Carlin Type Au Rocks

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Reviews in Economic Geology, v. 20, pp. 335–363
Chapter 10
Comparison of the Allchar Au-As-Sb-Tl Deposit, Republic of Macedonia,

with Carlin-Type Gold Deposits
Sabina Strmić Palinkaš,1,† Albert H. Hofstra,2 Timothy J. Percival,3 Sibila Borojević Šoštarić,4
Ladislav Palinkaš,5 Vladimir Bermanec,5 Zoltan Pecskay,6 and Blazo Boev7
1 UiT
The Arctic University of Norway, Faculty of Science and Technology, Department of Geosciences,
Dramsvegen 201, N-9037 Tromsø, Norway
2 U.S. Geological Survey, Denver Inclusion Analysis Laboratory (DIAL), P.O. Box 25046, MS 963, Denver, Colorado 80225, USA
3 Consulting Economic Geologist, 3240 Quartzite Drive, Reno, Nevada 89523, USA
4 University of Zagreb, Faculty of Mining, Geology, and Petroleum Engineering, Pierottijeva 6, HR-10000 Zagreb, Croatia
5 University of Zagreb, Faculty of Science, Geological Department, Horvatovac 95, HR-10000 Zagreb, Croatia
6 Institute of Nuclear Research, Hungarian Academy of Sciences, Bem tér 18/C, H-4001 Debrecen, Hungary
7 Goce Delčev University, Faculty of Natural and Technical Sciences, Goce Delčev 89, MK-2000 Štip, Republic of Macedonia
Abstract
The Allchar Au-As-Sb-Tl deposit is situated in the western part of the Vardar zone, the main suture zone along
the contact between the Adriatic and the Eurasian tectonic plates. It is spatially and temporally associated with
a Pliocene (~5 Ma) postcollisional high-K calc-alkaline to shoshonitic volcano-plutonic center.
The Allchar deposit shares many distinctive features with Carlin-type gold deposits in Nevada, including
its location near a terrain-bounding fault in an area of low-magnitude extension and intense magmatism. The
mineralization is mostly hosted in calcareous sedimentary rocks at intersections of high-angle faults in perme-
able stratigraphy. The alteration types (carbonate dissolution, silicification, and argillization), ore mineralogy
(auriferous arsenian pyrite and marcasite, stibnite, realgar, orpiment, and lorandite), high Au/Ag ratios, and low
base metal contents are also typical of Carlin-type gold deposits in Nevada.
However, the Allchar deposit differs from Nevada Carlin-type gold deposits as follows: it is an isolated Au
prospect with a close spatial and temporal relationship to a shoshonitic volcano-plutonic center in a mineral belt
dominated by intrusion-related Cu-Au porphyry, skarn, and hydrothermal polymetallic deposits. The deposit is
clearly zoned (proximal Au-Sb to distal As-Tl), it has a significantly higher Tl content, trace elements in pyrite
and marcasite are homogeneously distributed, and synore dolomitization is a widespread alteration type.
Gold mineralization is most abundant in the southern part of the deposit. It occurs mostly as invisible Au in
disseminated pyrite or marcasite and as rare native Au grains. Gold mineralization is accompanied by intense
decarbonatization and silicification. Fluid inclusions and the hydrothermal alteration mineral assemblage indi-
cate that Au was deposited from hot (>200°C), saline (up to ~21 wt % NaCl equiv), moderately acidic (pH <5)
fluids that carried traces of magmatic H2S and CO2. In the calcareous host rocks, mixing of such fluids with cool,
dilute, near-neutral groundwater triggered deposition of Au and Fe sulfides. In Tertiary tuff, isocon analysis
shows that sulfidation of preexisting Fe minerals was a critical factor for deposition of Au and Fe sulfides.
Antimony mineralization prevails in the central part of the deposit, and it is mostly associated with dark-gray
to black jasperoid. Stibnite, the most common Sb mineral in the Allchar deposit, occurs as fine-grained dissemi-
nations in jasperoid and as fine- to coarsely crystalline masses that fill vugs and fracture zones lined with drusy
quartz. Fluid inclusions entrapped by stibnite-bearing jasperoid, quartz, and calcite crystals suggest that stibnite
was deposited from more dilute and cooled fluids (aqueous-carbonic fluid inclusions: 6.0–3.5 wt % NaCl equiv,
TH = 102°–125°C; aqueous fluid inclusions: 14.5 and 17.1 wt % NaCl equiv, TH = 120°–165°C).
In contrast to stibnite, As sulfides (orpiment and realgar) and Tl mineralization are associated with argillic
alteration. Fluid inclusions hosted by realgar, orpiment, dolomite, and lorandite record deposition from more
dilute (2.6–6.9 wt % NaCl equiv) and relatively cold fluids (TH = 120°–152°C) enriched in K. Isocon diagrams
show a tight link between Tl and the low-temperature argillic alteration as well as a significant correlation
between Tl and K. The spatial relationship of Tl mineralization with dolomite suggests that Tl deposition was
also promoted by neutralization of acidic fluids.
The δD and δ18O data obtained from gangue minerals and fluid inclusions indicate that magmatic fluid
mixed with exchanged meteoric water at deep levels and with unexchanged meteoric water at shallow levels
in the system. The δ13C and δ18O values of carbonate minerals and extracted fluid inclusions suggest mixing
of carbonate rock buffered fluids with magmatic and atmospheric CO2. The sulfur isotope values of early dis-
seminated pyrite and marcasite show that H2S was initially derived from diagenetic pyrite in sedimentary rocks.
In contrast, Sb and As mineralization indicate a strong input of magmatic H2S during the main mineralization
stage. Late-stage botryoidal pyrite and marcasite are depleted in 34S, which indicates a diminishing magmatic
influence and predominance of sulfur from sedimentary sources during the late-mineralization stage. Frac-
tionation of isotopically light sulfide species from isotopically heavy sulfates due to oxidation under increased
oxygen fugacity cannot be excluded.
†Corresponding author: e-mail, sabina.s.palinkas@uit.no
doi: 10.5382/rev.20.10; 29 p.
Supplementary files available online at www.segweb.org/REV20-Appendices. 335
336 STRMIĆ PALINKAŠ ET AL.
Introduction submicron gold in association with pyrite and marcasite; and

The Allchar Au-As-Sb-Tl deposit (also spelled Alshar and (6) geochemical signatures of Au, As, Hg, Sb, and Tl (Radtke,
Alšar) is situated on the northwestern slopes of the Kožuf 1985; Hofstra and Cline, 2000; Muntean et al., 2011). How-
Mountains approximately 110 km southeast from Skopje, ever, it differs from Nevada Carlin-type gold deposits in sev-
Republic of Macedonia (Fig. 1). Mining activities began ~800 eral ways, including the following: (1) it is significantly smaller
to 300 B.C. with the Ancient Greeks. In the 19th century, All- in size; (2) some of the mineralization is hosted in Tertiary
char was an important source of As for the Ottoman Empire tuff; (3) mineralization is spatially associated with shoshonitic
and in the mid-20th century it reopened as an Sb mine. Due magmatism; (4) there is a zonal distribution of metals in the
to the elevated As content in the Sb concentrate, production deposit; (5) it includes homogeneous distribution of trace ele-
ceased after fewer than 10 years. In 1980s and 1990s, the area ments in Au-bearing pyrite and marcasite; (6) dolomitization
was prospected for Tl and Au. In 1990, Percival reported a is a widespread alteration type, especially in the northern part
large Au anomaly in the central and southern portions of the of the deposit; and (7) it has high Tl content.
deposit. Allchar is estimated to contain approximately 500 t This paper summarizes new and previously published data
of Tl, making it one of the largest Tl anomalies in the world on the geotectonic evolution of the region, age constraints
(Janković and Jelenković, 1994; Percival and Radtke, 1994; provided by alteration and mineralization in volcanic rocks,
Bačeva et al., 2014). lithogeochemical characteristics of country rocks and min-
The deposit has distinctive features of Carlin-type gold eralization, chemical composition of Fe-, Sb-, As-, and Tl
deposits in Nevada such as (1) strong structural control of min- sulfides, microthermometry of fluid inclusions, and stable iso-
eralization by faults and folds; (2) temporal and spatial associ- topic compositions of ore and gangue minerals and entrapped
ation with magmatism in an extensional setting; (3) calcareous fluid inclusions. These data are used to place Allchar into the
sedimentary host rocks; (4) alteration types including decar- metallogenic evolution of the region, determine the chemistry
bonatization, silicification, argillization, and sulfidation; (5) and origin of hydrothermal fluids and processes of mineraliza-
tion, and facilitate comparison to Carlin-type gold deposits in
Nevada.
19°E 21°E 23°E
Geologic Setting
Belgrade
N
W ard
Regional geology
es ar
V
Easte
te Zo
rn n
The Allchar Au-As-Sb-Tl deposit is situated in the western

(E e
rn (In
part of the Vardar zone, in close proximity to its contact with

xt
Dr
ina
er
-Iv RKB 44°N the Pelagonian crystalline basement (Fig. 1). The Vardar zone
n
an
al
terna
jica TMC represents the main suture zone along the contact between
)
Se
the Adriatic and the Eurasian plate with elements of both

l) Var
rb
Terrain
continental and oceanic rock types (Karamata et al., 2000;

o- Mas
Di
M s
na Dimitrijević, 2001; Zelić et al., 2010; Robertson et al., 2013).

ac if
rid
dar Z
e-H
ed
It extends from northwest to southeast across the central part

ell
on
en of the Balkan Peninsula and is situated between the Dina-

one
ia
ide
n
be rides, Drina-Ivanjica terrain, Korab-Western Macedonian

lt terrain, and Pelagonian crystalline basement on the west and
the Serbo-Macedonian massif on the east (Fig. 1).
During the Late Permian to Middle Triassic, incipient rift-
ing affected metamorphosed Precambrian-Paleozoic terrains
Skopje between the Pelagonian crystalline basement and the Serbo-
Ad Sea
ria
42°N Macedonian massif. Rifting was followed by the development

Pe rys eme b-W nia
tic
of a subsiding carbonate platform and formation of oceanic

la tall nt
c
go in
ba Ko ced
crust during Late Triassic-Early Jurassic time (Sharp and

ni e
s
N Robertson, 2006; Dilek et al., 2007; Robertson et al., 2013).

