12
(As1.14Te0.02)1.16S (Table 6). Small white grains (< 5 m) have
been found in chalcopyrite-rich chimneys of types 1 and 2
in the Saphyanovskoye deposit. Glaucodot is commonly
associated with hessite and the late-formed tennantite and
tetrahedrite. High Fe contents may be due to isomorphic
series of allocrasite-glaucodot-arsenopyrite. Some grains
contain elevated Cu (411 wt. %) suggesting isomorphism
between glaucodot and lautite (CuAsS) series in the microinclusions of tennantite. The elevated contents of Te (0.6
1.4 wt. %) and Ag (0.21.5 wt. %) may be due to either
substitution of Te for As, or micro-inclusions of hessite.
Pb-, Bi- and Pb-Bi tellurides and related minerals
Fig. 10 Reflected light photomicrographs of tellurium mineralization

in the chimneys from the Yaman-Kasy (ad, g, h), Valentorskoye (e),
Oktyabrskoye (f) deposits. a coloradoite (Cld) in association with
altaite (Alt) and frohbergite (Frb) in chalcopyrite (Cp); b tellurobismuthite (Tbs) at the boundary of the chalcopyrite (Cp) wall with the
sphalerite (Sl) channel; c sylvanite (Syl) twins with chalcopyrite (Cp)
in the sphalerite (Sl) matrix; d telluride mineralization (volynskite (Vol),
altaite (Alt), hessite (Hs), cobaltite (Cob), native tellurium (Te)) in association with sulfides (galena (Gn), marcasite (Mrc), chalcopyrite (Cp) and
sphalerite (Sl)) and quartz (Qz); e hessite (Hs) in association with
tellurobismuthite (Tbs) or kochkarite-like minerals, galena (Gn) and gold
(Au); f native gold (Au) with hessite (Hs), tetrahedrite (Td) and galena
(Gn) in sphalerite (Sl); g crystals of goldfieldite (Gld) in quartz (Qz); h
myrmekitic intergrowths of native tellurium (Te) and silver thiotellurite
sulphosalt (Sfs)
(Table 6). Possible substitutions of As and S for Te are also

inferred from our data. Extensive mixing between lllingite
and isostructural tellurides: mattagamite, melonite and
frohhbergite has been described by Ciobanu et al. (2008).
Te-rich cobaltite-like mineral Co(S,AsTe)2 (Fig. 10d).
This mineral occurs as relics of small pink cubic crystals
included in native tellurium. Commonly, grains of the
cobaltite-like mineral are corroded and replaced by other
tellurides, making their analysis by a microprobe virtually
impossible. Contents of Te in the mineral are up to 12-15 wt.
Altaite (PbTe) is by far the most common telluride present,

usually in the form of dispersed 2-3 m grains. Larger
grains (up to 2 mm) are found adjacent to later galena in
the narrow part of zone B in type 2 chimneys from the
Yaman-Kasy and Molodezhnoye deposits (Fig. 10a, d). In
conduits of type 3 chimneys from the Oktyabrskoye deposit,
altaite occurs in sphalerite as intergrowths with hessite and
galena. Successive overgrowths and replacement of altaite
by sttzite-hessite, native tellurium and galena are common
(Fig. 7d). The altaite is slightly non-stoichiometric, containing
an excess of Te. Other trace elements in altaite include Sb and
Ag (Table 4), with the likely substitution 2b2+ Ag1+ + Sb3+.
Altaite has high concentrations of Au, Bi and Ag. This is
consistent with published data, where altaite was also identified as a Au carrier (Ciobanu et al. 2009b; Vikentyev 2006).
High concentrations of Co and As are due to micro-inclusions
of the cobaltite-like mineral.
Tellurobismuthite (Bi2Te3). Pink-white platty ctystals of
tellurobismuthite (Fig. 10b) occur in the outer and inner
parts of zone B within the chalcopyrite-rich chimneys of
types 1 and 2 in the Yaman-Kasy and Valentorskoye deposits (Fig. 7a). Tellurobismuthite contains no S (Table 7), and
is similar to occurrences of this mineral in both pyrrhotite
and chalcopyrite-pyrite ores of Uralian type VMS deposits
(Sibai, Uchaly), which contrasts with bismuth sulfotellurides
found in galena-sphalerite-rich ores of the Baimak type VMS
deposits (Moloshag et al. 2002). An excess of Te is noted in
the tellurobismuthite measured here as compared with
the theoretical formula. In the quartz-pyrite-chalcopyrite
chimneys from the Yaman-Kay deposit, Sb contents reach 7.1
80
Table 4 Chemical composition of tellurides from the low-sulphidation assemblages in the Type 2 and 3 chimneys from the Urals VMS
deposits (wt. %)
Frohbergite
N
D
Ag
1
Y
Coloradoite
N
D
Ag
8
Y
9
10
11
12
13
U
14
15
Altaite
N
D
16
Y
17
18
19
20
M
21
22
23
O
24
25
Te
82.17
81.70
81.82
81.87
81.96
82.04
81.82
Sb
0.59
0.62
0.68
0.64
Fe
12.66
12.99
12.78
13.32
17.98
17.86
18.09
Co
4.97
4.49
4.98
4.23
Se
0.25
0.19
0.22
0.19
Tl
Pd
Total
100.64
99.99
100.48
100.25
99.94
99.90
99.91
Formula
(Fe0.69Co0.26)0.95(Te1.98Se0.01Sb0.01)2
(Fe0.72Co0.23)0.95(Te1.97Se0.01Sb0.02)2
(Fe0.70Co0.26)0.96(Te1.97Se0.01Sb0.02)2
(Fe0.73Co0.22)0.95(Te1.97Se0.01Sb0.02)2
Fe1.00Te2.00
Fe1.00Te2.00
Fe1.01Te2.00
Te
Sb
Hg
Bi
Se
Tl
Pd
Total
Formula
0.07
0.16
39.82
39.94
39.80
40.78
37.86
38.28
38.97
38.53
0.55
0.32
59.00
60.13
61.04
56.88
61.84
61.13
60.91
60.83
2.13
0.10
Ag
0.34
0.34
0.44
0.19
Te
38.09
39.01
37.76
38.12
37.54
37.72
38.14
38.12
Sb
0.30
0.24
0.27
0.00
Pb
60.22
60.44
61.25
61.03
62.39
62.25
61.64
61.18
Co
0.08
Se
Tl
1.87
38.77
37.36
59.02
62.42
0.09
0.08
0.44
0.54
0.30
0.16
0.39
99.56
100.77
101.14
100.50
100.36
99.41
99.88
99.36
(Hg0.94Tl0.03Pd0.01)0.98Te1
(Hg0.96Tl0.04Pd0.01)1.01Te1
(Hg0.98Pd0.01)0.99Te1
(Hg0.87Bi0.03)0.90(Te0.99Sb0.01)1
Hg1.03(Te0.99Sb0.01)1
Hg1.02Te1
Hg0.99Te1
Hg1.00Te1
Pd
Total
99.20
100.12
99.94
99.34
99.93
99.97
99.78
99.30
Formula
(Pb0.97Ag0.01)0.98(Te0.99Sb0.01)1
(Pb0.95Ag0.01)0.96(Te0.99Sb0.01)1
(Pb0.99Ag0.01)1.00(Te0.99Sb0.01)1
(Pb0.99Ag0.01)1.00Te1.00
Pb1.02Te1
Pb1.02Te1
Pb1.01Te1
Pb0.99Te1
99.65
99.78
(Pb0.94Ag0.03)0.97Te1
Pb1.03Te1
D VMS deposits: Y Yaman-Kasy; U Uzelga; M Molodezhnoye; O Oktyabrskoye; V Valentorskoye. element has not been analysed.
Analyses were carried out: 14, 11, 12, 16, 17 by JEOL JXA 8900 RL (the University of Tasmania, Hobart, Australia); 57, 1315, 2025 inby
REMMA-2 M SEM (the Institute of Mineralogy of UB RAS), 810 inby Camebax SX50 (NHM, London, England); 1819 in JEOL JXA
8900 RL (Freiberg Mining Academy, Freiberg, Germany)
wt. %, where it substitutes for bismuth. Measured Sb and Bi

contents are consistent with experimental data for ternary
system BiSbTe (Caillat et al. 1992). Elevated contents of
Cu, S and Fe (Table 7) are likely due to analytical overlap
caused by the small grain size.(Table 8)
Kochkarite-like ISS (Ag-Pb-Bi-Sb-Te intermediate solid
solution) occurs in chalcopyrite of zone B of pyrite-sphaleritechalcopyrite chimneys in the Valentorskoye deposit. Silverwhite platy crystals of these minerals are associated with sphalerite, hessite, galena and native gold, but not with altaite
(Fig. 10e). The values of Pb are highly varied in the minerals
(Table 7). Substitution of minor Pb for Bi is widespread
throughout the group of Bi-tellurides (Cook et al. 2007b). The
phases can be considered as members of the alexite group

(Cook et al. 2007a). However the most of compiled results of
analyses display the continuous compositional range from tellurobismuthite to ruckligeite, not overlapping with the tsumoite
and tetradymite-aleksite ranges (Fig. 11a, b). Contents of S and
Se are also low in the kochkarite-like minerals.
The most varieties of the kochkarite-like minerals have
Te contents within 5659 at. %. Some of those are probably
akin to the synthetic layered compounds with formula
PbBi6Te10 and PbBi8Te13. The series of structurally related
compounds, in close compositional proximity to one another, can be potentially stacked in a disordered manner. These
compounds may belong to a homologous series
Frohbergite (2)
Tellurium oxide (1)
Sttzite (1)
Altaite (1)
Galena (2)
Minerals
Tellurobismuthite (9)
mean
max
min
Sylvanite (2)
Frohbergite (2)
Tellurium oxide (1)

Sttzite (1)
Altaite (1)
Galena (2)
5
6
7
N
1
4
5
6
7
0.20
5401
0.48
0.72
Co
0.45
3.10
0.02
5.08
6.78
4.81
60.86
21.26
0.86
2208
<0.1
0.05
32.36
97.97
2.49
1.23
<24
2.15
1.98
13.80
7.50
0.86
<0.5
<0.6
490000
542000
431000
6.97
5.36
1.53
8.67
7893
459409
495619
404833
621000
600000
832000
824000
850000
455000
372000
55.89
70.88
Mn
Bi
Te
0.68
1.12
0.24
1.41
<23
0.99
<7
2.24
4.50
1.47
<0.5
0.08
2.70
7.52
0.03
0.83
35.03
14.54
5.46
436.2
3.74
5.99
16.15
15.53
103.8
54.55
0.02
0.65
Cd
2.51
8.07
0.33
217269
227244
3.00
18.00
4.11
4709
7491
3014
130536
130248
28
26
23947
543964
5187
54
39
Ni
Au
Ag
0.99
4.16
0.11
0.55
<10
1.79
1.20
16.27
2.50
1.02
0.46
0.42
15
2312
6
<18
Sn
4406
21639
64
13444
18576
164771
164658
1496
Fe
150.67
188.00
115.00
19
15
7
8
191
2
46
5
4
27
603135
866000
866000
Sb
30568
48294
16745
10
7
43
10
2780
Pb
39.47
120.30
5.30
5.03
<27
1.44
30.08
101.9
2.97
120.0
0.28
<1.0
24
2605
1
1
Mo
4640
23984
25
16767
23856
2489
9810
2135
Cu
2.67
22.34
0.01
0.20
<4.0
<1.0
0.40
5.56
0.72
1.65
0.08
0.03
47
3579
0
1
Ba
375
1976
0
136
106
203
998
6069
Zn
1.25
4.85
0.11
0.19
0.32
0.29
<0.6
0.05
0.25
0.20
<0.1
<0.1
<15
3031.4
3.38
111.5
W
2.54
6.21
0.52
0.28
30.35
55.97
21.04
196.2
As
0.36
0.59
0.18
0.47
0.45
0.20
0.68
1.37
0.21
25.53
0.09
0.08
21.54
25.39
<3.0
0.91
Tl
5189
5971
4358
<26
14.47
<28
<34
10.22
Se
7.72
69.13
0.00
<0.10
0.05
0.06
0.00
1.56
0.04
0.00
0.00
0.00
0.17
0.19
<0.1
0.02
U
31.24
103.70
0.23
0.23
<2.3
0.39
0.03
0.61
Deposits: 1 Valentorskoye. 27 YamanKasy. Number of analyses is shown in brackets. < detection limit. Major elements are highlighted in bold. Analyses were carried out at the University of
Tasmania (Hobart., Australia)
Minerals
Tellurobismuthite (9)
mean
max
min
Sylvanite (2)
N
1
Table 5 Trace element concentrations (ppm) in accessory minerals from the paleo-hydrothermal chimneys (LA-ICP-MS)

81
Cu
As
0.93
0.59
22.72
22.33
0.49
2.90
28.64
26.87
0.45
0.48
2.01
28.01
25.88
25.80
16.62
14.18
16.84
17.67
2.19
0.27
0.27
20.03
20.10
26.97
22.79
18.68
Fe
1.51
1.88
0.00
0.00
0.0
0.0
7.07
32.14
3.96
30.72
30.76
0.35
0.28
1.94
2.30
1.44
0.60
15.01
14.78
13.53
20.87
Te
0.47
0.52
10.94
2.15
2.43
8.39
4.66
0.00
0.37
1.71
1.72
0.17
0.27
Sb
0.01
1.32
0.35
0.34
0.01
0.19
Zn
0.00
0.00
0.48
43.88
44.68
0.08
0.03
0.06
1.50
0.24
4.34
0.09
0.20
Bi
Ag
0.08
0.30
Pb
0.32
14.81
11.18
32.93
32.51
2.46
6.21
Co
0.11
0.21
0.32
Se
0.21
0.47
Au
0.00
0.00
0.54
0.39
Hg
99.91
99.79
100.25
100.80
99.87
99.81
99.78
99.39
99.90
99.92
98.77
97.79
99.05
99.30
Total
(Ag2.30Cu0.13)2.43(Te1.36Fe0.09As0.02)1.47S4
(Ag2.38Cu0.09)2.47(Te1.38Fe0.06As0.03)1.47S4
(Cu10.26Fe0.13Hg0.04Ag0.01)10.44(Te4.06Sb0.06As0.04)4.16S13
(Cu10.53Fe0.14Hg0.03)10.70(Te4.05Sb0.07As0.04)4.16S13
u9.93(Fe0.61Zn1.67Co0.13)2.41(As2.28Sb1.39Te0.04)3.71S13
u9.58(Fe0.13Zn1.87)2.00(As3.48Sb0.26Te0.03Se0.02)3.79S13
u10.28(Fe0.80Zn1.11)1.92(As3.03Sb0.31Bi0.32Te0.24)3.89S13
u11.31(Fe0.53Co0.08)0.61(As3.62Te0.27)3.89S13
(Co0.48Fe0.57Cu0.12)1.12(As1.14Te0.02)1.16S
(Co0.34Fe0.46Cu0.32Zn0.04)1.16(As1.04Te0.01)1.05S
Co0.99As0.66(Te0.21S1.10)1.31
Co0.98As0.66(Te0.21S1.11)1.32
(Fe0.88Co0.09Cu0.01)0.98(As1.66Te0.23S0.10Se0.01)2
(Fe0.75Co0.24Cu0.02Zn0.01)1.02(As1.49Te0.37S0.13Se0.01)2
Formula
D VMS deposits: Y Yaman-Kasy, S Saphyanovskoye; A Alexandrinskoye; V Valentorskoye. element has not been analysed. Analyses were carried out: 1, 2 by Camebax SX100 (the
University of Tasmania, Hobart, Australia); 3, 4, 8 by JEOL JXA 8900 RL (Freiberg Mining Academy, Freiberg, Germany); 5, 6, 7, 10, 15, 16 by REMMA-2 M SEM (the Institute of Mineralogy
of UB RAS), 812 by Camebax SX50 (NHM, London, England). Low totals for analyses 3 and, 4 are due to small sizes of the grains
10 S 40.81 11.06
Goldfieldite
11 Y 40.49
0.20
12
41.42
0.19
CuAgsulfotelluride
15 Y
1.45
0.21
16
1.03
0.40
Lllingite
1
Y
0.44 57.58
2
0.63 49.48
Cobaltite
3
Y
0.02 28.18
4
0.17 27.70
Glaucodot
5
S
4.02 44.66
6
11.36 43.00
Tennantite
7
Y 48.40 18.28
Tennantitetetrahedrite
8
A 41.83 17.92
9
V 42.17 14.65
Table 6 Chemical composition of tellurium-bearing arsenic minerals in the chimneys from the Urals VMS deposits (wt. %)
82
83
Table 7 Chemical composition of Bi-tellurides and related intermediate solid solutions (ISS) (wt. %)
n
Ag
Tellurobismuthite
1
Y
0.10
2
Y
0.10
3
Y
0.03
4
V
0.00
5
V
0.00
Sb-rich tellurobismuthite
6
Y
0.05
Pb
Bi
Sb
Te
Se
Total
Formula
0.00
0.00
0.00
0.00
0.00
51.28
51.23
51.32
52.01
51.99
0.38
0.36
0.38
0.00
0.00
49.65
49.25
49.24
47.96
47.96
0.15
0.15
0.15
0.00
0.00
0.05
0.06
0.15
0.00
0.00
101.61
101.15
101.27
99.97
99.95
(Bi1.91Ag0.01Sb0.02)1.94(Te3.03Se0.01S0.01)3.06
(Bi1.92Ag0.01Sb0.02)1.95(Te3.02Se0.01S0.01)3.05
(Bi1.91Sb0.02)1.93(Te1.93Se0.01S0.04)3.06
Bi1.99Te3.01
Bi1.99Te3.01
0.00
42.63
6.73
51.76
0.15
0.03
101.35
(Bi1.53Sb0.41)1.94(Te3.04Se0.01S0.01)3.06
7
Y
0.05
0.00
42.85
8
Y
0.12
6.12
39.04
Tetradymite
9
V
0.06
0.34
58.74
10
V
0.02
0.38
59.05
11
V
0.06
0.05
58.95
Pb-rich tellurobismuthite-kochkarite-like ISS
12
V
0.95
6.35
45.54
13
V
0.87
6.48
44.45
14
V
0.89
2.26
50.95
15
V
1.21
3.10
50.78
16
V
0.81
5.32
47.62
17
V
0.95
6.35
45.54
18
V
0.89
6.56
46.56
19
V
0.71
6.56
46.36
20
V
0.76
6.78
47.06
21
V
0.75
6.89
46.20
22
V
0.72
7.40
47.44
23
V
0.67
7.67
47.97
6.52
5.50
51.40
49.91
0.16
0.17
0.04
0.00
101.02
100.86
(Bi1.54Sb0.40)1.94(Te3.03Se0.02S0.01)3.05
(Bi1.42Ag0.01Pb0.23Sb0.34)2.00(Te2.98Se0.02)3.00
0.00
0.00
0.00
35.99
35.50
35.63
0.23
0.22
0.71
4.61
4.55
4.31
99.97
99.72
99.71
0.32
0.33
0.00
0.00
0.36
0.32
0.35
0.37
0.00
0.33
0.00
0.00
47.77
47.06
46.44
45.81
45.63
47.77
45.59
46.74
45.61
45.57
44.49
44.66
0.00
0.00
0.31
0.28
0.00
0.00
0.00
0.00
0.00
0.00
0.34
0.39
0.07
0.07
0.11
0.18
0.08
0.07
0.05
0.09
0.10
0.07
0.09
0.00
101.00
99.26
100.96
101.36
99.82
101.00
100.00
100.83
100.31
99.81
100.47
101.36
(Bi1.71Ag0.07Pb0.24Sb0.02)2.04(Te2.94S0.02)2.96
(Bi1.70Ag0.06Pb0.25Sb0.02)2.03(Te2.95S0.02)2.96
(Bi1.92Ag0.07Pb0.09)2.08(Te2.87Se0.03S0.03)2.93
(Bi1.91Ag0.09Pb0.12)2.12(Te2.82Se0.03S0.04)2.89
(Bi1.83Ag0.06Pb0.21Sb0.02)2.12(Te2.86S0.02)2.88
(Bi1.71Ag0.07Pb0.24Sb0.02)2.04(Te2.94S0.02)2.96
(Bi1.78Ag0.07Pb0.25Sb0.02)2.12(Te2.86S0.01)2.87
(Bi1.75Ag0.05Pb0.25Sb0.02)2.07(Te2.90S0.02)2.92
(Bi1.80Ag0.06Pb0.26)2.12(Te2.86S0.02)2.88
(Bi1.77Ag0.06Pb0.27Sb0.02)2.12(Te2.86S0.02)2.88
(Bi1.82Ag0.05Pb0.29)2.16(Te2.79Se0.03S0.02)2.84
(Bi1.83Ag0.05Pb0.29)2.13(Te2.79Se0.04)2.83
24
0.00
44.21
0.35
0.12
100.65
(Bi1.63Ag0.07Pb0.47)2.17(Te2.76Se0.03S0.03)2.83
1.01
12.24
42.72
(Bi1.97Pb0.01)1.98(Te1.98Se0.02)1.43S1.01
(Bi2.00Pb0.01)2.01(Te1.97Se0.02)1.41S1.00
Bi2.00(Te1.98Se0.06)1.46S0.95
ISS intermediate solid solution. D VMS deposits: Y Yaman-Kasy; V Valentorskoye. Formulaes were calculated on the basis of 5 apfu.
Analyses were carried out: 13, 911 by Camebax SX50 (NHM, London, England); 68 by Camebax SX100 (the University of Tasmania,
Hobart, Australia); 4, 5, 12 24 by JCXA JEOL 733 (the Institute of Mineralogy of UB RAS)
nPbTe.mBi2Te3, in addition to ruckligeite and kochkarite

(Karpinsky et al. 2002; Shelimova et al. 2004a), characterised by elevated values of Ag (0.59 to 1.21 wt. %) and Sb
(0.280.36 wt. %) contents (Table 7). Probably, the
kochkarite-like minerals constitute a solid solution between (Bi,Sb)2Te3 and PbTe, as considered for the same
synthetic phase (Shelimova et al. 2004b). This is in agreement with the presence of Ag in a significant proportion of
published composition for the minerals of the same group
(Cook et al. 2007a, b). Small amounts of Ag maintain a
balance of electrostatic charges, as was predicted for the
similar Pb-Bi-Sb-Te solid solution compounds from Yanahara
VMS deposit (Japan) (Kase et al. 1993). Implication of heterovalence isomorphism of b2+ Ag+ + Bi3+ unmasks a
significant role of Bi2Te3 in these compounds (Table 7). Small
access of Bi can be derived from additional BiTe layers
(Shelimova et al. 2000) or the zero-valence Bi2. Possible
involvement of zero-valence Bi2 layers precludes application

of a simple arithmetic charge-balance calculation (Cook et al.
2007b). Similar extensive solid solution has been invoked by
Bayliss (1991) and termed disoder.
LA-ICP-MS analysis of kochkarite-like ISS has shown
that they carry Au in concentration up to 8 ppm. It was
suggested that Au incorporation is underpinned by statistical
substitution of Ag and Pb into Bi octahedron in Bi-telluride
or sulfosalt structure. Gold entrapment may also be linked to
the presence of Van der Waals bonds at chalcogen-chalcogen
contacts (Ciobanu et al. 2009).
Tetradymite( Bi2Te2S) has been found in hessite in the
chalcopyrite basement of chimney structure in the Valentorskoye deposit. Tetradymite grains are associated with native
gold and Bi,Te-rich tennantite. Significant contents of Se
(0.140.71 wt. %) mark isomorphism with kawazulite,
expressing simple well-known Se for S substitution (e.g.,
Cu
Ag
Te
0.13
0.08
0.08
0.20
0.14
0.03
0.02
0.00
0.09
0.03
0.00
0.00
0.00
0.05
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.75
0.00
Hg
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.10
0.19
0.17
0.00
0.00
0.00
0.00
0.72
0.17
Pb
0.06
0.13
0.02
0.19
0.06
0.09
0.06
0.09
0.04
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Se
101.01
100.99
99.56
100.28
99.87
100.42
100.95
99.90
99.08
100.66
101.69
99.63
102.56
97.46
99.58
100.05
99.01
99.91
99.79
99.91
99.90
99.70
98.96
Total
(Ag3.57Cu0.37)3.95Te1.06S0.99
(Ag3.68Cu0.37)4.05Te0.96S0.99
(Ag3.58Cu0.48)4.06Te0.91S1.03
(Ag3.37Cu0.61)3.98Te1.03S0.98
(Ag2.82Cu1.00)3.82Te1.04S1.14
(Ag3.64Cu0.39)4.03Te0.95S1.02
(Ag3.61Cu0.41)4.02Te0.98S1.00
(Ag3.60Cu0.39)3.99Te0.97S1.04
(Ag3.64Cu0.36)4.00Te1.00S1.00
(Ag3.38Cu0.06Fe0.05)3.49(Te1.30Sb0.01)1.31S1.20
(Ag3.50Cu0.01Fe0.01)3.52(Te1.21Sb0.01)1.22S1.26
(Ag3.45Cu0.02Fe0.02)3.49(Te1.37As0.14)1.51S1.00
(Ag3.41Cu0.05Fe0.04)3.50(Te1.22Sb0.01)1.23S1.28
(Ag3.72Cu0.04Fe0.04)3.80(Te1.14Sb0.01)1.15S1.05
(Ag1.87Cu0.04Fe0.02)1.93(Te1.03Sb0.01)1.04S3.05
(Ag1.86Cu0.03Fe0.02)1.91(Te1.20As0.01Sb0.01)1.22S2.87
(Ag1.74Cu0.03Fe0.02)1.79(Te1.20As0.01)1.21S3.00
(Ag1.74Cu0.14Fe0.10)1.98(Te1.03As0.01)1.04S3.05
(Ag1.79Cu0.10Fe0.06)1.95(Te1.04As0.02)1.06S3.03
(Ag1.72Cu0.09Fe0.07)1.88(Te1.05As0.06)1.11S3.06
(Ag1.70Cu0.19Fe0.14)2.03(Te0.96As0.03)0.99S3.07
(Ag1.85Cu0.06Fe0.04Pb0.02Hg0.02)1.99Te1.21S2.82
(Ag1.92Cu0.03Fe0.02)1.97(Te1.09As0.01)1.10S2.94
Formula
Analyses were carried out: 114 by Camebax SX50 (NHM, London, England); 1523 by Camebax SX100 (the University of Tasmania, Hobart, Australia)
0.00
0.22
0.11
0.12
0.10
0.00
0.00
0.00
0.00
0.00
5.54
5.52
5.79
5.44
6.70
19
20
21
22
23
23.75
21.50
20.49
22.88
24.52
0.15
0.15
0.14
0.11
0.00
0.00
0.00
0.00
67.31
69.35
67.68
62.81
56.15
0.16
0.15
0.10
0.12
0.24
0.00
0.00
1.80
0.00
0.04
4.14
4.12
5.35
6.73
11.72
0.19
0.27
0.08
0.00
0.00
0.00
0.00
0.11
0.07
Sb
0.01
0.17
0.25
0.21
0.40
0.97
0.51
As
3
0.45
46.28
30.05
22.30
0.18
4
0.30
44.49
34.00
20.32
0.16
5
0.30
42.14
34.42
21.44
0.19
6
1.45
43.88
30.72
22.72
0.93
7
1.03
44.68
30.76
22.33
0.59
8
0.97
43.14
31.40
22.81
0.62
9
1.96
43.53
29.26
23.31
1.33
Cervelleite-like mineral Ag4-xTeS (Yaman-Kasy)
10
0.64
63.61
29.01
6.72
0.52
11
0.11
66.82
27.44
7.11
0.06
12
0.24
62.55
29.40
5.39
0.15
13
0.55
66.17
27.99
7.36
0.37
14
0.45
66.69
24.14
5.56
0.34
Cu-rich cervelleite-like mineral (Ag,Cu)4xTeS (Valentorskoye)
15
4.30
68.75
21.34
5.71
0.04
16
4.60
68.33
22.11
5.62
0.02
17
4.37
67.73
21.69
5.78
0.03
18
3.93
67.45
21.96
5.47
0.03
Fe
0.00
0.12
19.66
20.90
0.35
0.21
Silver thiotellurite - Ag2TeS3 (Yaman-Kasy)