an
Allchar The western (external) Vardar zone represents a complex zone

M
ra o
a
that comprises ophiolites and ophiolitic mélange (Karamata

et al., 1980). At several localities the ophiolitic masses, com-
es n te
te rr
posed of spinel lherzolite, harzburgite, and dunite, preserve

rn ai
evidence of metamorphic soles at their base. The K/Ar age

between 160 and 123 Ma (Karamata et al., 2000) and Ar/Ar
n
100 km age between 175 and 170 Ma (Borojević Šoštarić et al., 2014)
Cu-Au porphyry deposits
Pb-Zn±Ag hydrothermal deposits obtained from the metamorphic soles suggest emplacement
of the ophiolites from Middle Jurassic to Early Cretaceous.
Fig. 1. Regional geologic setting of the Allchar Au-As-Sb-Tl deposit, Repub- The Jurassic-Cretaceous mélange of the western Vardar zone
lic of Macedonia, within the Balkan Peninsula (simplified after Dimitrijević,
2001, and Karamata, 2006). The locations of the most prominent Pb-Zn ± Ag is composed of large blocks and fragments of Middle to Upper
hydrothermal and Cu-Au porphyry deposits are also marked. Abbreviations: Triassic and Upper Jurassic limestones, terrigenous sediments
RKB = Ridanj-Krepoljin belt, TMC = Timok magmatic complex. (sandstone, graywacke), basalts, and cherts with Carnian to
THE ALLCHAR DEPOSIT, REPUBLIC OF MACEDONIA 337
Norian and Upper Jurassic radiolarians within an argillaceous massif basement is at least partly composed of Precambrian
to silty matrix (Sudar and Kovacs, 2006; Vasković and Matović, gneisses and marbles (Fig. 2) that are conformably overlain by
2010). In contrast, the eastern (internal) Vardar zone consists Paleozoic metasedimentary rocks—mostly phyllites, schists,
of weakly metamorphosed mélange of Jurassic age with pre- metasandstones, and marbles. The Mesozoic metasedimen-
dominantly basaltic fragments (Sudar and Kovacs, 2006, and tary complex comprises Triassic marbles, dolostones, and
references therein). shales; Jurassic schists, quartzites, and cherts; and Cretaceous
On the Balkan Peninsula, subduction-related igneous rocks limestones and conglomerates. Upper Eocene basal conglom-
of Upper Cretaceous age are exposed in the Timok Magmatic erates are overlain by flysch sediments, late Miocene to Pleis-
Complex and Ridanj-Krepoljin belt in eastern Serbia (Fig. 1; tocene shoshonitic volcanic rocks (Yanev et al., 2008), and
Janković, 1997; Karamata et al., 1997; von Quadt et al., 2005; Pliocene lacustrine sediments (Rakičević and Pendžerkovski,
Zimmerman et al., 2008). From the beginning of the Tertiary, 1970; Mercier, 1973; Boev, 1988).
the central Balkan Peninsula was affected by collisional to
transpressive deformation followed by several postcollisional Geology of the Allchar Au-As-Sb-Tl deposit
episodes of extension (Cvetković et al., 2004). The Allchar Au-As-Sb-Tl deposit is hosted by the Meso-
Postcollisional igneous rocks of Oligocene-Pliocene age zoic metasedimentary complex and unconformable Tertiary
(29.0–1.8 Ma) occur at numerous localities along the Vardar volcanic and carbonate rocks (Fig. 3; Ivanov, 1965; Percival
zone in Serbia, Kosovo, Macedonia, and Greece (e.g., Kolios and Radtke, 1994). The southwestern flank of the district is
et al., 1980; Janković et al., 1997, Cvetković et al., 2004; Yanev bordered by tectonically emplaced Jurassic ophiolites and
et al., 2008, Lehmann et al., 2013). Magmatism occurred ophiolitic mélange (Fig. 2). The Mesozoic metasedimentary
in an extensional tectonic setting and was accompanied by complex comprises Triassic marble, dolomite, and schists that
widespread hydrothermal activity that produced numerous are products of regional greenschist facies metamorphism.
porphyry, skarn, hydrothermal polymetallic replacement, and Marble is the most abundant pre-Tertiary rock in the district
vein deposits (Fig. 1; Janković, 1995; Veselinović-Williams, and consists of gray-white to bluish-gray, fine- to medium-
2011; Borojević Šoštarić et al., 2013; Lehmann et al., 2013; grained equigranular calcite intercalated with minor detrital
Strmić Palinkaš et al., 2013). material. The dolomite is gray-white to tan, fine to medium
grained, and locally recrystallized to dolomitic marble. The
Geology of the Kožuf massif schists vary in their composition from quartz-sericite and
The Kožuf massif (Voras massif in Greece; Fig. 2) is situ- chloritic schists to graphitic schists. They are well exposed in
ated on the border between the Republic of Macedonia and the eastern part of the deposit (Percival and Radtke, 1994).
Greece. In the east, it occurs in fault contact with the Demir Tertiary dolomite is usually massive to fine grained, and it
Kapija-Gevgelija ophiolite complex (Fig. 2). In the west, it is lies above the Eocene unconformity on Mesozoic metasedi-
in fault contact with the Pelagonian massif (Fig. 1). The Kožuf mentary rocks (Fig. 3; Percival and Radtke, 1994). The
De
op
mi gelija plex
Ge e com
hio
rK
v
lit
ap
Ko ija
Z
zu
RF
-
fM
ts.
M
Allchar s. 10 km
k Mt
zja
Ko Dudica
N
41.1oN
Legend
Quaternary sediments Jurassic ophiolitic sequence
Tertiary volcanic rocks Paleozoic complex
Tertiary sediments Precambrian rocks
Tertiary tuff Trust
Mesozoic carbonates Fault
Hydrothermal mineralization
22.1 E 22.3 E
o o
21.9oE
Fig. 2. Geologic map of the Kožuf massif (simplified after Boev, 1988, and Božović et al., 2013). Abbreviations: MRFZ =
Majdan River fault zone.
338
S N
Tl
Tl Tl
Tl
Sb
Tl
Tl
Argillic alteration Stibnite-bearing jasperoid

Silicification As-Tl mineralization
B Basal unconformity
N Stage 1 Stage 2 Stage 3 Stage 4

Mineralization stage Au mineralization Sb mineralization Tl mineralization Supergene stage
Alterations:
Alluvium and glacial deposits Sb
Decarbonatization
Pliocene latite tuff Sb 41.15°N
Sb Silicification
Pliocene intrusive porphyry Argillization
Tertiary tuffaceous dolomite Dolomitization
STRMIĆ PALINKAŠ ET AL.
Triassic marble and dolomite Sulfidation
Triassic schist Supergene alteration