1
0.63
43.54
33.82
2
0.36
46.11
30.93
Table 8 Chemical composition of silver thiotellurite and cervelleite-like minerals (wt. %)
84
Cook et al. 2007b). Some grains are related to plumboan

tetradymite with Pb up to 0.4 wt. %. This variety may be
considered as an initial member of an incremental chemical
series of lattice-scale homologues extending up to alexite and
then to PbBi4Te4S3 (Cook et al. 2007a). This series forms a
separate range of compositions from the above mentioned
tellurobismuthite-kochkarite-ruckligeite range (Fig. 11).
Hg, Ag-Au and Ag tellurides and related minerals
Coloradoite (HgTe) (Fig. 10a) occurs as thin disseminations
and separate pink-grey grains, 10 m in size, forming composite grains in the chalcopyrite-pyrite-quartz chimneys of
type 1 and chalcopyrite-sphalerite-pyrite-marcasite chimneys
of type 2 from the Yaman-Kasy deposit (Fig. 7c). In type 1,
coloradoite is associated with tellurobismuthite, frohbergite
and sttzite. In type 2, coloradoite grains contain greenockite,
sylvanite, sttzite, native tellurium and Hg-rich enargite. Microprobe analysis shows that both palladium-bearing and
palladium-free forms of coloradoite are present. Unusually
high contents of Tl are also noted (Table 4). Some analyses
display elevated contents of Co and Ag, due to inclusions of
frohbergite and sttzite. In the chalcopyrite-pyrite-sphalerite
chimneys of type 2 from the Uzelga deposit, coloradoite has
almost stoichiometric composition.
Sylvanite (AuAgTe4) occurs as creamy-white anhedral
grains in chalcopyrite-rich chimneys of types 1 and 2 from
the Yaman-Kasy and Valentorskoye deposits (Fig. 10c). In the
largest grains (up to 30 m), typical polysynthetic twins are
observed (Fig. 7b). Some grains are anisotropic and have
considerable bireflectance. Sylvanite was partly replaced by
grey Cu-Ag-sulphotellurides. The formula of sylvanite is close
to stoichiometric composition but some grains contain Hg
(Table 9). Sylvanite has low levels of trace elements in comparison with other tellurides. Low levels of Bi, Co, Mo, As, Pb,
Se, have been detected by LA-ICP-MS analyses (Table 5).
Sttzite (Ag5xTe3) minerals are represented by separate
grey-white grains up to 30 m in size observed in some
chalcopyrite-rich chimneys of types 1 and 2 from the
Yaman-Kasy and Valentorskoye VMS deposits. In these
deposits, sttzite is not common for barite-sphalerite-rich
chimneys of type 3 where hessite is most widespread. In
the outermost part of the tellurium-bearing chalcopyrite
zone (subzone B1), sttzite is replaced by native tellurium
and Ag-Cu arsenic sulfosalts.
According to various publications, the composition of
this phase may be as follows: Ag7Te4, Ag4.7Te3, Ag4.76Te3,
Ag3Te2, Ag12Te7, Ag5Te3 or Ag1,67Te. In the Yaman-Kasy
deposit, sttzite studied is also highly variable in composition Ag5.23Te3 to Ag4.85Te3 with an average of Ag4.9Te3
(Fig. 12). In the Valentorskoye deposit, the variations of
sttzite composition are not so pronounced (Ag5.05Te3 to
Ag4.67Te3) and the mean formula (Ag4.95Te3) is close to the
85
stoichiometric formula Ag5Te3 (Table 9). This data is in

accordance with the general formula of sttzite accepted as
Ag5xTe3 (homogenous field x00.240.36) (Echmaeva and
Osadchii 2009).
Sttzite is identified as a main carrier of Au in the
studied telluride assemblages, with Au either residing in
nano-inclusion of silvanite, or present as a lattice-bound
substitution.
Sttzite-hessite compounds (Ag1.88-xTe, where x00.02
08) are associated with sttzite in the chimneys of types 1
and 2 in the Yaman-asy deposit. In polished sections, this
almost homogenous phase differs from sttzite by a rougher
surface texture. The composition of the phase is slightly
variable over short distances, from Ag1.88Te to Ag1.76Te,
with an average formula Ag1.82Te (Fig. 12). The calculated
formula of the Ag-rich species is close to the composition of
the high-temperature -phase Ag1.88Te (Afifi et al. 1988a).
The other species display a Ag deficiency of at least 0.12
apfu. This Ag1.88-xTe phase may be akin to high-temperature
Ag1.9Te and phases unknown in nature (Karakaya
and Tompson 1991). The -phase, stable at 120460C, was
probably transformed to a fine mixture of hessite and sttzite due to cooling to less than 120 C (Afifi et al. 1988a).
The reaction Ag1.99TeAg5Te3 + Ag2Te was directly confirmed by the electromotive force (EMF) method in a recent
study (Echmaeva and Osadchii 2009).
Hessite (Ag2Te) occurs as brownish grey grains in association with native gold, tetrahedrite and galena, which are
widespread in sphalerite-rich chimneys of types 2 and 3 in
almost all deposits studied (Fig. 10e, f). In the Yubileynoye deposit, the presence of nano-inclusions of this mineral has been suggested from LA-ICP-MS analyses, only.
In most cases, the formula is very close to the stoichiometric proxy (Fig. 12, Table 9). In chimneys from the
Oktyabrskoye deposit, hessite contains elevated Au up to
0.8 wt. %, due to nano-inclusions of native gold. Isomorphic substitution of gold in hessite is also a possibility
(Echmaeva and Osadchii 2009).
Petzite (AuAg3Te2) is less common in types 1 and 2
chimneys. The associations of altaite-sylvanite and petzite are common in chimneys of type 2 from the
Yaman-Kasy deposit. The chemical composition of petzite is close to the theoretical (Table 9). Petzite is
commonly stoichiometric in association with native tellurium
(Markcham 1960).
Empressite (AgTe) is observed as small (up 5 m) grains
in chalcopyrite within zone B of type 2 chimneys, in association with hessite, sylvanite, petzite and Cu-Ag sulfosalts.
The composition of empressite is close to the theoretical,
with the exception of varieties with elevated Pb, up to 2.5
wt. %, and Hg, up to 0.18 wt. % (Table 9).
Silver thiotelluriteAg2TeS3. This Ag-Te-S phase forms a
blue-green cement in native tellurium in a micrographic
86
Table 9 Chemical compositions of silver tellurides (wt. %)

N
Ag
Sylvanite
1
Y
13.1
2
14.2
3
13.2
4
V
12.1
Sttzite
5
Y
58.38
6
57.2
7
58.63
8
V
58.4
9
58.43
10
57.70
Sttzite-hessite
11
Y
61.17
12
61.55
13
61.61
Hessite
14
Y
62.8
15
62.6
16
V
63.1
17
62.8
18
S
62.7
19
63.1
20
M
62.9
21
62.7
22
O
62.6
23
61.6
Empressite
24
Y
42.5
25
48.3
26
45.7
27
V
45.9
Petzite
28
Y
41.1
29
41.1
30
40.8
Volynskite
31
Y
17.6
32
18.1
Native tellurium
N
D
Te
33
Y
98.49
34
99.00
Tellurium hydrate
N
D
S
35
Y
0.33
36
0.40
Te
Au
63.3
62.6
63.4
62.9
41.57
42.8
41.38
41.5
41.50
42.26
Sb
Hg
Pb
Bi
Total
Formula
23.82
22.88
23.02
24.94
0.48
0.43
0.58
-
100.7
100.1
100.2
100.0
(Au0.98Ag0 98Hg0.02Cu0.02)2.00Te4
(Au0.95Ag0 97Hg0.02Cu0.02)1.96Te4
(Au0.94Ag0 98Hg0.02Cu0.02)1.96Te4
(Au1.03Ag0.91)1.94Te4
0.05
99.95
100.2
100.01
99.9
99.93
99.96
Ag1.66Te
Ag1.58Te
Ag1.68Te
Ag1.67Te
Ag1.67Te
Ag1.62Te
38.61
38.80
39.02
99.78
100.35
100.63
37.2
37.3
37.1
37.0
37.1
36.7
37.1
36.3
37.3
37.4
56.2
47.5
54.2
54.0
0.80
0.79
33.2
33.0
32.4
25.66
25.90
26.76
0.08
-
Ag1.87Te
Ag1.88Te
Ag1.87Te
1.87
1.88
1.87
-
100.0
99.9
100.2
99.8
99.9
99.8
100.0
99.8
99.9
99.8
Ag2.00Te
Ag1.99Te
Ag2.01Te
Ag2Te
Ag2Te
Ag2Te
Ag2.00Te
(Ag2.04Au0.01)2.05Te
Ag1.99Te
(Ag1.95Au0.01)1.96Te
101.3
97.3
99.9
99.9
(Ag0.89Pb0.03)0.92Te
(Ag1.19Pb0.01)1.20Te
Ag1.00Te
Ag1.01Te
100.0
99.9
100.0
(Au1.00Ag2.93)3.93Te2
(Au1.02Ag2.95)3.97Te2
(Au1.07Ag2.98)4.05Te2
0.53
4.99
34.7
28.6
98.4
99.3
0.08
-
0.26
-
0.18
-
2.52
1.10
(Ag0.91Bi0.93Sb0.02)1.86Te2
(Ag0.90Bi0.74Sb0.22)1.86Te2
45.6
47.5
Ag
0.73
0.84
S
0.22
0.15
Pb
0.11
0.04
Cu
0.52
0.23
Fe
0.21
0.13
Au
0.00
0.00
Bi
0.00
0.00
Total
100.28
100.39
Formula
Te
Te
Bi
0.17
0.20
Ag
0.39
0.42
Te
80.48
81.22
Pb
1.46
1.54
Zn
0.56
0.44
O
12.62
11.55
N
0.00
0.00
Total
96.01
95.77
Formula
TeH20
TeH20
D VMS deposits: Y Yaman-Kasy; V Valentorskoye; S Saphyanovskoye; M Molodezhnoye; O Oktyabrskoye. Analyses were carried out:
113, 3134 by Camebax SX50 (NHM, London, England); 1430, by RE2 SEM (the Institute of Mineralogy of UB RAS); 35, 36
by JEOL JXA 8900 RL (Freiberg Mining Academy, Freiberg, Germany). Low totals for analysis 31 is due to the small grain-size; for analyses 35,
36 is due to 4 wt. % of H
87
Fig. 11 Distinct compositions of the tellurobismuthite-kochkarite solid solutions in the Valentorskoye deposit compared to other similar series. Plot
(a) Ag + Pb vs Bi , plot (b) - ternary Te-Pb-Bi diagramm
texture within native tellurium in sphalerite-rich chimneys of

type 2 from the Yaman-Kasy deposit (Fig. 10h). The micrographic textures result from breakdown of unstable solid
solution of Cu-Fe-Ag-Te-S phases. Our analyses conform to
an approximate formula (Ag,Cu)2TeS3 (Table 8). In general,
the phase has almost constant composition (Fig. 13). A slight
variation in the Te/S ratio from 0.3 to 0.4 may be caused by
analytical overlap with adjacent native tellurium during analysis of small grains. A small deficit in Ag and Cu is partly
compensated by minor amounts of Fe, Hg, Pb and Bi. A small
Fig. 12 Histograms illustrating the Ag contents in the series from

hessite to sttzite, suggesting an intermediate sttzite-hessite phase
(see text for discussion)
deficit in Ag is partly compensated by other cations, resulting

in a total composition approximating (Ag,Cu,Pb,Fe)2-xTeS3.
Some studied grains contain elevated As (up to 0.93 wt. %)
and Sb (up to 0.33 wt. %). In trigonpyramidal [TeS3]2-, Te is in
a formal state of 4+, making it isoelectronic to [AsS3]3(Nguyen et al. 2010). The mineral is unknown in nature and
merits a further research (Pertlik 1997). In the current study,
the small size of grains prevents any crystallographic investigation to determine its structure.
Ag-rich cervelleite-like mineral - (Ag,Cu)4-xTeS. Minerals
of this group are isotropic with grey or dark grey colour in
reflected light. In the Yaman-Kasy deposit these minerals
occur as a net of veins in grains of sttzite and hessite.
This group is poorly studied (Voudouris et al. 2011). The
replacement features in sttzite and hessite are common for
chimneys of type 2 in the Yaman-Kasy deposit. Phases
similar in composition to benleonardite-like Ag8(Sb, As,
Te)3S3 and cervelleite-like Ag3.54Cu0.13Fe0.13Te1.06S1.13
minerals were previously described in a chimney from the
Yaman-Kasy deposit (Maslennikov et al. 1997; Maslennikov
1999). However, typical benleonardite and cervelleite are
absent in the deposit. These benleonardite-like phases have
significant, but much lower, contents of Sb, up to 2.26 wt. %,
and As, up to 1.8 wt. %, (Maslennikov et al. 1997) than
benleonardite (Stanley et al. 1986). In regards to the deficit
of Sb and As, the benleonardite-like mineral from the Yaman-
88
Fig. 13 Compositional ranges

of cervelleite-like phases. (a)
Plot of Cu vs S, (b) Plot of Cu
vs Ag, (c) Plot of Ag/(Ag + Cu)
vs Te/(Te + S)
Kasy deposit may probably be included in the same mineral

group with Ag-rich cervelleite-like minerals. The analyzed
grains of cervelleite-like minerals contain Cu ranging from 0
to 1.4 apfu (Table 8). A limited solid solution exists between Ag
and Cu. Most of cervelleite-like minerals studied have a deficiency in the cation site occupancy relative to cervelleite. Some
grains have a Te/(S + Te) ratio of~0.5, like cervelleite, however,
some grains, have a Te/(S + Te) ratio between 0.48 and 0.68 and
significant deficit in cation site occupancy relative to cervelleite
with formula Ag4TeS. Combining our data with previously
published data for cervelleite-like phases for different type of
deposits (Fig. 13), it is apparent that the cervelleite-like mineral
from the Yaman-Kasy deposit plots close to cervelleite from
other locations, but have lower contents of Cu.
Moloshag and Gulyaeva (1990) identified a mineral with
the formula close to Ag3TeS from the Gayskoye VMS deposit
in the Urals. A formula Ag3TeS was calculated for the
cervelleite-like mineral described previously (Maslennikov et
al. 1997). However, the formula displays deficit in the cation
site occupancy and the consequent inconsistency in valency
charges, if a substitution of Te2- by S2- is assumed (Novoselov
et al. 2006). This can be resolved if Te4+ is present in Ag2TeS3,
which is involved in the structure of the Ag-rich cervelleitelike mineral. Possibly, a solid solution also exists between
Ag4TeS and Ag2TeS3 which combines new compounds similar to Ag3TeS or Ag4-xTeS. This substitution may also involve
Ag2S which is a common byproduct of Ag2TeS3 formation,
resulting in addition of Ag (Nguyen et al. 2010). In
general, the cervelleite-like mineral occupies an intermediate position in a possible range Ag2TeAg4TeS
Ag3TeSAg2TeS3 (Fig. 13). Although replacement textures
are typical for this compositional series, the homogenous
areas within the cervelleite-like mineral were observed in

back-scattered SEM images, and these were used for
analyses. The layer of neutral [Ag2TeS3] may form complex chalcogenide compounds with unique structural elements, containing Te and S in different crystallographic
sites and even oxidation states as opposed to a simple
solid solution (Nguyen et al. 2010).
Cu-rich cervelleite-like mineral (Cu,Ag)4-xTeS. These
minerals are widespread in the bornite ore from the Valentoskoye deposit, where it forms the replacement rims around
hessite grains. This bornite ore is considered a product of
subseafloor alteration of clastic sulfide sediments derived
from the destruction of sulfide chimneys (Maslennikov 2006).
Some grains have a Te/(S + Te) ratio between 0.43 and
0.60 and a significant deficit in the cation site occupancy
relative to cervelleite with formula close to Ag4TeS. The
variable non-stoichiometric ratios shown by (Cu + Ag) and
(Te + S) could be either due to the presence of very thin
intergrowth of different mineral phases such as hessite and/
or other sulphotellurides (Novoselov et al. 2006), or different degrees of replacement or substitution with Cu+ and S-,
or possible interlayers of Cu2TeS3, although it was not found
as a discrete phase in the samples studied. Yarrouite Cu1.1S
is widespread in the bornite ore in association with native
gold, Te-rich tennantite, hessite and cervelleite-like mineral.
The strong correlation between Cu and S in the cervelleitelike minerals (Fig. 13, a) suggests a compositional series
between the cervelleite-like minerals and CuS may be anticipated. Likewise, the negative correlation of Ag and Cu, S and
Te (Fig. 13) may be evidence of isomorphism (Novoselov et
al. 2006). The cervelleite-like mineral has low contents of
trace elements with the exception of Se (0.050.18 wt. %)
(Table 8), Co (up to 0.3 wt. %), Hg (up to 0.08 wt. %) and Fe
(0.010.4 wt. %). The high Fe contents may point to the
presence of both Cu+ and Cu2+ in the primary sulphotellurides
(Criddle et al. 1989).
Volynskite (AgBiTe2) is a rare mineral with a grain-size of
about 36 m in types 2 and 3 chimneys from the YamanKasy deposit (Figs. 10d). Volynskite occurs close to galenamarcasite-sphalerite, native tellurium and gold assemblages,
whilst tellurobismuthite is absent. Some of the grains contain
significant Sb (up to 5 wt. %) and Pb, substituting for Bi and
Ag: Ag+ + Bi3+ Pb2+ or Ag+ + Sb3+ Pb2+ (Table 9).
Te-bearing fahlores
Te-bearing tennantite and tetrahedrite are widespread minerals in sphalerite- , barite- and quartz-rich chimneys of all
types. Tennantite varieties with As/Sb>1 are more common.
Te contents vary from 0.1 up to 4.6 wt. %. Te-rich tennatite
is widespread in the chimneys from the Yaman-Kasy, Valentorskoye, Alexandrinskoye and Saphyanovskoye deposits
(Table 6). Much higher contents of Te in tennantite are
found in the bornite ore of the Valentorskoye deposit. This
bornite ore formed due to subseafloor alteration of the
chimney fragments (Maslennikov 2006). The contents of
(As+Sb+Bi) decrease with increasing Te due to isomorphic
substitutions (Fig. 14). Cu contents in Te-bearing tennantite
are also a result of isomorphic substitutions. Fe2+ and Zn2+
substitute for Cu+ with increasing Te (Fig. 14), and there is a
distinct inverse correlation between (Fe2+ + Zn2+) and Te4+.
This is consistent with data on other Te-bearing fahlores
(Trudu and Knittel 1998).
Goldfieldite (Fig. 10g) with a calculated formula
Cu+10.22Te4+4S13 has been found as small (5 m) euhedral
crystals in the quartz-marcasite core of type 2 chimneys
Fig. 14 Composition of Tebearing tennantite and goldfieldite. Plot (a) shows different
types of covariations between
Te and (Cu + Ag). Plot (b) displays an inverse correlation of
Te vs (As + Sb + Bi), and the
position of an unknown endmember of golfieldite from the
Yaman-Kasy deposit. Plot (c)
displays an inverse correlation
of Te vs Fe + Zn
89
(Fig. 7e). The highest content of Te (32.33 wt. %) is well

above values recorded to date (24.04 wt. % in Novgorodova
et al. 1978) (Table 6). Golfieldite from the Yaman-Kasy
deposit contains Hg (0.1-0.5 wt. %). This is a common
feature of goldfieldite (Trudu and Knittel 1998). Many of
the chemical data on tetrahedrite-goldfieldite (Shimizu and
Stanley 1991) clearly deviate from stoichiometry and the
mineral is not charge balanced. It has been shown that the
substitution of (Sb, As)3+ for Te4+ in the goldfielditetetrahedrite series minerals may occur by the following
two mechanisms:
(i) Tetrahedrite, Cu10+(Cu,Fe,Zn)22+(Sb,As) 43+S13 and
goldfieldite, Cu+12(Sb,As)23+Te24+S13 form a continuous solid solution according to the coupled substitution
of Cu+Te4+ for (Cu,Fe,Zn)2+(Sb,As)3+,
(ii) Goldfieldite, Cu12+(Sb,As)23+Te24+S13 and the ideal endmember, Cu+10Te4+4S13 may also form a continuous solid
solution by the coupled substitution of [](vacancy)Te4+
for Cu+(Sb,As)3+. Therefore, the general formula of goldfieldite is Cu+12-yTe4+2+y (Sb,As)3+2-yS13, with y00-2.
This end-member was predicted by Shimizu and Stanley
(1991). A synthetic end-member goldfieldite with the
formula Cu10.23Te4.12S13 has been synthesised (KarupMller 1994). Its composition is consistent with the goldfieldite from the Yaman-Kasy chimneys.
In summary, the studied tellurium phases are characterized by unusually high Te contents compared to common
stoichiometric formula for recorded natural phases.
The correlation of Cu and Te in the formula of goldfieldite displays an inverse pattern in comparison with Terich tennantite with Te<2 apfu (Fig. 14). In goldfieldite, the
fomula coefficient of Cu decreases from 12 to 10 while Te
contents increase, and there is an appearance of vacancies in
90
the Me2+ to compensate for charge imbalance due to increased Te4+ (Trudu and Knittel 1998).
Native tellurium
Native tellurium occurs in subzones B1 and B3 (Fig. 10d).
White crystals of native tellurium occur in the innermost part
of zone B3 (Fig. 7d), where they are close to stoichiometric
composition, but contain appreciable S and Ag (Table 9).
White native tellurium may be evenly intergrown with galena
or with gray unresolved Cu, Ag-tellurium sulphosalts. At the
external boundary of chalcopyrite in zone B1 in some
chimneys of type 3, abundant grains of porous native tellurium are found intergrown with native gold. The analyzed
grains are black-brown in colour and show low totals,
possibly due to the presence of unresolved mixtures of
Te and TeO2 (O 04-13 at. %) or TeH 2O. Tellurium
hydrate is inferred based on degradation of the aggregates under vacuum conditions in the SEM. Tellurium
hydrate has elevated contents of Ag, Au, Bi, Pb, As and
Co, due to micro-inclusions of hessite, sylvanite, altaite,
volynskite and a cobaltite-like mineral. High concentrations of Cd, Sn and Zn are due to sphalerite microinclusions. No Mo-bearing phase has been identified.
Discussion
Structure of chimneys
A minimum of two structural zones have been identified in all types of sulfide chimneys: the centrifugal
external growth zone (zone A) and the centripetal internal growth zone (zones B, C). The chalcopyrite zone
B in these chimneys may have a rhythmic structure
reflecting the episodic character of hydrothermal activity. This two-zone structure is typical for many
chimneys of modern black smokers (Graham et al.
1988; Haymon 1983; Hannington and Scott 1988;
Halbach and Pracejus 1988). The two layers show the
opposite growth directions from the boundary layer
between zones A and B. Successive layers were formed
in response to the interaction of cold oxidized seawater
and hot hydrothermal fluids carrying H2S and metals
(Graham et al. 1988). The textures of sulfides in subzones A1 and A2 are very fine-grained, suggesting that
they have grown rapidly by quenching of hot fluids
interacting with cold seawater. In subzone A3, coarsegrained cubic pyrite is common, likely the result of
recrystallization of early fine-grained pyrite. Vuggy
aggregates of botryoidal and dendritic pyrite grow outwards from this zone suggesting that the chimneys had
highly permeable outer walls.
In the Yaman-Kasy material, there is little evidence for