Minerals:
Tl Tl mine adit
Native gold
Sb Sb mine adit Pyrite
Marcasite
Stibnite
Realgar
400 m Orpiment
A Tl-sulfides/sulfosalts
Barite C
21.95°E
Fig. 3. (A) Geologic map of the Allchar Au-As-Sb-Tl district, Republic of Macedonia. (B) North-south longitudinal section through the Allchar district showing geologic,
alteration, and mineralization relationships among the northern, central, and southern portions of the district (after Percival and Radtke, 1994). (C) The paragenetic
sequence of the Allchar Au-As-Sb-Tl.
unconformity is a zone with silt- to cobble-sized rocks of mixed Pervasive silicification occurs in both pre-Tertiary and
characteristics. This porous and permeable zone is often Tertiary rocks, and its intensity varies from weak to total
altered and variably mineralized. The dolomite was deposited replacement (jasperoid). Jasperoidal silicification is typically
in a lacustrine basin and contains dispersed and intercalated composed of dark-gray to black, fine-grained, dense, micro-
tuffaceous debris. Numerous lacustrine basins were formed crystalline quartz exhibiting xenomorphic and jigsaw textures
as a result of Miocene extensional tectonism in other areas that thoroughly obliterate original textures. Less silicified
underlain by carbonate and ultramafic rocks along the Vardar rocks contain varying proportions of argillic clays and sericite
zone (Ilić Jr., 1988; Dumurdzanov et al., 2004; Jurković et al., mixed with microcrystalline quartz that are crosscut by quartz
2012). Pliocene tuffaceous volcanic and volcaniclastic rocks veinlets containing disseminated pyrite, marcasite, and rare
overlie Tertiary dolomite and Mesozoic metasedimentary crystalline masses of stibnite, realgar, and barite. This type
rocks (Fig. 3; Percival and Radtke, 1994). of silicification is most prevalent in the tuffaceous volcanic
Hypabyssal intrusions cut the Mesozoic and Tertiary rocks, rocks and volcaniclastic horizons in the Tertiary carbonate
except the Pliocene tuffaceous units that are probably con- sequence.
temporaneous with the intrusions. The intrusions are typically Argillic and sericitic alterations are voluminous and occur in
porphyritic and intensely altered. They range in composition volcanic and sedimentary rocks. Alteration is pervasive adja-
from latite to andesite and commonly contain significant cent to faults and silicified zones and is strong in the Tertiary
amounts of sulfides. Similar hydrothermally altered intrusions tuffs and tuffaceous dolomites. Argillic assemblages typically
occur in the underground antimony and arsenic-thallium envelope silicified zones decreasing in intensity with increas-
mines (Fig. 3; Percival and Radtke, 1994). ing distance from silicification (Fig. 3). X-ray diffraction stud-
N-, NW-, and NE-trending, steeply dipping fault sets in the ies of the clay-altered rocks indicate that they contain varying
Allchar deposit (Fig. 2) are characterized by sheared, brecci- proportions of the following minerals: kaolinite, sericite, illite-
ated, and fractured wall rocks, stratigraphic juxtaposition, and group minerals (including celadonite), hydromicas, pyrophyl-
topographic discontinuities and are commonly the locus of lite, and subordinate chlorite (Percival and Radtke, 1994).
intense hydrothermal alteration and variable sulfide deposi- Dolomitization of Triassic marble is spatially associated
tion. The Majdan River fault zone and associated N-trending with mineralization (Fig. 3). Dolomitized rocks are typically
structures (Fig. 2) located to the west of the antimony mines lighter colored than the host marble and transitionally grade
are defined by a major topographic discontinuity between per- into undolomitized marble (Percival and Radtke, 1994).
vasively altered and mineralized cliff-like outcrops of carbon- Supergene alteration is widespread and typical of humid
ate rocks to the east and glacial till-covered, low-relief, rolling environments. Pyrite and marcasite are replaced by Fe oxides
hills to the west. This structure is believed to have originated and hydroxides; As, Sb, and Tl sulfides form oxides; and igne-
from north-south strike-slip movement along the Vardar zone. ous and sedimentary rocks are converted to mixtures of sec-
The NW- and NE-trending structures formed as dilational con- ondary clay minerals.
jugate sets of faults in response to the north-south shearing.
These faults are the most intensely brecciated and crackled car- Mineralization
bonate rocks in the district and provided permeability and open Mineralization in the Allchar deposit is zoned (Fig. 3). The
spaces that facilitated movement of hydrothermal fluids. southern part of the deposit is characterized by significant
amounts of siliceous Au mineralization. The Au content
Hydrothermal alteration decreases northward. In the central part of the deposit, Sb-
In the Allchar deposit, hydrothermal alteration is widespread bearing jasperoid prevails. The northernmost part of the
and has a zonal distribution relative to the mineralization (Fig. deposit is characterized by As- and Tl-bearing minerals in
3). The principal alteration types include (1) carbonate dis- strongly altered rocks.
solution (decarbonatization), (2) silicification, (3) argillization, Gold mineralization is hosted in weakly to moderately silici-
(4) dolomitization, (5) sulfidation, and (6) supergene altera- fied Tertiary tuffs and Triassic marbles (Fig. 4A). Silicified
tion of sulfide minerals (Janković, 1993; Percival and Radtke, ore contains finely disseminated pyrite with minor amounts
1993a, 1994). of stibnite, marcasite, and realgar. Gold occurs as submicron
Carbonate dissolution (decarbonatization) represents the invisible Au in disseminated pyrite or marcasite (Fig. 4B) or
earliest type of hypogene alteration. It affected Triassic and as rare native micron-sized grains (Fig. 4C). Gold grades are
Tertiary carbonate rock types, resulting in the removal of variable and commonly vary from 0.5 to 10 g/t Au (Percival
calcite and dolomite with resultant increases in porosity and and Radtke, 1994).
permeability. Decarbonatization is typically accompanied by Stibnite-bearing jasperoids were mined extensively for
silicification and argillization, and it exhibits a lateral transi- their Sb content (Janković, 1979). The jasperoids are dark-
tion from fresh to bleached, partially altered, and completely gray to black and are composed of fine-grained, mosaic-tex-
altered rocks. In places, Tertiary dolomite was decarbon- tured microcrystalline quartz (Fig. 5A). Most jasperoids are
atized without accompanying silicification. Decarbonatization fractured and brecciated and contain veinlets and irregular
resulted in dissolution of the fine-grained carbonate matrix, masses of coarser crystalline, gray to white quartz. The micro-
leaving predominantly granular dolomite sand, iron oxides, crystalline quartz matrix contains finely disseminated sulfides
jarosite, and greenish to yellowish unidentified secondary (1–5%), fine-grained sericite, and silicified host-rock clasts
minerals. Similar textures have been described in other Car- containing sericite and sulfides. Pyrite is commonly the most
lin-type deposits hosted in dolomite (e.g., Hofstra and Cline, abundant sulfide mineral. It occurs as fine (<0.5 mm) dissemi-
2000; Cline et al., 2003, 2005). nated grains, larger (>0.5 mm) subhedral to euhedral crystals,
A 1m
Au
Py
Au
Py
0.1 mm 100 µm
B C
Fig. 4. (A) Silicified Tertiary tuff in the southern part of the Allchar Au-As-Sb-Tl deposit. (B) Reflected-light photomicro-
graph of the siliceous Au mineralization. Gold occurs as invisible Au, usually as an enrichment in disseminated pyrite or
marcasite. (C) Scanning electron photomicrograph of rare individual Au grains disseminated within silicified tuff. Abbrevia-
tions: Py = pyrite.
and aggregates of coarse-grained crystals. Sparse, finely crys- (Fig. 7A). The most prominent Tl mineralization is con-
talline arsenopyrite, marcasite, and stibnite are also present centrated within the Crven Dol orebody (Ivanov, 1986;
(Fig. 5B). The later coarse sulfide stage is characterized by Janković, 1993; Janković and Jelenković, 1994). This part
coarse-grained sulfide minerals occurring as linings and infill- of the deposit is strongly affected by argillic alteration. The
ings of open spaces in breccia and fracture zones within jas- mineralization is composed of mixtures of orpiment, real-
peroidal silica. Marcasite and pyrite occur in banded veins gar, pyrite, marcasite, lorandite (TlAsS2), and rare Tl-bear-
and as botryoidal masses (Fig. 5C). Late stibnite occurs as ing sulfosalt minerals including vrbaite (Tl4Hg3Sb2As8S20),
fine to coarsely crystalline masses, acicular crystals filling vugs picopaulite (TlFe2S3), rebulite (Tl5Sb5As8S22), simonite
and fractures, and breccia cement (Fig. 5D). Paragenetically (TlHgAs3S6), bernardite (Tl[As,Sb]5S8), raguinite (TlFeS2),
late realgar occurs as distinct crystals, crystallized aggregates, parapierrotite (Tl[Sb,As]5S8), jankovićite (Tl5Sb9[As,Sb]4S22),
masses, and overgrowths on all other minerals (Fig. 5E). weissbergite (TlSbS2), fangite (Tl3AsS4), dorallcharite
The stibnite-bearing jasperoids commonly contain from 1 to (Tl0.8K0.2Fe3[SO4]2[OH]6), and thalliumpharmacosiderite
3 g/t Au, and locally the Au content exceeds 20 g/t (Percival (TlFe4[(AsO4)3(OH)4]⋅4H2O) (Pavi ćevi ć and El Goresy,
and Radtke, 1994). 1988; Percival and Radtke, 1993b, 1994; Balić-Žunić et al.,
The arsenic mineralization is hosted in argillized tuffs, in 1994; Frantz et al., 1994; Cvetković et al., 1995; Rumsey et
Tertiary dolomite, and rarely in Triassic carbonate rocks distal al., 2014). Sulfide and sulfosalt minerals typically occur as dis-
to the zones of jasperoidal silicification. Host rocks are per- seminations and as fracture, open space, and breccia infill-
vasively altered to clays and sericite mixed with sulfides and ings (Fig. 7B). Locally, As-Tl mineral assemblages occur as
subordinate hydrothermal silica. The sulfide minerals typi- massive sulfide (>5–30 vol %) replacements in the carbonate-
cally compose >10 and up to 50 vol % of the host rock (Fig. bearing rock (Fig. 7; Percival and Radtke, 1994).
6A). The sulfide assemblage includes disseminated marcasite
and pyrite associated with abundant finely to coarsely crystal- Analytical Methods
lized realgar and subordinate orpiment, stibnite, and minor This paper presents new data on mineral chemistry, stable
thallium-bearing sulfosalt minerals (Fig. 6B). The Au content isotopes, and fluid inclusions from the Allchar Au-As-Sb-Tl
is typically lower than the siliceous mineralization and usually deposit and combines them with previously published geochro-
varies from <1 to 3 g/t (Percival and Radtke, 1994). nological data (Table 1; Kolios et al., 1980; Jakupi et al., 1982;
The Tl-bearing mineralization is hosted by carbonate Lippolt and Fuhrmann, 1986; Boev, 1988; Troesh and Frantz,
and tuffaceous rocks in the northern portion of the deposit 1994; Neubauer et al., 2009; Strmić Palinkaš et al., 2012),
Py Sb
Py
1 cm B 0.1 mm
A
Mrc
Py
Sb
Sb
C 0.5 cm 0.5 mm
D
0.5 mm
Fig. 5. (A) Hand specimen of jasperoid composed of
fine-grained, mosaic-textured microcrystalline quartz. (B)
Rlg Reflected-light photomicrograph of disseminated sulfide
minerals hosted by jasperoid. (C) The later coarse-grained
stibnite crystalized in open spaces of breccia and fracture
zones within jasperoidal silica. (D) Scanning electron
photomicrograph of sulfide minerals hosted by jasperoid.
Late-stage sulfides are represented by botryoidal masses of
marcasite and pyrite and coarse-grained stibnite crystalized
in open spaces. (E) Distinct crystals of paragenetically late
realgar. Abbreviations: Mrc = marcasite, Py = pyrite, Rlg =
E realgar, Sb = stibnite.
Orp Rlg
Rlg
Orp
Orp
Orp
1 cm 0.1 mm
A B
Fig. 6. (A) Arsenic mineralization hosted by argillized Tertiary tuff. (B) Reflected-light photomicrograph of arsenic mineral-
ization. Abbreviations: Orp = orpiment, Rlg = realgar.
Rlg
Rlg
Orp
A 1 cm B 2 mm
Fig. 7. (A) The Tl-bearing mineralization is hosted by brecciated Tertiary dolomite. (B) Lorandite crystals deposited along
fractures of brecciated Tertiary dolomite. Abbreviations: Orp = orpiment, Rlg = realgar.
lithogeochemical data (Electronic App. 1; Percival and Radtke, Stable isotope studies of hydrogen, carbon, oxygen, and sul-
1994; Yanev et al., 2008; Boev and Jelenković, 2012), Pb isotope fur were carried out in the stable isotope laboratory at the
data (Electronic App. 2; Frantz et al., 1994), stable isotope data USGS. Carbonate minerals were analyzed by reaction with
(Tables 2, 3; Janković, 1993; Frantz et al., 1994; Volkov et al., 100% phosphoric acid at 25°C based on McCrea (1950). The
2006), and fluid inclusion data (Strmić Palinkaš et al., 2012). acid fractionation factors of Friedman and O’Neil (1977) were
Microanalyses of sulfide minerals were conducted using used. Sulfur isotope analyses were carried out using a con-
laser ablation-inductively coupled plasma-mass spectrometry tinuous flow method similar to that described by Giesemann
(LA-ICP-MS; Ridley and Lichte, 1998) at the U.S. Geological et al. (1994). Hydrogen, carbon, and oxygen isotope analyses
Survey (USGS), Denver, Colorado, to investigate the siting of were also performed on fluid inclusion extracts liberated by
Au and the distribution of major and trace elements includ- thermal decrepitation in stainless steel tubes. Isotopic compo-
ing As, Bi, Co, Fe, Ga, Ge, Hg, In, Mn, Mo, Ni, Pb, Re, S, sitions of gases were measured using either a Finnigan MAT
Sb, Se, Te, Tl, U, W, and Zn. Where Au, Ag, and Sb in sulfide 252 or a Micromass Optima isotope ratio mass spectrometer.
minerals were near or below the detection limits of the micro- Isotopic compositions are reported in δ notation relative to
probe, LA-ICP-MS was used. Fe, S, and As concentrations Vienna-standard mean ocean water (V-SMOW) for oxygen
measured by microprobe analysis were used to standardize and hydrogen, Pee-Dee belemnite (PDB) for carbon, and
between methods. Canyon Diablo Troilite (CDT) for sulfur.
Table 1. Geochronological Data from the Allchar Au-As-Sb-Tl Deposit, Republic of Macedonia
Mineralogy Host rock/mineralization Locality Age (Ma) Method Reference
Biotite High-K calc-alkaline to Kožuf massif 1.9 ± 0.1–5.0 ± 0.2 K/Ar Kolios et al. (1980)
shoshonitic volcanic rocks
K-feldspar High-K calc-alkaline to Kožuf massif 1.8 ± 0.1– 4.5 ± 0.2 K/Ar Kolios et al. (1980)
shoshonitic volcanic rocks
Whole rock High-K dacitic lava Kožuf massif 4.6 ± 0.2 K/Ar Kolios et al. (1980)
Biotite Latite Kožuf massif 1.8 ± 0.1–5.0 ± 0.2 K/Ar Boev (1988)
Biotite Qtz latite Kožuf massif 6.5 ± 0.2 K/Ar Boev (1988)
Biotite Andesite Kožuf massif 4.8 ± 0.2 K/Ar Boev (1988)
Whole rock Qtz latite Kožuf massif 4.62 ± 0.19 K/Ar Strmić Palinkaš et al. (2012)
Amphibole Qtz latite Kožuf massif 5.79 ± 0.21 K/Ar Strmić Palinkaš et al. (2012)
Biotite Qtz latite Kožuf massif 5.61 ± 0.20 K/Ar Strmić Palinkaš et al. (2012)
K-feldspar Qtz latite Kožuf massif 5.15 ± 0.21 K/Ar Strmić Palinkaš et al. (2012)
Orpiment Tl mineralization Crven dol, Allchar deposit 5 Fission track Jakupi et al. (1982)
K-feldspar Andesite Crven dol, Allchar deposit 4.8 ± 1.9 K/Ar Lippolt and Fuhrmann (1986)
Biotite Andesite Crven dol, Allchar deposit 5.1 ± 1.9 K/Ar Lippolt and Fuhrmann (1986)
Whole rock Andesite Crven dol, Allchar deposit 3.9 ± 0.2 K/Ar Lippolt and Fuhrmann (1986)
K-feldspar Tuff Crven dol, Allchar deposit 4.4 ± 0.5–4.6 ± 0.4 K/Ar Lippolt and Fuhrmann (1986)
Biotite Tuff Crven dol, Allchar deposit 4.1 ± 0.7–4.4 ± 0.4 K/Ar Lippolt and Fuhrmann (1986)
K-feldspar Andesite Crven dol, Allchar deposit 4.2 ± 0.1 40Ar/39Ar Troesh and Frantz (1992)
Amphibole Latite Allchar deposit 4.8 ± 0.2 40Ar/39Ar Neubauer et al. (2009)
Biotite Latite Allchar deposit 4.6 ± 0.2–4.8 ± 0.2 40Ar/39Ar Neubauer et al. (2009)
K-feldspar Latite Allchar deposit 3.3–4.0 40Ar/39Ar Neubauer et al. (2009)
Biotite Tuff Vitačovo, Allchar deposit 5.1 ± 0.1–5.1 ± 0.1 40Ar/39Ar Neubauer et al. (2009)
K-feldspar - Rudina, Allchar deposit 4.31 ± 0.02 40Ar/39Ar Neubauer et al. (2009)
Sericite and Sericite-quartz Allchar deposit 119.8 ± 1.2–125.1 ±1.8 40Ar/39Ar Neubauer et al. (2009)
K-feldspar alteration zone
Abbreviations: Qtz = quartz

Table 2. Carbon and Oxygen Isotope Data of Country Rock, Gangue Minerals, and Fluid Inclusions from the the Allchar Au-As-Sb-Tl Deposit
Sample Mineralogy δ13C (‰ V-PDB) δ18O (‰ V-SMOW) Reference
1 Calcite 2.4 14.9 Volkov et al. (2006)