the initial shell of anhydrite that characterizes modern chimney growth. Relict bladed pyrite textures here are interpreted
as forming by replacement of pyrrhotite. Silica is ubiquitous
as a matrix phase in many of the chimney fragments. The
broad sulfide zonation and specific location of telluriumbearing phases in the Yaman-Kasy chimneys can be interpreted in terms of extreme gradients of temperature and
oxygen and sulphur fugacities across the vent chimney
walls, as a result of interactions between high-temperature
hydrothermal fluid in the central conduit of the chimney and
cold seawater outside the external layers. Such a model
implies increasing oxidation state of the fluids from type 1
to type 3 chimneys.
Temperature conditions
The prevalence of chalcopyrite or sphalerite in certain samples of chimney likely reflects different formation temperatures. The concentration of copper in reduced, hot and acid
hydrothermal fluids of sea water salinity, displays a sharp
decrease at temperatures below 320 C (Metz and Trefry
2000), while a similar change of Zn solubility happens
below 250 C (Janecky and Seyfried 1984). Thus, chimneys
formed from moderate temperature fluids consist mainly of
sphalerite, silica and barite, and their formation is related to
conductive cooling and mixing of the hydrothermal fluid
with seawater (Halbach et al. 2003). It follows that the three
chimney types are comparable to a range of formation conditions from black to white smokers that follow a temperature gradient with some representing intermediate gray
smoker chimneys.
Temperature zonation across the sulfides of the chimneys
was assessed by using mineralogical geothermometers.
Zone A Colloform pyrite found in the outermost subzone
A1 clearly formed at low temperature (Fig. 6a) measured
decrepitation ~ 80C (Maslennikov 1999). This is consistent
with temperature measured directly from the surface of
modern active black smoker chimneys (Juniper et al. 1992;
Halbach et al. 2003). The appearance of marcasite in subzone A2 in chimneys of types 2 and 3 indicates a temperature formation < 240 C, as marcasite generally inverts to
pyrite above this temperature (Murowchick and Barnes
1986). The formation of cubic crystals of pyrite in subzone
A3 and at the boundary with zone B probably reflects an
increase of temperature relative to subzone A2. The appearance of marcasite close to subzone B3 in association with
cubic pyrite suggests that the temperature was ~ 240 C at
the boundary between zones A and B. The cobalt pyritechalcopyrite geothermometer (Eremin 1983) suggests that
pyrite formation in zones A2-A3 occurred at 110200 C
(Maslennikova and Maslennikov 2007).
Zone B No marcasite was found in all chalcopyrite-pyrite

chimneys studied, consistent with temperatures of formation >
240 C (Murowchick and Barnes 1986) for type 1 chimneys
(Fig. 6d). Coexistence of marcasite and cubic pyrite in a single
zone of chimney types 2 and 3 suggests temperatures ~
240 C. The cobalt geothermometer yields 240-260 C for
subzones B1 and B3 (Eremin 1983; Maslennikova and
Maslennikov 2007).
In the type 2 chimneys, the temperature range can be
reconstructed from the telluride composition. The -phase
(Ag1.88Te) is stable over the temperature range 120 to
460 C, but it breaks down on cooling below 120 C to
a mixture of hessite and sttzite. This assemblage is stable
at room temperature (Afifi et al. 1988a). Sylvanite, Te and
sttzite-hessite association may be useful as a geothermometer since Cabri (1965) has shown that this represents
an equilibrium assemblage in the appropriate compositional range below 330 C. Gold-rich sylvanite characterizes a
high-temperature assemblage of about 300 C. This data
may be extrapolated to suggest that only at temperatures
around 230 C and below would the ideal sylvanite (Au
23.524.2 wt. %) composition be formed. The composition of sylvanite is close to ideal in the Yaman-Kasy
deposit, suggesting the tellurium mineralization formed
between 120 and 230 C. This is in agreement with the
presence of empressite which also indicates a formation
temperature of around 210 C (Honea 1964). The favourable temperature for native gold precipitation is interpreted
to be between 150 and 200 C (Bortnikov et al. 2003;
Hannington and Scott 1989). The paragenesis of native
metals (gold, silver and tellurium), tellurides, and sulphosalts usually formed later than sulfides at temperatures of
between 130 and 200 C (Vikentyev 2006). Abundant
low-temperature, late mineral assemblages include galena
and sulphosalts, indicating fluid temperatures < 150 C
(Halbach et al. 2003).
The absence of tellurides in some chimneys of type 1
indicates that they formed at temperature above 250350 C. This is also true for some parts of zone B
(subzone B2) of type 2 chimneys. This suggests that
the first tellurides precipitated at moderate temperatures,
200-250 C, in subzone B1. Then precipitation was
inhibited by higher temperatures (subzone B2), followed
by precipitation of the latest tellurides during cooling as
hydrothermal flow declined, leading to the formation of
subzone B3. The solid solutions are common in the
chimneys indicating growth during rapid quench (Cook
et al. 2007b).
Zone C An electrum-sphalerite geothermometer (Shikazono
1985) yields temperatures of sphalerite formation at ~ 285
338C for all chimney types (Maslennikova and Maslennikov
2007) (Fig. 6e-h).
91
Fluid inclusion homogenization temperatures of quartz

infillings from type 1 chimneys in Yaman Kasy are 126
280 for quartz-chalcopyrite-pyrite chimneys of type 1
and 15-185 C for sphalerite-chalcopyrite-pyrite chimneys
of type 1 (Herrington et al. 1998; Simonov et al. 2006).
Homogenization of fluid inclusions in barite occurs at 103187 C (Herrington et al. 1998; Simonov et al. 2006).
In zone C, a ghost wurtzite structure in sphalerite was
identified by its distinctive hexagonal crystal habit. Wurtzite
is found primarily in the cores of recent active chimneys, likely
reflecting higher formation temperatures. This also may be a
feature of the kinetics of precipitation, since wurtzite seems to
be stable relative to sphalerite under conditions of active venting, but becomes unstable once venting ceases (Hannington
and Scott 1988). Wurtzite may contain significant amounts of
copper whilst the structure of sphalerite will not accommodate
copper. The occurrence of significant chalcopyrite disease in
sphalerite may be the result of inversion of wurtzite to sphalerite with expulsion of copper to form chalcopyrite.
The abundance of chalcopyrite and ISS disease in sphalerite of type 1 chimneys suggests that the assemblages were
formed at high temperature (Fouquet et al. 1993). The cores
of sphalerite grains in types 2 and 3 chimneys are higher in
Fe and Cu relative to the margins, which may reflect a
decrease in temperature during growth of sphalerite.
Thus, between zones B and A, the difference of temperatures is at least 100-200 C. This is consistent with
chimneys being formed by interaction of high temperature
fluids and cold seawater. This extreme temperature gradient
explains the appearance of tellurium mineralization at the
boundaries between the layers in zone B, characterized by
intermediate temperatures. Synchronous deposition of tellurides and growth of sulfide phases in the chimneys is
consistent with the cyclic structure of zone B.
Temperature is an important control on the stability of
HTe in hydrothermal solutions and thus on the formation
of tellurides. The stability fields of both tellurides and native
tellurium are broader at lower temperatures (Afifi et al.
1988a, b; Jaireth 1991), and we thus assume that hydrothermal tellurides precipitation at the boundaries within zone B
is due to moderate temperatures.
Sulfur fugacity f(S2)
Formation conditions for the various chimneys a summarized on a diagram f(S 2 ) versus f(Te 2 ) diagram
(Fig. 15). The diagrams at 100 and 300C show that
the topology remains similar at these temperatures (Afifi
et al. 1988a), despite some changes to the number of
phases and the absolute values of f(S2) and f(Te2). Some
telluride-sulfide-sulfosalts associations are shown in
Fig. 15, pertaining to assemblages, which could be
formed at around 200C.
92
Fig. 15 Log(Te2)log(S2) diagram indicating approximate positions

of the chimney types studied (modified after Lehmann et al. 1999; Afifi
et al. 1988a, b; Ahmad et al. 1987; Jaireth 1991; Voicu et al. 1999). The
data illustrate an increase in (Te2) within a range from Type 1 to Type
2 chimneys, followed by an increase of (S2) and decrease of (Te2)
from Type 2 to Type 3 chimneys. Abbreviations: Po pyrrhotite, Py
pyrite, Tn tennantite, Hem hematite, En enargite, Cp chalcopyrite, Bn bornite, Mgt magnetite. Names of studied deposits (Y Yaman-Kasy; Yb - Yubileinoye; O - Oktyabrskoye; M - Molodezhnoye; S - Saphyanovskoye; V - Valentorskoye; A Alexandrinskoye;
U - Uselga) and chimney types are indicated by capital letters and
numbers (1, 2, 3)
The occurrence of pseudomorphs of pyrite and marcasite

after presumed platy crystals of pyrrhotite testify to the
likely pyrite-pyrrhotite equilibrium during the earliest stages
of the mineralization process in chimneys of types 1 and 2.
The lowest f(S2) relates to the presence of frohbergite in
chimneys of type 1 and occasionally of type 2. The transition from frohbergite to pyrite suggests an increase in f(S2)
for the type 3 chimneys. The change from tellurides to AgBi-rich galena and sulphosalts documents the relative increase in f(S2) with the maximum levels constrained by
chalcopyrite and bornite + pyrite equilibrium, since bornite
is absent in chalcopyrite-telluride assemblages. The presence of tennantite and enargite in zone B, instead of arsenopyrite, lllingite and cobaltite, constrains the maximum
values of f(S2) for most of the type 3 chimneys. The transition from sylvanite and altaite to native gold and galena
assemblages suggests an increase of f(S2) with respect to
f(Te2) in type 3 chimneys.
Tellurium fugacity f(Te2)
Tellurium fugacities for chimneys of different types are shown
on the diagram of logf(S2)-logf(T2) at 200 C (Fig. 15).
Telluride-poor chalcopyrite-pyrite chimneys of type 1 (Yubileynoye and Yaman-Kasy deposits) probably formed at low
f(T2) conditions in equilibrium with pyrrhotite. Trend 1
probably displays medium oxidation of HTe- and local increase in f(Te2). The highest values of f(Te2) are indicated by
the presence of native tellurium, frohbergite and sttzite-hessite -phase (Ag1.88Te) in chimneys of types 1 and 2. The
transition from frohbergite to pyrite suggests a decline of
f(Te2) for type 3 chimneys with respect to f(S2). The occurrence
of volynskite instead of tellurobismuthite in type 2 chimneys
and the presence of native gold rather than sylvanite in chimneys
of type 3 shows a further decrease of f(Te2). This tendency is
coincident with the depletion of altaite and volynskite and the
prevalence of AgBi-rich galena in type 3 chimneys.
The appearance of native tellurium reflects the highest
activity of Te2 with logf(Te2) > 9.3 at 200 C, but the
presence of native gold in the chimneys of type 3 puts a
limit of logf(Te2) 11.1 at 200 C.
The occurrence of native gold and tellurium together in some
chimneys is rare in other natural systems, an observation not
supported by thermodynamic data (Afifi et al. 1988a, b; Jaireth
1991). In some fragments of the type 2 chimneys, a close
intergrowth of native tellurium, tellurium oxide and Au-Ag alloy
in association with cubic pyrite and galena is observed. This may
represent disequilibrium conditions during seawater alteration of
tellurides. It is assumed that the total oxidation of tellurides has
resulted in abundant isolated grains of native tellurium and
tellurium oxides at the outermost margin of zone B.
The occurrence of native gold-galena assemblages with
rare altaite and the absence of tellurides with high Te content
(frohbergite, sylvanite and tellurobismuthinite) and native
tellurium, infer a lower f(Te2) in chimneys of type 3. Thus, a
relative increase of sulphur species over HTe is seen
across the range of chimneys. This trend is inferred from
the decrease of the HTe/H2S ratio during seawater / hydrothermal fluids interaction.
Oxidation and oxygen fugacity f(O2)
The surfaces of modern chimneys are readily oxidized in
seawater. Colloform pyrite is replaced by hematite or magnetite (Fouquet et al. 1993; Graham et al. 1988; Haymon 1983).
The occurrence of hematite in zone A in some Yaman-Kasy
chimneys clearly reflects this high activity of O2, and the
absence of tellurides in this zone is explained by the unfavorably high oxidation conditions. This zone is also likely to
reflect temperatures lower than 100-225 C so Te should be
mobile as HTeO3 whilst tellurides are unstable (Jaireth
1991). Oxidation within zone A likely increases from
chimneys with chalcopyrite-rich outer walls to those with
iron-poor sphalerite-rich outer walls, since sphalerite-pyrite
association is stable at more oxidized conditions compared to
chalcopyrite-pyrite (Eremin 1983; Barton and Toulmin 1966).
The external boundary of chalcopyrite zone B is where
oxygenated cold seawater and reduced hydrothermal solutions from the chimney channel meet. This boundary in
modern chimneys is characterized by the formation of bornite and covellite after chalcopyrite oxidation (Graham et al.
1988; Haymon 1983). In the Yaman-Kasy chimneys, tellurides disappear close to where covellite is found and altaite is
replaced by galena, native Au-Ag and Te, followed by
sylvanite and sttzite-hessite. The presence of later native
tellurium likely testifies to these higher oxidation conditions
at the end of the mineralization process in the chimneys. It is
assumed that most of native tellurium is formed due to
oxidation of tellurides by seawater. However, it is possible
that some crystals of native tellurium formed as drusy infillings by the primary oxidation of hydrothermal HTe. Replacement of sylvanite, hessite-sttzite, and cobaltite by Cu,
Ag-tellurium, and arsenic sulfosalts is additional evidence
for an increase in oxidation state with falling temperature
due to seawater penetration. The later formation of tellurium
oxides, sulfosalts, and abundant barite demonstrates higher
oxidation conditions during the waning hydrothermal stage
and infilling of axial part of the channel. This is also indicated by changes in the stability fields of the minerals with
respect to f(O2) in the following order: FeTe2 CoTe2
Bi2Te3 PbS + PbTe (Afifi et al. 1988b) in the studied
range of the chimneys. This range can explain the preservation of altaite in some chimneys of type 3.
Modern black smoker chimneys show abundant evidence
for oxidation on the seafloor. The mineralogical zonation of
these chimneys has been successfully explained by a model
of seawater interaction with hydrothermal fluid (Haymon
1983). Seawater provides O2 whilst the hydrothermal fluids
contain H2S (Graham et al. 1988). The initial stage of the
deposition of tellurides in the temperature range 250200 C
can happen at lower f(O2) close to and a little below the
pyrrhotite/pyrite buffer at pH04.5. The precipitation of
gold-galena-fahlore-hessite assemblages occurs in high fluid
oxidation states close to the magnetite/hematite buffer
(Cook et al. 2009). Deposition of native tellurium occurred
in a place of cooling and oxidation of hydrothermal fluid as
suggested by thermodynamic data (Jaireth 1991; Cook et al.
2009).
Covariation of main and rare mineral assemblages
In the general range of chimneys types from 1 to 3, sphalerite, quartz, and barite contents increase relative to chalcopyrite. Across the range, Te-rich minerals pass to low-Te
species with native gold and galena-sulphosalts associations. Similar changes are attributed to the ranges of
chimneys varieties within types 1 and 2 in the YamanKasy deposit (Table 10). The best proxies for the comparison are the diverse chimneys selected from the Yaman-Kasy
and Alexandrinskoye deposits (Fig. 16). In the Yaman-Kasy
deposit, a tellurobismuthite-altaite-frohbergite assemblage
with occasional sylvanite is typical for chalcopyrite-rich
93
chimneys. The quartz-, barite- and/or sphalerite-rich

chimneys contain tennantite, tetrahedrite, and galena with
occasional altaite, native tellurium (Yaman-Kasy) or hessite
and native gold (Alexandrinskoye). The intermediate
chimneys varieties from the Yaman-Kasy deposit contain
diverse rare minerals including coloradoite, sylvanite, sttzite, empressite, hessite, volynskite, Ag-sulfotellurides with
occasional galena, native gold and later (Cu, Ag, Pb, Hg)arsenic sulfosalts.
This mineralogical change may be interpreted as being
related to decreasing temperature and f(Te2) with a relative
increase in S2 activities (Afifi et al. 1988a, b) due to mixing of
high temperature reduced hydrothermal fluids with oxygenated seawater. Simultaneous precipitation of native gold and
hessite is probably due to an increase in pH of fluids due to
mixing with alkaline oxygenated seawater. Temperatures of ~
150200C and pH ~ 68 are the most favorable conditions
for precipitation of these minerals (Bortnikov et al. 1988,
2003). Probably, these conditions were typical of sphaleriterich and marcasite-poor chimneys from all deposits studied.
Correspondence between mineral assemblages and host
rocks compositions
The mafic, bimodal mafic and bimodal felsic classes of
VMS deposits are characterized by having their own specific chimney types. The mafic hosted Yubileynoye VMS
deposit yields mainly chalcopyrite-pyrite and pyritechalcopyrite varieties containing minor sphalerite. Similar
chimneys have been found in Mesozoic Cyprus and Figaro
(California) VMS deposits (Little et al. 1999; Oudin and
Constantinou 1984). Abundant colloform pyrite is typical of
this type of chimneys. The basalt-hosted modern black
smokers are chalcopyrite-pyrite and sphalerite-chalcopyrite
varieties.
Accessory minerals are absent in most chimneys with the
exception of relic pyrrhotite in chimneys from the Yubileinoye deposit. Most of ancient and modern chimneys hosted
by basalts are lack rare minerals like tellurides. A possible
rare exception is unconfirmed Bi-telluride occurrences
(Maslennikov et al. 2010). Hydrothermal fluids were likely
under-saturated in tellurides due to high temperature and/or
reducing conditions (Maslennikov et al. 2009).
In the bimodal mafic class of VMS deposits (YamanKasy, Molodezhnoye, Uzelga, Valentorskoye), the type 2
chimneys are most common, although type 1 chimneys are
also present in the ores of the Yaman-Kasy deposit. Abundant arsenides and tellurides in chalcopyrite indicate optimal
temperature and redox conditions for their precipitation. An
exception is the chalcopyrite-pyrite variety of type 1, which
effectively lack accessory minerals likely due to high temperature and/or reducing conditions (Maslennikov et al.
2009). Type 3 chimneys occur in all VMS deposits of this
94
Table 10 Mineralogical associations of different types of
chimneys (Yaman-Kasy deposit)
(modified after Maslennikova
and Maslennikov 2007)
Minerals
Ranges into chimney types

Type 1
Pyrite FeS2 after pyrrhotite

Pyrite FeS2
Marcasite FeS2
Chalcopyrite CuFeS2
Sphalerite ZnS
Quartz SiO2
Barite BaSO4
Type 1 chimneys: 1
chalcopyrite-pyrite; 2 pyritechalcopyrite-marcasite-quartz; 3
pyrite-quartz-marcasite-chalcopyrite. Type 2 chimneys: 4
chalcopyrite-pyrite-sphaleritemarcasite; 5 sphalerite
chalcopyrite-marcasite-pyritequartz; 6 sphalerite-pyritequartz barite-chalcopyrite. ***
predominant minerals, **
subordinate minerals; * minor
or rare minerals
Co- and Te-rich lllingite (Fe0.8Co0.2)(As1.5Te0.4S0.1)

Te-rich cobaltite Co1.1(As0.8Te0.2)S1.1
Frohbergite FeTe2
Tellurobismuthite Bi2Te3
Sylvanite AgAuTe4
Petzite AuAg3Te2
Coloradoite HgTe
Sttzite Ag5Te3
Hessite Ag2Te
Empressite AgTe
Altaite PbTe
Volynskite AgBiTe2
Native tellurium Te
TeO2 + Te or TeH2O
Native gold Au0.8Ag0.2
CuAg-sulfotellurides
(CuAgHgPb)-enargite group
Goldfieldite Cu10Te4S13
Tennantite Cu10(Zn,Fe)2(As,Sb)4S13
Tetrahedrite Cu10(Zn,Fe)2(Sb,As)4S13
Greenockite CdS
Bornite u5FeS4
Galena PbS
Digenite Cu1.88S
Covellite CuS
Magnetite FeOFe2O3
class as an end-member in the range from chalcopyritepyrite-sphalerite to barite-quartz-sphalerite-pyrite-chalcopyrite varieties.

Chimneys of type 3 are dominant in the bimodal felsic class
of the VMS deposits (Alexandrinskoye, Oktyabrskoye, Jusa,
Tash-Tau). These chimneys are very similar to the barite-rich
sphalerite chalcopyrite-galena chimneys from Hokuroko
VMS deposits (Maslennikov et al. 2010). Most chimneys lack
tellurides and arsenides due to the high-sulfidation conditions,
resulting in native gold in association with tennantite, tetrahedrite and galena being most common minerals. Rare native
gold hessite-tetrahedrite-tennantite-galena assemblages occur,
Type 2
***
***
*
***
**
***
***
***
*
***
**
**
***
***
***
***
*
**
**
**
***
**
**
*
*
*
**
*
***
**
**
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
**
*
**
*
*
*
*
*
*
*
*
*
*
*
hosted by sphalerite of some chimneys from the Oktyabrskoye

and Alexandrinskoye deposits. Occurrence of tellurides in
sphalerite, instead of chalcopyrite, suggests that telluride saturation in fluids occurred at lower temperatures than in
chimneys of types 1 and 2, where tellurides are found largely
within chalcopyrite.
Our data suggest there were higher sulfidation (and oxidation) conditions of the mineralization hosted by felsic
rocks in comparison to mafic and bimodal mafic sequences.
The coherence of mineral assemblages and host rock compositions can be explained by a lower buffering potential of
felsic units, compared to mafic units, at a similar extent of
95
Fig. 16 Assemblages of
accessory minerals in a range of
chimneys: 1a
tellurobismuthite-altaitefrohbergite; 1b the same, but
with sylvanite; 2a diverse tellurides including sylvanite, coloradoite, sttzite, hessite,
altaite, volynskite, empressite in
association with galena and
(Cu, Pb, Ag, Hg)-arsenic sulfosalts of enargite group; 2b
same, but with native gold; 3a
galena-tellurium with minor
altaite; 3b same, but with native gold; 4a tennantitegalena; 4b same, but with native gold; 13 and 4a YamanKasy deposit; 4b Alexandrinskoye deposit
hydrothermal fluid / seawater interaction. This buffering

potential depends on Fe2+ contents in the rocks. The disappearance of pyrite and marcasite pseudomorphs after pyrrhotite is related to the general decrease in Fe2+ contents in
hydrothermal fluids associated with mafic to felsic hosts of
VMS deposits.
Te-bearing minerals are generally scarse in chimney material from mafic and bimodal felsic hosted VMS deposits,
but are abundant in chimney fragments from the Uralian
type VMS deposits related to bimodal mafic volcanic units.
The general Te-enrichment in bimodal mafic VMS deposits
may be explained by the contribution of Te from subducted
sediments in the Urals island arc systems. Inasmuch as the
vapour-phase affinities of Te are known (Cooke and
McPhail 2001), phase separation may be considered as a
significant factor in the concentration of Te-rich fluids.
Probably, immature magmatic-hydrothermal systems developed in the mafic units are characteristic of a lower degree
of phase separation in comparison to the bimodal mafic and
felsic volcano-magmatic sequences. On the other hand, in
felsic units, most of the tellurides may have precipitated in a
subseafloor environment due to oxidation of hydrothermal
fluids due to their interaction with oxygenated seawater.
Bimodal mafic sequences provide intermediate conditions
of hydrothermal fluid and seawater-rock interaction, likely
to be favorable not only for Te-rich fluid generation but also
for its preservation until discharge on the seafloor.
Conclusions
1. The broad sulfide zonation of chimneys, and the specific site of tellurium-bearing phases within them, can be
interpreted in terms of the extreme gradients of temperature, oxygen and sulfur fugacities across the vent
chimney walls. The position of tellurides is constrained

by intermediate temperature zones of the chimneys,
located close to the boundary of chalcopyrite zone with
sphalerite- or pyrite-marcasite-rich zones. This position,
and the higher concentration of most tellurides in narrow parts of the chalcopyrite zone, may indicate that
cooling of fluids or vapor-phase condensation are the
main processes of telluride and native tellurium precipitation. The position of tellurides is controlled by the
interplay between generally reduced, high-temperature,
sulfide-rich hydrothermal fluids and oxygenated cool
seawater. Fluids in equilibrium with pyrrhotite are
likely to be undersaturated in tellurium as displayed on
S2 vs. Te2 diagrams. High-sulfidation conditions are
also unfavorable for most of telluride formation with the
exception of hessite associated with native gold and
galena-sulfosalt assemblages.
2. In the Urals, the chimneys are ranged into Fe-Cu to CuZn-Fe and Zn-Cu types with decrease in a) isocubanite
ISS, b) colloform pyrite and marcasite and c) pseudomorphs of these after pyrrhotite, accompanied by an
increase in sphalerite, quartz and barite. Each chimney
type displays its own mineralogical characteristics with
a decrease of chalcopyrite and increase in quartz and/or
barite and talc. This general transition is accompanied
by a change from low- to high-sulfidation assemblages
and a decrease of Te solubility in hydrothermal fluids.
Tellurides are absent or rare in the Fe-Cu chimney types.
In the intermediate chimney types, a low-sulfidation
assemblage of Fe-, Co- tellurium sulfoarsenides and
Fe-, Bi-, and Pb- tellurides pass to Hg-, Ag-, and AuAg- tellurides, which are stable in moderate sulfidation
condition. The high-sulfidation assemblages (hessite,
native gold, electrum, bornite, digenite, galena, tetrtrahedrite and tennantite) are typical for the end-members
96
of the range enriched in quartz, barite and hematite

instead of magnetite. The specific change in telluriumbearing phases can be interpreted in terms of enhanced
contributions of seawater and oxidized sulphur to the
processes of mineralization.
3. The same general mineral changes are observed with the
progression from bimodal mafic- to bimodal felsichosted massive sulfide deposits: Yubileynoye
Yaman-Kasy Molodezhnoye Uzelga Valentorskoye Oktyabrskoye Alexandrinskoye TashTau Jusa. Thus, appearance of tellurides is due to not
only the degree of phase separation and the general
influence of host rocks, but is also linked to the degree
of interaction between hydrothermal fluids and seawater. This interpretation provides an explanation for the
presence or absence of tellurides in the chimneys. The
coherence of mineralogical features of the chimneys,
VMS deposits and host rocks can explain the causes
for telluride enrichment in VMS deposits of the bimodal
mafic class in terms of a model of hydrothermal fluid and
seawater interactions with the host rocks. Nevertheless,
phase separation and vapour Te-rich phase condensation
may be important processes of telluride enrichment in
some VMS deposits. It is suggested that for higher
degrees of phase separation there must be higher degrees
of magmatic and hydrothermal system maturation. If this
is correct, the discovery of tellurides in modern black and
grey smokers can be anticipated especially in bimodal
sequences, but also in some mafic and ultramafic hosted
black smokers where magmatic hydrothermal fluids may
undergo phase separation.
4. Comparative analysis of chimney textures, paragenesis
and compositional variation in tellurium-bearing minerals is a previously unrecognized petrogenetic and mineralgical tool. Further study of invisible Te-phases
located in sulfides is anticipated with the increasing use
of LA-IPMS analysis in ore petrology. High physicochemical gradients in these chimney systems, together
with conditions of rapid fluid quenching, provide unusual minerals assemblages. Unresolved Cu-Ag-Te-S
and Ag-Pb-Bi-Te-S-Se solid solutions and new sulfosalts described in this paper merit further research.
Acknowledgements The authors are grateful to John Spratt, Terry