ADP-232 Tertiary sanded dolomite 3.5 30.0 This study
100 Tertiary dolomite, barren 3.7 29.4 This study
Ad-823 Tertiary dolomite, barren 3.5 29.2 This study
Tl-Adit Mineralized dolomite with orpiment 1.1 19.8 This study
TR-ADP-49 Triassic marble, barren 2.8 19.6 This study
Adit I Mineralized Triassic marble with realgar 3.3 16.1 This study
Adit River Late calcite with stibnite 4.7 13.5 This study
S2 Late calcite 0.7 10.4 This study
5NE 1/4 Late calcite within marble –8.6 –4.5 This study
CD-7 orp Fluid inclusions in orpiment 4.3 9.0 This study
SM-Adit bar Fluid inclusions in barite –4.2 10.4 This study
Abbreviations: V-PDB = Vienna-Pee Dee belemnite, V-SMOW = Vienna-standard mean ocean water
Table 3. Sulfur Isotope Data of Sulfides from the Allchar Au-As-Sb-Tl Deposit
δ34S δ34S
Sample Mineralogy (‰ V-CDT) Reference Sample Mineralogy (‰ V-CDT) Reference
Marc Marcasite –4.7 Jankovic (1993) B1 Botryoidal

Real/Orp max Realgar/orpiment –1.6 Jankovic (1993) marcasite/pyrite –4.9 This study
Real/Orp min Realgar/orpiment –3.8 Jankovic (1993) B2 Botryoidal
Real/Orp mean Realgar/orpiment –2.2 Jankovic (1993) marcasite/pyrite –4.7 This study
Stb max Stibnite 0.4 Jankovic (1993) Py1 Disseminated
Stb min Stibnite –5.6 Jankovic (1993) pyrite/marcasite –3.2 This study
Stb mean Stibnite –2.2 Jankovic (1993) Py2 Disseminated
Lor-823 Lorandite –5.7 Frantz et al. (1994) pyrite/marcasite –4.1 This study
Real-823 Realgar –1.7 Frantz et al. (1994) Py3 Disseminated
Marc-823 Marcasite –1.7 Frantz et al. (1994) pyrite/marcasite –3.7 This study
Lor-817 Lorandite –2.1 Frantz et al. (1994) Py4 Disseminated
Real-817 Realgar –2.6 Frantz et al. (1994) pyrite/marcasite –4.7 This study
Orp-817 Orpiment –2.6 Frantz et al. (1994) ADP-275 Disseminated
Lor-800 Lorandite –2 Frantz et al. (1994) pyrite/marcasite –3.8 This study
Real-800 Realgar –2.7 Frantz et al. (1994) AI-9 py-1 Disseminated
Orp-800 Orpiment –2.2 Frantz et al. (1994) pyrite/marcasite –4.7 This study
Lor-763 Lorandite –2 Frantz et al. (1994) AI-9 py-2 Disseminated
Orp-763 Orpiment –2.5 Frantz et al. (1994) pyrite/marcasite –5.2 This study
14564 Stibnite 0.4 Volkov et al. (2006) CD-5 orp Orpiment –2.4 This study
14565 Stibnite –0.3 Volkov et al. (2006) CD-7 orp Orpiment –2.9 This study
14566 Stibnite –0.4 Volkov et al. (2006) Tl-Adit orp A Orpiment –0.8 This study
14567 Stibnite –4.7 Volkov et al. (2006) Tl-Adit orp B1 Orpiment –1.6 This study
14568 Stibnite –5.6 Volkov et al. (2006) Tl-Adit orp B2 Orpiment –1.9 This study
14569 Stibnite –1.8 Volkov et al. (2006) AD-2 real Realgar –3.1 This study
14571 Stibnite –5.2 Volkov et al. (2006) Adit I real1 Realgar –0.9 This study
14576 Stibnite –3.6 Volkov et al. (2006) Adit I real2 Realgar –3.1 This study
16 Stibnite –2.7 Volkov et al. (2006) ADP-58A real1 Realgar –4.2 This study
17 Stibnite –2.7 Volkov et al. (2006) ADP-58B real1 Realgar –3.6 This study
14572 Realgar –1.6 Volkov et al. (2006) ADP-58A real2 Realgar –4.4 This study
14573 Realgar –3.8 Volkov et al. (2006) ADP-58B real2 Realgar –3.8 This study
20 Realgar –0.2 Volkov et al. (2006) ALH-3 real1 Realgar –0.5 This study
21 Realgar –1.5 Volkov et al. (2006) ALH-3 real2 Realgar –0.1 This study
14574 Orpiment –3.7 Volkov et al. (2006) Alsh real Realgar –2.1 This study
14570 Marcasite –6.8 Volkov et al. (2006) Highgr. real Realgar –0.7 This study
18 Marcasite –0.7 Volkov et al. (2006) A-1 stb Stibnite –4.7 This study
19 Marcasite –0.9 Volkov et al. (2006) ADP-275 stb Stibnite –2.5 This study
Al-9 marc Botryoidal Al-11 Stibnite –3.7 This study
marcasite/pyrite –5.5 This study ALP-21 Stibnite –2.9 This study
C.a. riv1 Botryoidal Alsh SbS3 Stibnite –4.9 This study
marcasite/pyrite –8 This study Alsh Stb blad Stibnite –4.9 This study
C.a. riv2 Botryoidal C.a. riv stb Stibnite –2.4 This study
marcasite/pyrite –9.8 This study Highgr. stb Stibnite –3.5 This study
Abbreviations: V-CDT = Vienna-Canyon Diablo Troilite

Microthermometric measurements of fluid inclusions (52 and 66 wt % SiO2; Electronic App. 1) with high-K calc-
within transparent minerals were performed at the Univer- alkaline to shoshonitic affinities (Fig. 8A-C). In the major ele-
sity of Zagreb. Double polished, ~0.5-mm-thick, transparent ment classification of Le Bas et al. (1986) and the trace element
mineral wafers were used. Measurements were carried out classification of Hastie et al. (2007), the volcanic rocks of the
on a Linkam THMS 600 stage mounted on an Olympus BX Kozuf Mountains plot in the field of basaltic trachyandesite,
51 microscope using 10× and 50× Olympus long-working trachyandesite, andesite, and trachyte/trachydacite (Fig. 8A,
distance objectives for visible light. Two synthetic fluid inclu- C). Their TiO2, MgO, Fe2O3, and MnO contents show pro-
sion standards (SYN FLINC; pure H2O and mixed H2O-CO2) nounced negative correlations with the SiO2 concentration.
were used to calibrate the equipment. The precision of the Aluminum oxide, K2O, and P2O5 do not show clear trends, and
system was ±2.0°C for homogenization temperatures and Na2O shows a positive correlation (Fig. 9). The Pliocene igne-
±0.2°C in the temperature range between –60° and 10°C. ous rocks of the area are mostly characterized by high Sr/Y and
La/Yb ratios (Fig. 8D, E). Their multielement patterns show
Geochronology high large ion lithophile element/high field strength element
The geochronology data obtained from altered and mineral- (LILE/HFSE) ratios with strong depletions of Nb, Ta, and Ti
ized samples as well as associated volcanic rocks are summa- and pronounced U and Pb peaks (Fig. 8F). The chondrite-
rized in Table 1. The K/Ar, 40Ar/39Ar, and fission track ages normalized rare earth element (REE) patterns display an
suggest that hydrothermal activity was contemporaneous enrichment in light rare earth elements (LREEs) compared to
with Pliocene calc-alkaline to shoshonitic volcanism (~5 Ma). heavy rare earth elements (HREEs) and weak to pronounced
Exceptions are 40Ar/39Ar data collected on sericite and K-feld- negative Eu anomalies (Fig. 8G). The lithogeochemical char-
spar from a sericite-quartz alteration zone spatially associated acteristics of igneous rocks associated with the Allchar Au-As-
with Tl mineralization that yielded Cretaceous ages between Sb-Tl deposit (high Sr/Y, La/Yb, LILE/HFSE, and LREE/
119.8 ± 1.2 and 125.1 ± 1.8 Ma (Neubauer et al., 2009). The HREE ratios; depletions in Nb, Ta, and Ti; and enrichment in
paragenetic and geochemical relationships, described in the U and Pb) are characteristic of subduction-related magmatism
hydrothermal alteration and mineralization sections, sug- (e.g., Stolz et al., 1996; Gao et al., 2007; Booden et al., 2011).
gest that this alteration zone was overprinted by the Pliocene Tertiary igneous rocks with identical geochemical signatures
hydrothermal fluids that introduced Au, Sb, As, and Tl. have been described at numerous localities along the Vardar
zone and the Serbo-Macedonian massif of the Balkan Penin-
Lithogeochemistry sula (Fig. 1). They are usually associated with base and/or pre-
The mineralization at the Allchar Au-As-Sb-Tl deposit is spa- cious metal occurrences that formed in an extensional tectonic
tially associated with Pliocene hypabyssal intrusions and volca- regime (e.g., Crnac Pb-Zn-Ag deposit, Borojević Šoštarić et al.,
nic rocks that are well exposed throughout the Kozuf Mountains 2012; Buchim Cu-Au deposit, Lehmann et al., 2013; Trepca
(Janković et al., 1997; Yanev et al., 2008; Boev and Jelenković, Pb-Zn-Ag deposit, Strmić Palinkaš et al., 2016). The late Ter-
2012). These rocks are felsic to intermediate in composition tiary igneous rocks of the Balkan Peninsula have generally been
7
Ultrabasic Basic Intermediate Acid

15
Phonolite Trachyte
6
Trachydacite
Foidite Tephri-
5
phonolite
Trachy- Shoshonite Series
10
Phono- andesite High-K calc-alkaline

4
tephrite Series
Na2O+K2O
Rhyolite
K2O
Tephrite Basaltic
trachy-
3
Basanite andesite
Trachy- Calc-alkaline
basalt
Series
5
2
Andesite
andesite
Basaltic
Dacite
Basalt
Picrobasalt
e
1
lin
Tholeiite Series
ka
oleiitic
Al
Subalkaline/Th
0
0
40 50 60 70 80 45 50 55 60 65 70 75
SiO2 SiO2
A B
Fig. 8. Lithogeochemical data obtained from the Pliocene magmatic rocks spatially associated to the Allchar Au-As-Sb-Tl
deposit (Janković et al., 1997; Yanev et al., 2008; Boev and Jelenković, 2012). (A) Total alkali vs. SiO2 diagram (according to Le
100
Bas et al., 1986). (B) K2O vs. SiO2 classification diagram (according to Peccerillo and Taylor, 1976). (C) Th vs. Co classifica-
High-K calc-alkaline
tion diagram
and Shoshonite Series (according to Hastie et al., 2007). (D) Sr/Y vs. Y classification diagram (according to Castillo et al., 1999). (E)
Adakite
(La/Yb)N vs. YbN classification diagram (according to Martin, 1999). (F) Primitive mantle-normalized multivariation diagram
120
(according McDonough and Sun, 1995). G. Chondrite-normalized rare earth element pattern (according to Boynton, 1984).
10
100
Th
80
te
Calc-alkaline
hy
Sr/Y
1
Trac
Series
e
Bas
Bas
And
Da
and
Picrobasalt
e
1
in
l
Tholeiite Series
ka
oleiitic
Al
Subalkaline/Th
0
0
40 50 60 70 80 45 50 55 60 65 70 75
SiO2 SiO2 345
A 100
THE ALLCHAR DEPOSIT, REPUBLIC
B OF MACEDONIA
High-K calc-alkaline
and Shoshonite Series Adakite
120
10
100
Th
80
chyte
Calc-alkaline
Sr/Y
1
Series
- Tra
ite
60
ndes
Latite
ite - A
te -
40
Tholeiite
0.1
hyoli
ndes
Series e-R
ltic A
lt
20
Basa
Dacit
Normal arc
Basa
0.01
0
70 60 50 40 30 20 10 0 0 10 20 30
C Co D Y
1000
120
100
Sample/Primitive mantle
100
80
60
(La/Yb)N
Adakite
10
40 20
Normal arc Cs Ba U Ta Ce Pr P Zr Eu Dy Yb
0
0 5 10 15 20 25 Rb Th Nb La Pb Sr Nd Sm Ti Y Lu
E YbN F
Low-Mg K trachyte
1000
High-Mg K trachyte
Low-Mg K latite
Low-Mg K shoshonite
Andesite-latite
Quartz-latite
Sample/Chondrite
100
Unaltered Pliocene tuff

Unaltered Pliocene tuff breccia
Unaltered Pliocene subvolcanic intrusion
10
La Pr Pm Eu Tb Ho Tm Lu
1
G Ce Nd Sm Gd Dy Er Yb
Fig. 8. (Cont.)
A B C
1.2
20
5
1.0
19
4
0.8
18
3
TiO2
MgO
Al2O3
0.6
17
2
0.4
16
1
0.2
15
0
50 55 60 65 70 75 50 55 60 65 70 75 50 55 60 65 70 75
SiO2 SiO2 SiO2
D E F
8
7
7
6
5
6
5
CaO
Na2O
5
K2O
4
4
4
3
3
2
1
2
50 55 60 65 70 75 50 55 60 65 70 75 50 55 60 65 70 75
SiO2 SiO2 SiO2
G H I 0.16
0.8
0.14
8
0.6
0.12
7
0.10
6
P2O5
Fe2O3
0.4
MnO
0.08
5
0.06
4
0.2
0.04
3
0.02
0.0
50 55 60 65 70 75 50 55 60 65 70 75 50 55 60 65 70 75
SiO2 SiO2 SiO2
Fig. 9. Harker diagrams illustrating (A) TiO2, (B) Al2O3, (C) MgO, (D) CaO, (E) Na2O, (F) K2O, (G) P2O5, (H) Fe2O3, and
(I) MnO variations for the Pliocene igneous rocks spatially associated with the Allchar Au-As-Sb-Tl deposit. Symbols as in
Figure 8.
attributed to postcollisional collapse of the Dinaride orogen fol- The mineralization at the Allchar Au-As-Sb-Tl deposit is
lowed by extension of the Pannonian (Miocene) and Aegean hosted by various rock types including Triassic marble, Ter-
areas (Eocene-Pliocene) (Cvetković et al., 2000, 2004; Prelević tiary dolomite, Tertiary tuff, and the basal unconformity
et al., 2005; Jolivet and Brun, 2010; Koroneos et al., 2011; Sche- between Tertiary and Triassic rocks (Janković, 1993; Percival
fer et al., 2011; Borojević Šoštarić et al., 2012; Lehmann et al., and Radtke, 1994). The whole-rock geochemical data obtained
2013; Melfos and Voudouris, 2017). Available Sr and Nd iso- on host rocks and their unaltered equivalents published by
tope data from the Kozuf Mountains area (87Sr/86Sr = 0.7085– Percival and Radtke (1994) are summarized in Electronic
0.7093; 143Nd/144Nd = 0.51230–0.51233) suggest significant Appendix 1. Isocon analysis (Grant, 2005) has been applied
assimilation of continental crust (Yanev et al., 2008). to mineralized rocks and their unaltered equivalents (Fig. 10).
7 Au 7 Au
10 Triassic marble 10 Tertiary dolomite
Argillic alteration Argillic alteration
6 SiO2 6 SiO2
10 Silicification 10 Silicification
As MgO Fe2O3
Sb Fe2O3
5 5
10 Se Al2O3 10
Bi
FeO K2O
K2O FeO
104 104 Sb As
Al2O3
TiO2 CaO
3 Tl MnO P2O5 3
TiO2 P2O5 CaO
10 10 Tl
Co Ni Cr
Rb Ni Hg MgO
Cu Ba CoY
Mo MoPb
100 Zr 100 MnO
Hg Zn Zn
Te Na2O Ag Na2O
10 10 Te Zr Ba
Sr Se Sr
Ag Cu
1 Cr 1 Rb Bi
2 Pb
Concentration in altered rock

iO
tT Y iO 2
n s tan l 2O 3
A tT
0.1 0.1 tan 3
Co and s l 2O
C on dA
n
ss s sa
0.01 ma 0.01 ma
nt ta nt
sta ns
-3 Con -3 Co
10 -3 3 4 5 6 7 10 -3 3 4 5 6 7
10 0.01 0.1 1 10 100 10 10 10 10 10 10 0.01 0.1 1 10 100 10 10 10 10 10
A Concentration in unaltered rock B Concentration in unaltered rock
7
107 Pliocene tuff Au 10 Subvolcanic intrusion
Argillic alteration SiO2
6 SiO2
106 Silicification 10 Au
As Fe2O3
Sb K2O 5 Fe2O3
105 10 Al2O3
MgO As CaO
TiO2 Al2O3 K2O
104 P2O5 104 MgO
FeO
FeO
TiO2
3
Na2O 3
10 Cr MnO 10 Tl Na2O
Ni Zr Sb Ba P2O5
Zn CaO Rb
Tl Co Cu
100 100 Pb
THE ALLCHAR DEPOSIT, REPUBLIC OF MACEDONIA
Ag Pb Y Cr Zr MnO
Te Mo Rb Ni
Hg Se Te Se Zn Sr
10 Ba 10 Hg
Bi Sr Y Cu
Bi
1 1 Mo Co
Ag

0.1 s 0.1 3
as ss l 2O
n tm 2 ma dA
t a i O t 2
an
0.01 ns d T O3 0.01 tan TiO
Co an Al 2 ns t
t ant Co tan
ns ns
-3 Co -3
Co
10 -3 10 -3 3 4 5 6 7
10 0.01 0.1 1 10 100 103 104 105 106 107 10 0.01 0.1 1 10 100 10 10 10 10 10
C Concentration in unaltered rock D Concentration in unaltered rock
Fig. 10. Isocon diagrams for (A) Triassic marble, (B) Tertiary dolomite, (C) Pliocene tuff, and (D) Pliocene subvolcanic intrusion. The concentrations of all elements are
shown in ppm, except for Au, which is expressed in ppb.
347
In silicified and argillized Triassic marble, TiO2, Al2O3, Lead Isotope Data
MnO, Ag, Bi, Pb, Cu, and Zn are relatively immobile and Ca, Lead isotope compositions of sulfide minerals and country
Na, Sr, and Y are depleted (Fig. 10A). Magnesium is depleted rocks associated with the mineralization at the Allchar Au-As-
in silicified rocks and introduced in argillized rocks. Although Sb-Tl deposit are listed in Electronic Appendix 2 and plotted
Au, Co, Cr, Fe, Hg, Ni, Sb, Se, Te, and Zr are introduced in Figure 13. The Pb isotope compositions of two Pliocene
in each alteration type, silicified rocks are more enriched in subvolcanic intrusions are very similar to one another and
these elements than argillized rocks. In contrast, argillic alter-
plot in the mature arc or upper continental crust fields (Fig.
ation is more strongly enriched in Tl, Rb, and K2O than silici-
13). They mostly overlap with the average values obtained for
fied rocks (Fig. 10A).
galena and volcanic rocks from the Belo Brdo Pb-Zn hydro-
In Tertiary dolomite, argillic alteration is associated with
thermal deposit in Kosovo (Veselinovic-Williams, 2011) and
the introduction of Fe2O3, As, Tl, Pb, Sb, Hg, and Ag and
the average values for galena from the Inkaya Cu-Pb-Zn pros-
depletion of CaO, MgO, Al2O3, Na2O, K2O, and Sr (Fig.
pect, northwestern Turkey (Ozen and Arik, 2015). Both the
10B); TiO2 is immobile. In contrast, silicification is associ-
ated with depletion of CaO, MgO, Na2O, MnO, and Sr and Belo Brdo deposit and the Inkaya prospect have been inter-
introduction of SiO2, K2O, Fe2O3, Rb, As, Sb, Cr, Tl, and Hg preted as products of voluminous postcollisional calc-alkaline
(Fig. 10B). to ultrapotassic magmatism that followed closure of the Vardar
In Pliocene tuff, altered rock is depleted in CaO, Na2O, Ba, ocean in Oligocene to early Miocene time (Erkul and Erkul,
and Sr and enriched in Hg, Te, Mo, As, Sb, Tl, Ag, and Au 2010; Veselinovic-Williams, 2011; Ozen and Arik, 2015).
(Fig. 10C). The Au, Ag, and Hg enrichments are more pro- In contrast, sulfide minerals are similar to Tertiary dolo-
nounced in silicified tuff than in argillized tuff, whereas Tl is mite, and most are widely scattered across the oceanic island
more enriched in argillized tuff (Fig. 10C). volcanic rock field on the 208Pb vs. 206Pb diagram and the
In a Pliocene subvolcanic intrusion, the altered rock is upper continental crust field on the 207Pb vs. 206Pb diagram.
depleted in CaO, K2O, MgO, FeO, P2O5, MnO, Cu, Zn, Sr, The distribution of data suggests that the Pb in ore minerals
and Co. It is enriched in Hg, Te, Tl, Ag, Au, As, and Sb. Silica, was derived primarily from the country rocks.
Al2O3, TiO2, Cr, Ni, Bi, and Mo are relatively immobile (Fig. Stable Isotope Studies
10D).
In all altered host rocks (Fig. 10), Au/Ag ratios are relatively To determine the source of water, CO2, and H2S in ore flu-
high (100–10,000) and the abundance of base metals is low ids, new and previously published stable isotope data (δD,
(Cu + Zn + Pb + Mo + Co + Ni <1,000 ppm), suggesting that δ18O, δ13C, δ34S) on hydrothermal minerals and fluid inclu-
the solubility of Ag and base metals was suppressed by a high sions were synthesized. Hydrogen and oxygen isotope data
activity of H2S in ore fluids (e.g., Hofstra and Cline, 2000). were used to constrain the source of water and to estimate
The isocon diagrams reveal hydrothermal solutions at the water-rock ratios. Sulfur isotope data reflect the source of H2S
Allchar deposit introduced much more Fe, Mg, and K than and, in samples where isotopic equilibrium was achieved, the
hydrothermal fluids in Nevada Carlin-type gold deposits (e.g., temperature of mineral precipitation. Carbon and oxygen iso-
Hofstra and Cline, 2000). topes can potentially discriminate between sedimentary car-
bonates, organic matter, and magmatic sources of CO2.
Mineral Chemistry The δD and δ18O data obtained from gangue minerals and
LA-ICP-MS multielement analyses of pyrite grains in miner- fluid inclusions are listed in Table 4. The calculated and mea-
alized samples from the Allchar Au-As-Sb-Tl deposit reveal sured δDH2O and δ18OH2O values define a triangular field that
that the grains are enriched in Mn, Te, Sn, Cu, W, Cs, Pb, extends from the primary magmatic water box toward the
and Au without significant chemical zonation (Fig. 11A, B, meteoric water line (Fig. 14). The data indicate that magmatic
D). On the Au vs. As diagram, some of the pyrite samples plot fluid mixed with exchanged meteoric water at deep levels and
in the Carlin pyrite field, but the majority are in the diagenetic with unexchanged meteoric water at shallow levels in the sys-
pyrite or intrusion-related pyrite fields. All data plot below the tem (Fig. 14).
Au saturation line (Fig. 12) with Au concentrations less than The δ13C and δ18O values of barren and altered host rocks,
1,000 ppm. vein calcite, and fluid inclusion extracts are listed in Table 4.
Stibnite is enriched in Se and Te and has detectable amounts The δ13C value of barren Triassic marble is within the range
of Tl, Hg, Ag, and Pb (Fig. 11E, F). Some stibnite crystals of Phanerozoic marine carbonates (Veizer and Hoefs, 1976),
have rims with elevated concentrations of As and Cu (Fig. and its δ18O value is consistent with Triassic marine carbon-
11E). Orpiment and lorandite contain significant amounts of ate values (Claypool et al., 1980), indicating that the original
Sn, Pb, Sb, and Hg (Fig. 11G). Realgar shows a zonal trace isotopic composition of the Triassic limestone was not signifi-
element distribution with cores enriched in Sb and Te and cantly disturbed by metamorphic recrystallization (Fig. 15).
rims enriched in Tl and Pb. It also contains detectable con- The δ13C values of barren Tertiary dolomite are similar to
centrations of Sn and Hg (Fig. 11C ). Phanerozoic marine carbonate (Veizer and Hoefs, 1976), but
The geochemical signature characterized by elevated con- their δ18O values are higher than average Tertiary marine car-
centrations of Se, Te, Hg, As, Sb, Cu, Sn, Pb, Mn, and Cs in bonate (Fig. 15). The calculated isotopic composition of fluid
these sulfides may be indicative of a magmatic source. It is in equilibrium with altered and mineralized marble and dolo-
also possible that Pb, Sn, and W were leached from under- mite, vein calcite, and inclusion fluid extracted from orpiment
lying continental crust, whereas Mn could be derived from and barite defines a field that extends between three sources:
ophiolites that occur near the Allchar deposit (Fig. 2). carbonate rock-buffered fluid, magmatic fluid, and meteoric
water (Fig. 15). The calcite vein with the lowest δ18O and δ13C dissolution of calcite and dolomite as well as precipitation of
values may contain CO2 produced by the oxidation of organic marcasite and kaolinite point to a low redox potential and low
carbon in the host rocks. pH values of hydrothermal fluids associated with deposition
The sulfur isotope data are summarized in Table 3 and of siliceous Au mineralization. Under such Eh-pH condi-
Figure 16. The absence of hypogene sulfate minerals and tions, H2S predominates over other sulfur species. Early-stage
1
1
2
2
1
2 1
1 cm 2
1 cm
pyrite
1,000,000 pyrite pyrite
1,000,000
1 1,000,000 pyrite
1 1,000,000
1
100,000
100,000 S34 100,000
1
Mn55 S34 100,000
Fe57 Mn55 S34
10,000 Fe57
As75 Fe57 S34
10,000 Sn118 10,000 Cu65 Fe57
As75
Sb121 Sn118 10,000 As75 Cu65
ppm
1,000 Te125 Sb121 Sb121 As75