Greenwood (Natural History Museum), Klaus Bekker (Freiberg Mining Academy), Dave Steel (University of Tasmania), Vasiliy Kotlyarov,
Evgeniy Churin (Institute of Mineralogy UB RAS) for assistance with
analytical work. Constructive comments from Cristina Ciobanu and an
anonymous reviewer helped us to improve the manuscript. The study
was supported by the Australian Research Council funding to the
Centre of Excellence in Ore Deposits (CODES); Royal Society and
the Natural History Museum; Presidium of the Russian Academy of
Sciences program N 23 (12P51003); and Russian Ministry of
Education (544/14).
References
Afifi AM, Kelly WC, Essene EJ (1988a) Phase relations among tellurides, sulfides, and oxides: I. Thermodynamical data and calculated equilibria. Econ Geol 83:377394
Afifi AM, Kelly WC, Essene EJ (1988b) Phase relations among
tellurides, sulfides, and oxides: II. Application to telluridebearing ore deposits. Econ Geol 83:395404
Ahmad M, Solomon M, Walshe JL (1987) Mineralogical and geochemical studies of the Emperor gold telluride deposit, Fiji. Econ
Geol 82:345370
Barton PB, Toulmin P (1966) Phase relations involving sphalerite in
Fe-Zn-S system. Econ Geol 61:815849
Bayliss P (1991) Crystal chemistry and crystallography of some minerals in the tetradymite group. Am Mineral 76:257265
Bortnikov NS, Cabri LJ, Vikentyev IV (2003) Invisible gold in sulfides
of modern sulfide edifices. Geol Ore Deposits 45:232245 (in
Russian)
Bortnikov NS, Kramer H, Genkin AD, Krapiva LY, Santa-Crus M
(1988) Paragenesis of gold-silver tellurides in gold deposit Florensy (Cuba). Geol Ore Deposits 30:4961, in Russian
Buschmann B, Maslennikov VV (2006) The late Ordovican or earliest
Silurian hydrothermal vent fauna from Yaman Kasy VMS deposit
(South Uralides, Russia). Palont Stratigr Fazies 14:139172
Cabri LJ (1965) Phase relations in the Au-Ag-Te system and their
mineralogical significance. Econ Geol 60:15691606
Caillat T, Carle M, Perrin D, Scherrer H, Scherrer S (1992) Study
of the Bi-Sb-Te ternary phase diagram. J Phys Chem Solids
53:227232
Ciobanu CL, Cook NJ, Spry PG (2006) Preface special issue:
telluride and selenide minerals in gold deposits how and why.
Miner Petrol 87:163169
Ciobanu CL, Cook NJ, Pring A, Damian G (2008) Another look at
nagygite from the type locality, Scrmb, Romania: replacement, chemical variation and petrogenetic implications. Mineral
Petrol 93:273307
Ciobanu CL, Pring A, Cook NJ, Self P, Jefferson D, Dima GI,
Melnikov V (2009) Crystal-structural modularity in the tetradymite group: a HRTEM study. Am Mineral 94:517534.
doi:10.2138/am.2009.2906
Cooke DR, McPhail DC (2001) Epithermal Au-Ag-Te mineralization,
Acupan, Baguio Philippines; numerical simulations of mineral
deposition. Econ Geol 96:109131
Cook NJ, Ciobanu CL, Spry PG, Voudouris P, and the participants of
IGCP-486 (2009) Understanding gold-(silver)-telluride-(selenide)
deposits. Episodes 32:249263
Cook NJ, Ciobanu CL, Stanley CJ, Paar W, Sunblad K (2007a)
Compositional data for Bi-Pb tellurosulfides. Can Mineral
45:417435. doi:10.2113/gscanmin.45.3.417
Cook NJ, Ciobanu CL, Wagner T, Stanley J (2007b) Minerals of the
system BiTeSeS related to the tetradymite archetype: review
of classification and compositional variation. Can Mineral
45:665708
Criddle AJ, Chisholm JE, Stanley CJ (1989) Cervelleite, Ag4TeS, a
new mineral from the Bambolla mine, Mexico, and a description
of a photo-chemical reaction involving cervelleite, acanthite and
hessite. Eur J Mineral 1:371380
Danyushevsky LV, Robinson R, Gilbert S, Norman M, Large R,
McGoldrick P, Shelley JMG (2011) Routine quantitative multielement analysis of sulfide minerals by laser ablation ICP-MS:
standard development and consideration of matrix effects. Geochim Explor Environ Anal 11:5160
Danyushevsky L, Robinson P, McGoldrick P, Large R, Gilbert S
(2003) LAICPMS of sulfides: Evaluation of an XRF glass disc
standard for analysis of different sulfide matrixes. 2003

Goldschmidt Conference, Japan. Geochim Cosmochim Acta 67,
18, A73 Suppl
Echmaeva EA, Osadchii EG (2009) Determination of the thermodynamic properties of compounds in the Ag-Au-Se and Ag-Au-Te
systems by the EMF method. Geol Ore Dep 51:247258
Eremin NI (1983) Differentiation of volcanogenic sulfide deposits.
Moscow state university press, Moscow, p 256, in Russian
Fouquet Y, Wafic A, Cambon P, Mevel C, Meyer C, Gente P (1993)
Tectonic setting and mineralogical and geochemical zonation in
the Snake Pit Sulfide Deposit (Mid Atlantic Ridge at 23 N). Econ
Geol 88:20182036
Franklin JM, Gibson HL, Jonasson IR, Galley AG (2005) Volcanogenic massive sulfide deposits. In: Hedenquist JW, Thompson
JFH, Goldfarb RJ, Richards JP (eds) Economic geology One
hundredth anniversary volume. 19052005. Society of Economic
Geologist, Inc, Littleton, pp 523560
Glasby GP, Prozherova IA, Maslennikov VV, Petukhov SI (2006) Jusa
and Barsuchi Log volcanogenic massive sulfide deposits from the
Southern Urals of Russia: tectonic setting, structure and mode of
formation. Resour Geol 57:2436
Grabezhev AI, Moloshag VP, Sotnikov VI, Murzin VV, Korovko AV,
Zhuxlistov AP (2001) Metasomatic aureole of Saphyanovskoye
zinc-copper deposit (Middle Urals). Petrology 9:294312 (in
Russian)
Graham UM, Bluth GJ, Ohmoto H (1988) Sulfide-sulphate chimneys
on the East Pacific Rise, 11 and 13 N latitudes. Part 1: mineralogy and paragenesis. Can Mineral 26:487504
Gusev GS, Gushchin AV, Zaykov VV, Maslennikov VV, Mezhelovsky
NV, Perevolozchnikov BV et al (2000) Geology and metallogeny
of island arcs. In: Mezhelovsky NN et al (eds) Geodynamics and
metallogeny: theory and implication for applied geology. Ministry
of Natural resources of the RF and GEOKART Ltd, Moscow, pp
213295 (in Russian)
Halbach P, Fouquet Y, Herzig P (2003) Mineralization and compositional patterns in deep-sea hydrothermal systems. In: Halbach PE,
Tunnicliffe V, Hein JR (eds) Energy and mass transfer in marine
hydrothermal systems. Dalhem University Press, Berlin, pp 85
122
Halbach P, Pracejus B (1988) Geology and mineralogy of massive ores
from Central Okinawa Trough, Japan. Econ Geol 88:22102225
Hannington MD, Scott SD (1988) Mineralogy and geochemistry of a
hydrothermal silica-sulfide -sulphate spire in the caldera of Axial
Seamount, Juan de Fuca Ridge. Can Mineral 26:603626
Hannington MD, Scott SD (1989) Sulphidation equilibria as guides to
gold mineralization in volcanogenic massive sulfides: evidence
from sulfide mineralogy and composition of sphalerite. Econ Geol
84:19781995
Haymon RM (1983) Growth history of hydrothermal black smoker
chimneys. Nature 305:695698
Herrington RJ, Maslennikov VV, Spiro B, Zaykov VV, Little CTS (1998)
Ancient vent chimney structures in the Silurian massive sulfides of
the Urals. In: Mills RA, Harrison K (eds) Modern ocean floor
processes and the geological record. Geol Soc Lond 148: 241257
Herrington R, Maslennikov V, Zaykov V, Seravkin I, Kosarev A,
Buschmann B et al (2005a) Classification of VMS deposits:
lesson from the South Uralides. Ore Geol Rev 27:203237
Herrington R, Zaykov V, Maslennikov V, Brown D, Puchkov V
(2005b) Mineral deposits of the Urals and links to geodynamic
evolution. Economic Geology: One Hundredth Anniversary Volume 10691095
Herrington RJ, Armstrong RN, Zaykov VV, Maslennikov VV, Tessalina
SG, Orgeval J-J et al (2002) Massive sulfide deposits in the South
Urals: geological setting within the framework of the Uralide orogen. In: Brown D, Juhlin C, Puchkov VN (eds) Mountain building in
the Uralides: Pangea to the present. Geophysical monograph 132.
American Geophysical Union, Washington, pp 155182
97
Honea RM (1964) Empressite and stuetzite redefined. Am Mineral
49:325338
Iizasa K, Yuasa M, Yokota S (1992) Mineralogy and geochemistry of
volcanogenic sulfides from the Myojinsho submarine caldera, the
Shichito-Iwojima Ridge, Izu-Ogasawara Arc, northwestern Pacific. Mar Geol 108:3958
Jaireth S (1991) Hydrothermal geochemistry of Te, Ag2Te and
AuTe2 in epithermal precious metal deposits. EGRU Contrib
37:121
Janecky DR, Seyfried WE (1984) Formation of massive sulfide deposits on oceanic ridge crust: incremental reaction models for mixing
between hydrothermal solutions and seawater. Geochim Cosmochim Acta 48:27232738
Juniper SK, Jonasson IR, Tunnicliffe V, Southward AJ (1992) Influence
of a tube-building polychaete on hydrothermalchimney mineralization. Geology 20:895898
Karakaya I, Thompson WT (1991) The Ag-Te (silver-tellurium) system. J of Phase Equilibria 12(1):5663
Karpinsky OG, Shelimova LE, Avilov ES, Kretova MA, Zemskov VS
(2002) X-ray diffraction study of mixed layer compounds in the
PbTe-Bi2Te3 system. Inorg Mater 38:1724
Karup-Mller S (1994) Phases and phase relations in the Cu-Te-S
system at temperatures between 350 and 900 C. N Jb Miner
Abh 166:13136
Kase K, Kusachi I, Kishi S (1993) Rucklidgeite solid-solution I the
Yanahara deposit, Japan. Can Mineral 31:99104
Keutsch FN, Frster H-J, Stanley CJ, Rhede D (2009) The discreditation of hastite, the orthorhombic dimorph of CoSe2, and observations on trogtalite, cubic CoSe2, from the type locality. Can
Mineral 47:969976
Kontar ES (2001) Condition of location and history of formation of
copper, zinc and lead in the Urals. Department of Natural resources of the Urals, Ekaterinburg, p 133, in Russian
Kontar ES, Libarova LE (1997) Metallogeny of copper, zinc, lead at
the Urals. Uralgeolcom, Ekaterinburg, p 233, in Russian
Koroteev VA, de Boorder H, Necheukhin VM, Sazonov VN (1987)
Geodynamic setting of the mineral deposits of the Urals. Tectonophys 276:91300
Large RR, Danyushevsky LD, Hollit C, Maslennikov VV, Meffre S,
Gilbert S, Bull S, Scott R, Emsbo P, Thomas H, Singh R, Foster J
(2009) Gold and trace element zonation in pyrite using a laser
imaging technique; implications for the timing of gold in orogenic
and Carlin-style sediment-hosted deposits. Econ Geol 104:635668
Lehmann B, Heinhorst J, Hein M et al (1999) The Bereznjakovskoje gold trend, Southern Urals, Russia. Mineral Deposita
34:241249
Little CTS, Herrington RJ, Maslennikov VV, Morris NJ, Zaykov VV
(1997) Silurian high-temperature hydrothermal vent community
from the southern Urals, Russia. Nature 385:36
Little CTS, Maslennikov VV, Morris NJ, Gubanov AP (1999) Two
Palaeozoic hydrothermal vent communities from the Southern
Ural Mountains, Russia. Palaeontol 42:10431078
Longerich HP, Jackson SE, Gunte D (1996) Laser ablation inductively
coupled plasma mass spectrometric transient signal data acquisition and analyte concentration calculation. J Anal At Spectrom
11:899904
Marchig V, Rsch H (1988) Mineralogical zonation and radiochronological relations in a large sulfide chimney from the East Pacific
Rise at 18 25 S. Can Mineral 26:541554
Markcham NL (1960) Synthetic and natural phases in the system AuAg-Te. Econ Geol 55:14601477
Maslennikov VV (1991) Lithological control of cupper massive sulfide
ores (after the example of Sibai and Oktyabrskoye deposits, Ural).
UB AS USSR, Sverdlovsk, p 139, in Russian
Maslennikov VV (1999) Sedimentogenesis, halmyrolysis, and ecology
of massive sulfide-bearing paleohydrothermal fields (after
98
example of the Southern Urals). Geotur press, Institute of Mineralogy of UB RAS press, Miass, p 348, in Russian
Maslennikov VV (2006) Lithogenesis and massive sulfide deposits
formation. Institute of Mineralogy of UB RAS press, Miass, p
384, in Russian
Maslennikov VV, Herrington RJ, Buslaev FP, Stanley CJ (1997)
Native tellurium, tellurides and sulfurtellurides in sulfide
chimneys of black smokers of the Yaman-Kasy Cu-Znmassive sulfide deposit (South Ural). Ural Mineral Sb 7:53
67 (in Russian)
Maslennikov VV, Lein AY, Maslennikova SP, Bogdanov YA (2010)
Phanerozoic black smokers as indicators of ore hosting complexes
contents. Lithosphere 3:153162 (in Russian)
Maslennikov VV, Maslennikova SP, Large RR, Danyushevsky LV
(2009) Study of trace element zonation in vent chimneys from
the Silurian Yaman-Kasy VHMS (the Southern Urals, Russia)
using laser ablation inductively coupled plasma mass spectrometry (LA-ICP MS). Econ Geol 104:11111141
Maslennikova SP, Maslennikov VV (2007) Sulfide chimneys of Paleozoic black smokers (after the example of Ural). UB RAS,
Ekaterinburg-Miass, p 312, in Russian
McPhail DC (1995) Thermodynamic properties of tellurium species between 25 and 350 C. Geochim Cosmochim Acta
59:851866
Metz S, Trefry JH (2000) Chemical and mineralogical influences on
concentration of trace elements in hydrothermal fluids. Geochim
Cosmochim Acta 64:22672279
Moloshag VP, Gulyaeva TYa (1990) Telluride mineralization of
the Urals massive sulfide deposits. In: Koroteev VA (ed)
Annualcollection-1989. Sverdlovsk: Institute of Geology and
Geochemistry Academy of Scoence of USSR, pp 9495, in
Russian
Moloshag VP, Grabezhev AI, Gulyaeva TY (2002) Conditions of
telluride formation in ores of the Urals massive sulfide and
copper-gold-porphyry deposits. Zap Vser Mineral Obsch 131
(5):4053, in Russian
Murowchick JB, Barnes HL (1986) Marcasite precipitation from
hydrothermal solution. Geochim Cosmochim Acta 50:2615
2629
Nguyen SL, Jang JI, Ketterson JB, Kanatzidis MG (2010) (Ag2TeS3)2A2S6 (A0Rb, Cs): layeres of silver thiotellurite intergrown
with alkali-metal polysulfides. Inorg Chem 49:90989100.
doi:10.1021/ic1011346
Novgorodova MI, Tsepin AI, Dmitrieva MT (1978) The new isomorphic series in grey ore group. Zap Vses Mineral Obsch 107:100
110 (in Russian)
Novoselov KA, Belogub EV, Zaykov VV, Yakovleva VA (2006) Silver
sulfotellurides from volcanic-hosted massive sulfide deposits in
the Southern Urals. Mineral Petrol 87:327349
Oudin E, Constantinou G (1984) Black smoker chimney fragments in
Cyprus sulfide deposits. Nature 308:349353
Paradis S, Jonasson IR, Le Cheminant GM, Watkinson DH (1988) Two
zinc-rich chimneys from the plume site, Southern Juan de Fuca
Ridge. Can Mineral 26:637654
Pertlik F (1997) Crystal structure of Ag2TeS3 and Na(Na1-xAgxTeS3 (x
0.5) and the geometry of Te(IV)S3 polyhedra. Monatsh Chem
128:157163
Peter JM, Scott SD (1988) Mineralogy, composition, and fluidinclusion microthermometry of seafloor hydrothermal deposits
in the Southern Trough of Guaymas Basin, Gulf of California.
Can Mineral 26:567587
Prokin VA, Buslaev FP (1999) Massive copper-zinc sulfide deposits in
the Urals. Ore Geol Rev 14:169