ppm
ppm
1,000 Au197 Te125 1,000 Cs133 Sb121

Hg202 Au197 ppm 1,000
W182
Au197
Cs133
Tl205 Hg202 W182
100 Hg202
Pb208 Tl205 Au197
100 100 Tl205 Hg202
Pb208
100 Pb208 Tl205
10 Pb208
10 10
10
1
29 1 49 69 90 109 1
29 Time
49 in Seconds
69 90 109 31 1 51 71 91 111 131 151
Time in Seconds
pyrite 31 51 Time 71
in Seconds
91 111 131 151
1,000,000 pyrite py Time in Seconds
py
1,000,000
2 1,000,000 py py
100,000 2 1,000,000
2
100,000
S34
Mn55 S34 100,000 2
S34
Fe57 Mn55 100,000
10,000 Fe57 S34
As75 Fe57 Cu65 Fe57
10,000 Sn118 As75 10,000 As75 Cu65
Sb121 Sn118
10,000 Sb121 As75
ppm
1,000 Te125 Sb121 Cs133 Sb121

Au197
ppm
1,000 Te125 Au197

ppm
Hg202 1,000 Cs133

Au197 Hg202 Au197
ppm
Tl205 Hg202 1,000

100 Tl205 Hg202
Pb208 Tl205 Pb208 Tl205
100 Pb208 100 Pb208
100
10
10 10
10
1
1 1
28 48 68 88
A 28 Time
48 in Seconds68 88 30 1 60 90 120 150 180 210
A Time in Seconds B 30 60 Time 90
in Seconds
120 150 180 210
B Time in Seconds
Fig. 11. Laser ablation-inductively coupled plasma-mass spectrometry multielement profiles. (A) Profiles across a pyrite crys-
tal in the mineralized sample (AD-9; disseminated pyrite/marcasite; δ34SPy = –4.7 to –5.2‰). Profile 1 shows pyrite enriched
in Mn, Te, and Sn. The left side of the profile with higher Sb and lower S, Fe, As, and Tl concentrations may indicate the
presence of tetrahedrite. Profile 2 shows pyrite enriched in Mn, Te, and Sn. (B) Profiles across a pyrite crystal in an As ore
sample (AD-2). Profile 1 shows pyrite enriched in Cu, W, Cs, and Pb. Profile 2 shows two pyrite crystals enriched in Cu, Cs,
and Pb. (C) Profile across realgar in an As ore sample (AD-2; δ34SRlg = –3.1‰). Realgar contains zones enriched in Sb and Te
and rims enriched in Tl and Pb. It also contains Sn and Hg. (D) Profile across two pyrite crystals in an As ore sample (AD-1).
Pyrite is enriched in Te, W, and Pb. (E) Profile across Se- and Te-bearing stibnite crystal in a quartz vein (FI-2). The rims
are enriched in As and Cu. The flat blue line shows that Sb saturated the ion counter. (F) Profile across two stibnite crystals
associated with drusy quartz (Sample ALP-21; δ34SSb = –2.9‰). Arsenic, Se, and Te are the main trace elements, and Tl, Hg,
Ag, and Pb have been detected. The flat blue line shows that Sb saturated the ion counter. (G) Profile across orpiment and
lorandite crystals (Sample CD-5; δ34SOrp = –2.4‰). Lorandite contains more Pb, Sb, and Hg than orpiment. Both minerals
contain elevated concentrations of Sn. The flat red and orange lines show that As and Tl saturated the ion counter. Abbrevia-
tions: Asp = arsenopyrite, Lor = lorandite, Orp = orpiment, Py = pyrite, Rlg = realgar.
Py Asp Py
1,000,000 100,000
100,000 S34
10,000
Fe57
Selected Variables
S34 As75
10,000 As75 Sb121
Sn118 1,000 Te125
Sb121 W182
Te125 Au197
ppm
1,000 Hg202 Hg202

Tl205 100 Tl205
Pb208 Pb208
100 Bi209
10
10
1
1
36 56 76 96 116 136
90 140 190 240
Time in Seconds
C Time in Seconds D
1,000,00
100,000
100,000
100,00
10,000
10,000
S34
S34 As75 10,00
1,000
1,000 Cu65 Se77
As75 Ag107
ppm
ppm
ppm
Se77 Sb121
Te125 1,00
Sb121 100
100 Hg202
Te125
Tl205
Pb208 10
10
10
1
1
1
0.1
0.1
45 70 95 120 145 170 195 220 245 270 295 320 345
104 124 144 164 184 204 224 244 264 284 304 G
E Time in Seconds F Time in Seconds
Fig. 11. (Cont.)

2.6‰, reflecting a strong input of magmatic H2S during the

main mineralization stage. Late-stage botryoidal pyrite and
marcasite, depleted in δ34S and with calculated δ34SH2S values
between –6.5 and –11.6‰, point to diminishing influence of
magmatic volatiles and predomination of H2S from sedimen-
tary sources during the late-mineralization stage. Presence
of barite in the later stages of the mineralization indicates
increase in oxygen fugacity that could have contributed to
partial oxidation of bulk sulfur and resulted in fractionation of
isotopically light sulfide from isotopically heavy sulfate (e.g.,
Ohmoto, 1972; Kesler et al.,1981).
1,000,000
Fluid Inclusion Studies
100,000
Microthermometric measurements of fluid inclusions in vari-
S34 S34
ous minerals from different stages of ore deposition in the
As75 10,000
Se77
As75 Allchar Au-As-Sb-Tl deposit document changes in the temper-
Sn118
Ag107 ature and salinity of hydrothermal fluids. Fluid inclusions were
ppm
Sb121 Sb121
1,000 Hg202
Te125
Hg202 Tl205
classified as primary, pseudosecondary, or secondary according
Tl205 Pb208 to petrographic features proposed by Roedder (1984).
Pb208 100
Quartz crystals selected from siliceous Au mineralization
host several generations of two-phase, liquid + vapor fluid
10
inclusions, but only primary inclusions were large enough to
allow reliable microthermometric measurements (Fig. 17A).
1
28 48 68 88 108
The uniform degree of fill (F) around 0.85 suggests entrap-
G Time in Seconds ment of a single-phase fluid. The great majority of the fluid
Fig. 11. (Cont.)
inclusions have first melting temperatures (eutectic tempera-
ture, Te) between –44° and –58°C (Fig. 18A) that are charac-
teristic of the H2O-NaCl-CaCl2 ± MgCl2 system. Final melting
disseminated pyrite and marcasite have calculated δ34SH2S temperature of hydrohalite (Tm hyd1) was recorded in the tem-
values between –5.0 and –7.0‰, suggesting that H2S was perature interval between –24.2° and –42.0°C (Fig. 18B). Ice
initially derived from diagenetic pyrite in sedimentary rocks melting temperatures (Tm ice) from –2.4° to –18.1°C (Fig. 18C)
(Ohmoto and Rye, 1979). In contrast, stibnite, orpiment, correspond to salinities between 4 and 21.3 wt % NaCl equiv.
and realgar have calculated δ34SH2S values between –2.7 and Homogenization (Th) by vapor disappearance occurred from
10,000
1,000
100
10
Au ppm
0.1
0.01
0.001
0.0001
1 10 100 1,000 10,000 100,000 1,000,000
As ppm
Fig. 12. Au vs. As plot based upon laser ablation-inductively coupled plasma-mass spectrometry analyses of pyrite in the
Allchar mineralized samples. Most of the data plot in the diagenetic pyrite or intrusion-related (Int.-rel.) pyrite fields. Some
of the data plot in the Carlin pyrite field. All data plot below the Au saturation line of Reich et al. (2005). Fields adapted from
Large et al. (2011).
A 40.0
Upper
crust
39.5
Lower
Pelagic
crust
sediments
39.0
Mature
Pb/ 204Pb
38.5 Arc
Primitive
208
ks
roc
38.0 n ic
lca
vo
nd
sla
ni ci
MORB ea
Oc
37.5
Lorandite Belo Brdo Pb-Zn deposit, Kosovo
(Veselinovic-Williams, 2011)
Realgar Galena
Orpiment Tertiary volcanic rocks
37.0
Pliocene subvol. intrusion
Inkaya Cu-Pb-Zn prospect, NW Turkey
Triassic marble (Ozen and Arik, 2015)
Tertiary dolomite Galena
36.5
16.5 17.5 18.5 19.5 20.5
Pb/ Pb
206 204
B 16.0
Upper
crust
15.8
Pelagic
sediments
s
ock
anic r
15.6 Mature volc
nd
Arc isla
Primitive anic
Oce
MORB
MORB
Lower
Pb/ 204Pb
15.4 crust
207
15.2
15.0
16.50 17.00 17.50 18.00 18.50 19.00 19.50 20.00 20.50
206
Pb/ 204Pb
Fig. 13. (A) 208Pb/204Pb vs. 206Pb/204Pb and (B) 208Pb/204Pb vs. 207Pb/204Pb diagrams for selected country rocks and ore miner-
als at the Allchar Au-As-Sb-Tl deposit (Frantz et al., 1994), compared with average values for data published from the Belo
Brdo Pb-Zn hydrothermal deposit (Veselinovic-Williams, 2011) and the Inkaya Cu-Pb-Zn prospect (Ozen and Arik, 2015).
Pb isotope composition of fields adapted from Zartman and Doe (1981). Abbreviations: MORB = mid-ocean ridge basalt.
Table 4. Hydrogen and Oxygen Isotope Data of Country Rock, Gangue Minerals, and Fluid Inclusions from the Allchar Au-As-Sb-Tl Deposit
Sample Mineralogy δDH2O (‰ V-SMOW) δ18Omineral (‰ V-SMOW) δ18OH2O (‰ V-SMOW) Reference
AD-2 Fluid inclusions, realgar –99 This study

SM-Adit Fluid inclusions, barite –97 10.4 2.6 This study
CD-7 Fluid inclusions, orpiment –75 9.0 This study
5NE 1/4 Fluid inclusions, late calcite –114 –4.5 –12.3 This study
FI-2 Fluid inclusions, milky quartz vein –71 8.0 –3.6 This study
AD-2 Jasperoid 11.5 –0.1 This study
AD-2 Quartz 8.6 –3 This study
ADP-275 Jasperoid 10.7 –0.9 This study
ADP-275 Quartz 8.2 –3.4 This study
ADP-145 Jasperoid 10.4 –1.2 This study
AI-1 Quartz 10.4 –1.2 This study
High gr. Jasperoid 9.6 –2 This study
ALP-21 Quartz 9.9 –1.7 This study
AI-9 Jasperoid 11.5 –0.1 This study
AI-11 Jasperoid 10.3 –1.3 This study
Abbreviations: V-SMOW = Vienna-standard mean ocean water
131° to 200°C (Fig. 18D). Several fluid inclusions nucleate a homogenization to vapor phase is recorded between 31.0° and
recognizable clathrate phase that melted between –0.5° and 33.0°C. Total homogenization to liquid phase was recorded
3°C, suggesting the presence of CO2 and salinities between between 102° and 125°C (Fig. 18).
12.6 and 16 wt % NaCl equiv. Homogenization temperatures The hydrocarbon-bearing inclusions contain one or more
for this type of fluid inclusion were recorded between 185° immiscible liquids or solid phases (Fig. 17C). They remain
and 202°C. unfrozen at the minimum fluid inclusion stage temperature
The physicochemical characteristics of mineralizing fluids of –180°C. During subsequent heating, the only recorded
associated with stibnite-bearing jasperoids were estimated change was a reduction in size or shape of some of the com-
from primary fluid inclusions hosted by jasperoid, quartz, ponents without complete phase transitions. None of these
and rare calcite crystals (Fig. 18). Jasperoid hosts aqueous- inclusions homogenized before decrepitation, which occurred
carbonic and hydrocarbon-bearing fluid inclusions (Fig. at temperatures from 170° to 180°C. Ultraviolet fluorescence
17B). At room temperature, the aqueous-carbonic inclusions of hydrocarbon-bearing fluid inclusions is in yellow and green
contain two immiscible liquids and a vapor phase. Melting colors, suggesting immature organic matter (e.g., Hagemann
of clathrates occurred from 2.4° to 7.0°C corresponding to and Hollerbach, 1986; McLimans, 1987; Bodnar, 1990). The
salinity between 6.0 and 13.5 wt % NaCl equiv. The CO2 intensity of fluorescence increases with the size of inclusions.
Quartz and calcite associated with the stibnite-bearing
mineralization usually host primary inclusions that, at room
0 temperature, have two phases (L + V) and a uniform degree
Quartz of fill around 0.85 (Fig. 17D, E). The initial melting tempera-
Orpiment/Realgar
Calcite ture between –50° and –56°C indicates presence of divalent
–20 Barite cations (Fig. 18). Final melting of hydrohalite (Tm hyd1) was
recorded between –27.2° and –39.0°C (Fig. 18). Ice melt-
–40 ing temperatures (Tm ice) from –10.5° to –13.1°C (Fig. 18)
suggest the salinity between 14.5 and 17.1 wt % NaCl equiv.
δDH2O ‰
Homogenization into liquid phase occurred from 120° to

–60 165°C (Fig. 18).
Microthermometric measurements carried out on primary
L + V inclusions hosted by realgar, orpiment, dolomite, and
–80 lorandite (Fig. 17F-I) have first melting temperatures (Te)
between –50° and –54°C, indicating the presence of divalent
–100 cations (Fig. 18). Melting runs between –35° and 0°C pro-
vide evidence for the existence of two hydrates. Melting of
the first hydrate (Tm hyd1; sylvite) occurred between –22.0° and
–120 –24.5°C (Fig. 18). The final melting of the second hydrate
–15 –10 –5 0 5 10 15 (Tm hyd2; hydrohalite) was recorded between –11.0° and
δ18OH2O ‰ –15.4°C (Fig. 18). The final ice melting temperature (Tm ice)
interval between –1.5° and –4.1°C (Fig. 18) corresponds to a
Fig. 14. Isotopic composition of water in equilibrium with, or extracted from, salinity of 2.6 to 6.9 wt % NaCl equiv. The molar K/Na ratio
hydrothermal minerals relative to seawater (SW), meteoric water line (MWL)
and primary magmatic water (PMW). Mixing and water/rock (W/R) exchange calculated from hydrate melting temperatures varies between
lines are shown in blue. The results suggest the deposit formed from mixtures 0.19 and 0.21 (Hall et al., 1988). Homogenization of inclu-
of magmatic water and variably exchanged meteoric water. sions hosted by realgar and dolomite occurred into liquid
30
Triassic marble
Tertiary dolomite
Marine carbonates
25 Altered marble
Altered dolomite
Influence of organic matter
Vein calcite
20
δ18O (‰, V-SMOW)
Calcite, Volkov et al., 2006
Orpiment, fluid inclusion
15 Barite, fluid inclusion

CO2 in equilibrium with hydrothermal calcite
10
PIC
5
Fluid
0
-5
-10
MW
-15
-12 -10 -8 -6 -4 -2 0 2 4 6 8
δ C (‰, V-PDB)
13
Fig. 15. Isotopic composition of carbonate host rocks, calcite, and fluid inclusion extracts from orpiment and barite relative
to primary igneous carbonatite (PIC; Taylor et al., 1967), Phanerozoic marine carbonates (Veizer and Hoefs, 1976), and local
meteoric water (MW). The blue fluid field shows the isotopic composition of water and CO2 extracted from or in equilib-
rium with hydrothermal minerals. The results are indicative of carbonate rock buffered fluid, magmatic fluid, and variably
exchanged meteoric water. Abbreviations: V-PBD = Vienna-Pee Dee belemnite, V-SMOW = Vienna-standard mean ocean
water.
phase between 120° and 152°C (Fig. 18). Similar microther- Since no evidence of boiling was observed in the fluid
mometry data from realgar were published by Beran et al. inclusion assemblages studied, we infer that all were trapped
(1990). The temperature of total homogenization within orpi- in the one phase field along isochores that emanate from
ment and lorandite was not recorded due to massive decrepi- the solvus in the H2O-NaCl-KCl-CaCl2 ± CO2 system. The
tation of fluid inclusions at lower temperatures. wide range of Th (102°–202°C) and salinities (2.6–21.3 wt %
To identify major elements in hydrothermal fluids, scanning NaCl equiv) within and across the alteration zonation pat-
electron microscope-energy dispersive analyses of evaporate tern is a clear evidence of mixing between saline and dilute
mounds produced by the thermal decrepitation of fluid inclu- liquids with different temperatures at the sites of ore deposi-
sions were carried out according to the procedure described tion (Fig. 19). The occurrence of CO2 in low- and high-tem-
by Kontak (2004). Evaporate mounds that formed on the perature inclusions with different salinities probably reflects
surfaces of quartz, realgar, and orpiment wafers were com- condensation of CO2-rich vapor into aqueous liquids. The
posed primarily of Cl, Na, and K. Traces of Ca were detected CO2-rich vapor may have been produced by phase separa-
as well. Some inclusions hosted by realgar contain measur- tion of ascending magmatic fluids and/or by dissolution of
able amounts of Al and Si, probably indicating the presence of the carbonate host rocks by acid magmatic volatiles (e.g.,
accidentally entrapped clay minerals. HCl, SO2 => H2SO4 + H2S).
15
15 Orpiment, realgar
Stibnite
Orpiment, realgar
Pyrite,
Stibnitemarcasite
10 Lorandite
Pyrite, marcasite
10 Lorandite
5
Frequency
5
Frequency
0
0
5
5
-12 -10 -8 -6 -4 -2 0 2 4
A -12 -10 -8 -6 -4 δ S (‰)
34
-2 0 2 4
A δ34S (‰)
15
15 H2S, 200°C
H2S, 200°C
10
10
5
5
Frequency
0
Frequency
5
5
Botryoidal pyrite/marcasite
Disseminated pyrite/marcasite
Botryoidal pyrite/marcasite
Disseminated pyrite/marcasite
-12 -10 -8 -6 -4 -2 0 2 4
B -12 -10 -8 -6 -4 δ S (‰) -2
34
0 2 4
Fig. 16. B Sulfur isotope composition of Fe, Sb, and As sulfide minerals
(A) δ S (‰)
34
from the Allchar Au-As-Sb-Tl deposit. (B) Calcu-
lated composition of H2S in equilibrium with the minerals at 200°C.
PS
L1 L2
PS
50µm 15µm 20µm 10µm

A B C D
V
L L
V
10µm 25 µm
10µm F 5µm
E G
Fig. 17. Photomicrographs of fluid inclusions from the Allchar Au-As-Sb-Tl deposit. (A) Clusters of primary (P) and trails of
pseudosecondary (PS) fluid inclusions hosted by quartz associated with the siliceous Au mineralization. (B) Primary aqueous-
carbonic fluid inclusion hosted by stibnite-bearing jasperoid. (C) The hydrocarbon-bearing inclusions hosted by stibnite-
bearing jasperoid contain one or more liquid (L1, L2) and/or solid (S) phases. (D) Primary aqueous fluid inclusion hosted by
quartz associated with the stibnite-bearing mineralization. (E) Primary aqueous fluid inclusions hosted by calcite associated
with the stibnite-bearing mineralization. (F) Primary aqueous fluid inclusion within realgar associated with the Tl-bearing
mineralization. (G) Primary aqueous fluid inclusions hosted by orpiment associated with the Tl-bearing mineralization. (H)
Primary aqueous fluid inclusions hosted by lorandite crystals. Abbreviations: L = liquid, V = vapor.
Chemical Reactions and Modeling In both cases, the neutralization of ore-forming fluids by
The isocon diagrams for the carbonate host rocks show that the host carbonates will drive the reactions forward and pro-
Au and Fe were introduced by hydrothermal solutions. mote deposition of Au and pyrite. These reactions would also
Since Fe resides primarily in pyrite, S must also have been be driven forward by an increase in pH produced by dilution
introduced (Fig. 10). As indicated by the absence of hypo- with near-neutral groundwaters (Fig. 20).
gene sulfate minerals, dissolution of calcite ± dolomite, and In contrast, the isocon diagram for tuff shows that Fe was
precipitation of marcasite and kaolinite, Eh-pH conditions immobile (Fig. 10C), suggesting that sulfidation of preexisting
favored H2S° over other S species. According to experimen- Fe minerals, such as magnetite, in tuff was a critical factor for
tal data published by Stefansson and Seward (2004), in acid deposition of Au and pyrite:
hydrothermal solutions with high aCl–/aHS– ratios, Au chloride 3Au(HS)2– + Fe3O4 + 2H+
complexes predominate over Au bisulfide complexes. The fol- ↔ 3Au0 +3FeS2 + 4H2O ∆rH << 0. (3)
lowing equation illustrates coprecipitation of Au and pyrite
from a single fluid containing dissolved Au, Fe, and S: Whereas all three reactions are exothermic over a wide
range of pressures and temperatures, mixing of hot ore-bear-
AuCl2– + FeCl2 + 2H2S(aq) ing fluids with cold groundwaters will contribute to coprecipi-
↔ Au0 + FeS2 + 4H+ + 4Cl– ∆rH << 0. (1) tation of Au and pyrite (Fig. 20).
In most hydrothermal solutions, As and Sb are transported
At lower aCl–/aHS– ratios the stability of Au bisulfide com-
by hydroxyl complexes (Pokrovski et al., 2002; Zotov et al.,
plexes is promoted, and Au and pyrite may precipitate by mix-
2003; Seward et al., 2014), and their mobility depends on
ing between contrasting fluids, such as condensed magmatic
temperature, pressure, sulfur fugacity, redox potential, and
vapor containing Au bisulfide complexes and saline liquids
pH value of the solution. The isocon diagrams indicate that
containing Fe chloride complexes:
deposition of As and Sb was accompanied by both silicification
Au(HS)2– + FeCl2 ↔ and argillic alteration. However, deposition of these minerals
Au0 + FeS2 + 2H+ + 2Cl– ∆rH << 0. (2) was more effective during low-temperature argillic alteration
40 Siliceous Au mineralization 18 Tmhyd1 Tmhyd2
Aqueous fluid inclusions 16
35 Aqueous-carbonic fluid inclusions
Sb-bearing mineralization 14
30
Aqueous fluid inclusions; quartz, calcite
Aqueous-carbonic fluid inclusions; jasperoid 12
25
Tl-bearing mineralization 10
20 Aqueous fluid inclusions
8
Frequency / N
15
Frequency / N
6
10 4
5 2
0 0
-58 -56 -54 -52 -50 -48 -46 -44 -42 -40 -38 -42 -38 -34 -30 -26 -22 -18 -14 -10
A Temperature / °C B Temperature / °C
25 20
18
20 16
14
15 12
10
10 8
Frequency / N
Frequency / N
THE ALLCHAR DEPOSIT, REPUBLIC OF MACEDONIA
6
5 4
2
0 0
-20 -16 -12 -8 -4 0 4 8 100 120 140 160 180 200
C Temperature / °C D Temperature / °C
Fig. 18. Frequency distribution of (A) eutectic melting temperature, (B) final melting temperature of hydrates, (C) final melting temperature of ice, and (D) total homog-
enization temperature. The diagrams synthesize the new fluid inclusion data with the data previously published by Strmić Palinkaš et al. (2012).
357
Siliceous Au mineralization
Aqueous fluid inclusions
Aqueous-carbonic fluid inclusions
35 ratio
n
Sb-bearing mineralization atu
Aqueous fluid inclusions; quartz, calcite N aCl s 0
Aqueous-carbonic fluid inclusions; jasperoid 1.0
30 Tl-bearing mineralization
0
Aqueous fluid inclusions 1.1
Salinity (wt % NaCl equiv)
25
Cooling FLUID 1
0
0.9
20
Isothermal mixing
15
0
0.8
10
ng
ixi
M 0
0.7
5
FLUID 2
100 200 300