Puchkov VN (2010) Geology of the Urals and Preurals (actual questions of stratigraphy, tectonics, geodynamics, and metallogeny).
DizainPoligraphServis, Ufa, p 280, in Russian
Saphina NP, Maslennikov VV (2008) Ore clastites of the Yaman-Kasy
and Saphyanovka VMS deposits (Urals). the scientific edition.
Institute of Mineralogy of UB RAS press, Miass, p 260, in
Russian
Seravkin IB (2010) The metallogeny of the Southern Urals and the
Central Kazakhstan. Gilem, Ufa, p 281, in Russian
Shadlun TN (1942) On colloform structural ores of the Yaman-Kasy
deposit in Southern Ural. Zap Vses Mineral Obsch 3:151159 (in
Russian)
Shadlun TN (1991) Some sulfide intergrowths typical for modern
oceanic and ancient massive sulfide ores. Geol Ore Deposits
33:110118 (in Russian)
Shelimova LE, Karpinsky OG, Kosykov VI, Shestakov VA, Zemskov
VS, Kuznetsov FA (2000) Homologous series of layered
tetradymite-like compounds in Bi-Te and GeTe-Bi2Te3 systems.
J Struct Chem 41:8187
Shelimova LE, Karpinsky OG, Konstantinov PP, Avilov ES, Kretova
MA, Zemskov VS (2004a) Crystal structures and thermoelectric
properties of layered compounds in the ATe-Bi2Te3 (A0Ge, Sn,
Pb) systems. Inorg Mater 40:451460
Shelimova LE, Karpinsky OG, Svechnikova TE, Avilov ES, Kretova
MA, Zemskov VS (2004b) Synthesis and structure of layered
compounds in the PbTe-Bi2Te3 and PbTe-Sb2Te3 systems. Inorg
Mater 40:12641270
Shikazono NA (1985) Comparison of temperatures estimated from the
electrum-sphalerite-pyrite-argentite assemblage and filling temperatures of fluid implications from epithermal Au-Ag vein type
deposits in Japan // Econ Geol 80(5): 14151424
Shimizu M, Stanley CJ (1991) Coupled substitutions in goldfielditetetrahedrite minerals from the Iriki mine, Japan. Miner Mag
55:515519
Simonov VA, Kovyazin SV, Terenya EO, Maslennikov VV, Zaykov
VV, Maslennikova SP (2006) Physical-chemical parameters of
magmatic and hydrothermal processes in the Yaman-Kasy massive sulfide deposit (South Ural). Geol Ore Deposits 48:423438
(in Russian)
Stanley CJ, Criddle AJ, Chisholm JE (1986) Benleonardite, a new
mineral from the Bambolla mine, Moctezuma, Sonora, Mexico.
Miner Mag 50:681686
Tessalina SG, Bourdon B, Maslennikov VV, Orgeval J-J, Birck J-L,
Gannoun A, Capmas F, Allgre C-J (2008) Osmium isotope
distribution within the Palaeozoic Alexandrinka seafloor hydrothermal system in the Southern Urals, Russia. Ore Geol Rev
33:7080
Tessalina SG, Maslennikov VV, Surin TN (1998) Alexandrinka VMS
deposit (East Magnitogorsk paleoisland arc, Urals). Institute of
Mineralogy of UB RAS press, Miass, p 228, in Russian
Trudu AG, Knittel U (1998) Crystallography, mineral chemistry
and chemical nomenclature of goldfieldite, the tellurian member of the tetrahedrite solid-solution series. Can Mineral
36:11151137
Vikentyev IV (2006) Precious metal and telluride mineralogy of large
volcanic-hosted massive sulfide deposits in the Urals. Mineral
Petrol 87:305326
Vikentyev IV, Belenkaya YA, Ageev BI (2000) Alexandrinskoye massive sulfide polymetallic deposit (the Urals, Russia). Geol Ore
Deposits 42:248274 (in Russian)
Vikentyev IV, Yudovskaya MA, Mokhov AV, Kerzin AL, Tsepin AI
(2004) Gold and PGE in massive sulfide ore of the Uzelginsk
deposit, Southern Urals, Russia. Can Mineral 42:651665

Voicu G, Bardoux M, Jebrak M (1999) Tellurides from the Paleoproterozoic Omai gold deposit, Guiana Shield. Can Mineral 37:559
573
Voudouris P, Spry PG, Sakellaris GA, Mavrogonatos C (2011) A
cervelleite-like mineral and other Ag-Cu-Te-S minerals
[Ag2CuTeS and (Ag,Cu)2TeS] in gold-bearing veins in metamorphic rocks of the Cycladic Blueschist Unit, Kallianou,
Evia Island, Greece. Mineral Petrol 101:169183
Zaykov VV (2006) Volcanism and sulfide mounds of paleoocean
margins. Nauka, Moscow, p 428, in Russian
Zaykov VV, Shadlun TN, Maslennikov VV, Bortnikov NS (1995)
Yaman-Kasy sulfide deposit ancient black smoker of
99
Urals paleoocean. Geol Ore Deposits 37:511529 (in
Russian)
Zhabin AG, Samsonova NS (1975) Traces of disappeared pyrrhotite in
massive sulfide deposits. Zap Vses Mineral Obsch 104:346350
(in Russian)
Zierenberg RA, Koski RA, Morton JL, Bouse RM (1993) Genesis of
massive sulfide deposits on a sediment-covered spreading center,
Escanaba trough, Southern Gorda Ridge. Econ Geol 88:2069
2099
Zonenshain LP, Korinevski VG, Kazmin VG, Pecherski DM, Knain
VV, Matveenkov VV (1984) Plate tectonic model of the South
Urals development. Tectonophys 109:95135

Maslennikov 2013 - Tellurium-Bearing Minerals in Zoned Sulfide Chimneys From Cu-Zn Massive Sulfide Urals

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Maslennikov 2013 - Tellurium-Bearing Minerals in Zoned Sulfide Chimneys From Cu-Zn Massive Sulfide Urals

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Miner Petrol (2013) 107:6799

Tellurium-bearing minerals in zoned sulfide chimneys

Abstract Tellurium-bearing minerals are generally rare in

range of the Urals deposits from bimodal mafic- to bimodal

Urals have been discovered and are presented here. Diverse

Methods and samples studied

V.V. Maslennikov et al.

Geological setting and types of VMS deposits

Tellurium-bearing minerals in zoned sulfide chimneys

Fig. 1 The locations of the Urals VMS deposits with documented

Yaman-Kasy) are ascribed to either a marginal sea (Zaykov

V.V. Maslennikov et al.

Table 1 Te contents in the bulk ore (Data from open reports of

General ore mineralogy

Saphyanovskoye Baymak or Altai >300

Pyrite, chalcopyrite, sphalerite, marcasite, pyrrhotite,

mounds degraded on the seafloor (Fig. 3). The central part of

Tellurium-bearing minerals in zoned sulfide chimneys

Fig. 3 The position of sulfide

phyrrhotite, pseudomorphs of pyrite and marcasite after initial

Preservation of chimney material

Urals, the rocks of the Tagil arc are dominated by volcanic

V.V. Maslennikov et al.

Fig. 4 Type 1 (ad) and Types 23 (eh) chimneys specimens from

at the Molodezhnoye, Uzelga-4 and Valentorskoye

Tellurium-bearing minerals in zoned sulfide chimneys

Colloform pyrite grades to a vuggy, fine to medium

Fig. 6 The most important microfabrics of the chimneys studied:

V.V. Maslennikov et al.

Types of VMS deposits

Zone B The interior of the chimneys is formed by rhythmic

Deposits: Yb Yubileynoye, Y Yaman-Kasy, V Valentorskoye, M

tellurides occur in chalcopyrite-pyrite-quartz transitional

Tellurium-bearing minerals in zoned sulfide chimneys

partly replaced by As, Cu, Ag-sulfosalts (e.g., (Cu,Ag)3AsS4)

by anhedral sphalerite, chalcopyrite or quartz in the innermost

V.V. Maslennikov et al.

native gold were found in association with hessite, galena

Zone A The outer wall of this zone comprises predominant

Tellurium-bearing minerals in zoned sulfide chimneys

deposit. Sphalerite-barite-chalcopyrite chimneys from the

Composition of tellurium-bearing phases

of Te compared to chalcopyrite and sphalerite: Yubileynoye

Tellurium-bearing minerals in zoned sulfide chimneys

%. The calculated formula is Co1.0(As0.7Te0.2)S1.1. Some of

Fig. 10 Reflected light photomicrographs of tellurium mineralization

(Table 6). Possible substitutions of As and S for Te are also

Altaite (PbTe) is by far the most common telluride present,

V.V. Maslennikov et al.

wt. %, where it substitutes for bismuth. Measured Sb and Bi

phases can be considered as members of the alexite group

Tellurium oxide (1)

Tellurium oxide (1)

Tellurium-bearing minerals in zoned sulfide chimneys

Tellurium-bearing minerals in zoned sulfide chimneys

nPbTe.mBi2Te3, in addition to ruckligeite and kochkarite

involvement of zero-valence Bi2 layers precludes application

Silver thiotellurite - Ag2TeS3 (Yaman-Kasy)

Table 8 Chemical composition of silver thiotellurite and cervelleite-like minerals (wt. %)

Tellurium-bearing minerals in zoned sulfide chimneys

Cook et al. 2007b). Some grains are related to plumboan

stoichiometric formula Ag5Te3 (Table 9). This data is in

V.V. Maslennikov et al.