Temperature (°C)
Fig. 19. Correlation of homogenization temperature and salinity for fluid inclusions hosted by the early siliceous Au miner-
alization, the main-stage Sb-bearing mineralization, and the late Tl-bearing mineralization.
(Fig. 10). Since stibnite, orpiment, and realgar have prograde hydrothermal conditions. In contrast, Tl3+ behaves similar to
solubility, this relationship suggests that cooling, acidification, Al3+ and shows very limited mobility under hydrothermal con-
and an increase in sulfur fugacity were key factors for precipi- ditions (e.g., Kemper and Bertram, 1991; Sobott, 1993). Mon-
tation of Sb and As sulfide minerals (Fig. 21): ovalent Tl+ prevails in reducing environments characterized
by the predomination of sulfide over sulfate. Complexing of
As(OH)3(aq) + H2S(aq) + H+
Tl+ in hydrothermal solution greatly depends on temperature
↔ AsS + 3H2O ∆rH << 0 (4)
and pH conditions (Bebie et al., 1998; Xiong, 2007). Accord-
(realgar)
ing to thermodynamic data published by Xiong (2007) for
2As(OH)3(aq) + 3H2S(aq) 200°C, Tl+ is the dominant species in acidic solutions, TlHS0
↔ As2S3 + 6H2O ∆rH << 0 (5) is dominant in the neutral to moderate alkaline pH range,
(orpiment) whereas TlCO−3 and TlOH0 prevail in extremely alkaline solu-
tions. Lorandite is the major solubility-controlling phase in
2Sb(OH)3(aq) + 3H2S(aq)
As-bearing hydrothermal systems (Xiong, 2007).
↔ Sb2S3 + 6H2O ∆rH << 0. (6)
The lack of Tl enrichment in the Au-rich part of the All-
(stibnite)
char deposit suggests that sulfidation of Tl+ at low pH and
Although Au, Sb, and As occur together in hydrothermal relatively high temperature was not an effective precipitation
solutions, differences in the stability of their complexes as mechanism:
hydrothermal conditions change affects their solubility (Auso-
Tl+ + Au(HS)2– + As(OH)3 + H+
lubility << Sbsolubility < Assolubility; Figs. 20, 21), which may account
↔ Au + TlAsS2 + 3H2O (7)
for the geochemical zonation observed at Allchar (Fig. 3).
(lorandite).
Although the chemical properties of Tl are well known, its
behavior in geologic processes is still vague. Thallium is an The isocon diagrams show a tight link between Tl and the
incompatible heavy metal that in aqueous solutions mostly low-temperature argillic alteration as well as significant cor-
exists in monovalent (thallous) oxidation state, although the relation between Tl and K (Fig. 10). Fluid inclusion data also
trivalent (thallic) oxidation state is stable under extremely suggest that the Tl-bearing mineralization was deposited from
oxidizing conditions. Monovalent Tl+ behaves like alkali cooled and diluted fluids (Fig. 18) enriched in KCl. The Tl
metals (e.g., K+), and it is mobile under acid to near-neutral mineralization is spatially related to dolomite suggesting that,
0 l/L) 0
pH = 5.5 –6 mo pH = 5.5
salinity =10 wt.% NaCl equiv
= 10
c(Fe-species) = 10 mol/L
-6 –
S) Au(H S)2
–
-5 a S
-5
l2 ( Au(H
– H2 2
C
Au l/L)
mo
Au / log mol/L
Au / log mol/L
–3
0
-10 =1 -10
– ( a H2S
Cl 2
Au
-15 -15
-20 -20
-25 -25
100 150 200 250 300 350 400 450 500 100 150 200 250 300 350 400 450 500
A Temperature / °C D Temperature / °C
10 T = 250°C 0
salinity =10 wt.% NaCl equiv T = 250°C
Au
5 Cl – c(Fe-species) = 10-6 mol/L
2 (a -5 –
=1 Au(H S)2
H2
S
0 0 –6
mo
Au / log mol/L
Au / log mol/L
l/L -10
-5 )
-10 Au -15
Cl –
2 (a
-15 H2
S =1
0 –3 Au(H -20
-20 mo S)2–
l/L
)
-25 -25
1 2 3 4 5 6 7 8 9 10 11 1 2 3 4 5 6 7 8 9 10 11
B pH E pH
0
T = 250°C
pH = 5.5
c(Fe-species) = 10 mol/L
–6
-5
Au / log mol/L
–
-10 Au(H S)2 Fig. 20. The solubility of Au as a function of (A) temperature,
(B) pH value, and (C) salinity of hydrothermal solutions, assum-
AuCl2– (aH2S = 10–6 mol/L ing coprecipitation of native Au and pyrite (see eq. 1, 2). The
-15
solubility of Au as a function of (D) temperature and (E) pH
value of hydrothermal solutions, assuming sulfidation of preex-
-20 AuCl2– (aH2S = 10–3 mol/L) isting Fe minerals as a critical factor for Au deposition (see eq.
3). The stabilities of Au complexes were constructed after the
thermodynamic data published by Helgeson et al. (1978), Shock
-25 et al. (1997), and Sverjensky et al. (1997) and using the SUPCRT
1 3 5 7 9 11 13 15 17 19 21 23 25 model and database (Johnson et al., 1992).
C Salinity / wt.% NaCl equiv
in addition to cooling, an increase in the pH of mineralizing of an Eocene erosion surface, the Vardar zone tectonic mélange
fluids was critical to deposition of Tl: was the site of Oligocene to Pleistocene episodes of extensional
Tl+ + As(OH)3 + 2H2S(aq) faulting and calc-alkaline to shoshonitic magmatism that pro-
duced an assortment of Cu-Au porphyry, skarn, hydrothermal
↔ TlAsS2 + 3H2O + H+ (8)
polymetallic (Pb-Zn ± Ag) replacement, and epithermal depos-
(lorandite).
its. Field relationships and geochronology show that the All-
This reaction is driven forward by neutralization of acid char Au-Sb-As-Tl deposit is spatially and temporally associated
hydrothermal fluids by carbonate rocks and hydrolysis of with a Pliocene (~5 Ma) shoshonitic volcano-plutonic center
framework silicates. on the northern side of a NE-trending volcanic field with min-
eralization hosted in Pliocene tuff and subvolcanic intrusions,
Discussion tuffaceous dolomite, and Triassic marble (Fig. 3). Stable iso-
topic, fluid inclusion, and trace element data suggest that con-
Model for the formation of the Allchar Au-As-Sb-Tl deposit cealed intrusions in this center were the source of metal- and
After collision of the Adriatic and Euroasian plates along the ligand-bearing fluids and heat that drove circulation of mete-
Vardar zone, overprinting Cretaceous subduction-related mag- oric ground water. Although isotopic data show that some lead
matism, early Tertiary contraction, exhumation, and formation and sulfur were leached from country rocks, the abundance
15 groundwater on the northern side of the system. The localiza-

c(As(OH)3) or c(Sb(OH)3) / log mol/L
pH=5.5
a(H2S,aq) = 10-6 mol/L tion of jasperoids and mineralization at structural intersections
10 within fault breccias and fracture zones and along the Eocene
unconformity shows that fluid flow was controlled by perme-
5 able structures and stratigraphy (Fig. 3B).
Fluid inclusion studies preclude boiling as a depositional
0
mechanism but provide evidence that fluids with different
salinities and temperatures mixed at the site of ore deposi-
Realgar tion. Isocon diagrams and chemical modeling suggest that
-5 Orpiment decarbonatization, silicification, argillic alteration, and Au,
Stibnite
Sb, As, and Tl mineralization formed in response to cooling
-10
100 150 200 250 300 350 400 450 500
and neutralization of acidic ore fluids by reactions with car-
bonate rocks and external ground water. Auriferous arsenian
A Temperature / °C
pyrite precipitated by cooling, mixing, and neutralization in
carbonate host rocks and by sulfidation of Fe in tuff. Quartz
15
and stibnite precipitated in response to cooling, realgar and
T = 250°C orpiment by cooling and acidification, and lorandite by cool-
c(As(OH)3) or c(Sb(OH)3) / log mol/L
a(H2S,aq) = 10-6 mol/L

10 ing and neutralization. The acidic character of the ore fluids
was probably due to the condensation of magmatic vapor and
dissociation of acid volatiles (CO2, SO2, HCl) into cool rocks
5 and ground water. Quaternary faulting, uplift, and erosion
exposed the deposits at the surface.
0
Comparison with Carlin-type gold deposits in Nevada
The Allchar deposit is similar to Nevada Carlin-type gold
-5 Realgar deposits in that it occurs near a terrain-bounding fault (Var-
Orpiment dar zone) in an area of low-magnitude extension and intense
Stibnite
-10
magmatism. It is mostly hosted in subvolcanic calcareous and
1 2 3 4 5 6 7 8 9 10 11 dolomitic sedimentary rocks, and mineralization occurs at
B pH intersections of high-angle faults and permeable stratigraphy
(e.g., Eocene unconformity). It has similar alteration types
15 (carbonate dissolution, silicification, argillization), ore minerals
a(As(OH)3) or c(Sb(OH)3) / log mol/L
T = 250°C (auriferous arsenian pyrite and marcasite, stibnite, realgar, orpi-

pH = 5.5
10
ment, lorandite), high Au/Ag ratios, and low base metal con-
tents (e.g., Radtke, 1985; Hofstra and Cline, 2000; Muntean
et al., 2011). It lacks fluid inclusion evidence of boiling, some
5
of the ore pyrite precipitated by sulfidation of tuff, late-stage
minerals precipitated primarily by cooling, and the late-stage
0
minerals contain S and Pb derived from country rocks.
It differs in that it is an isolated Au prospect with a close spa-
-5 Realgar
Orpiment
tial and temporal relationship to a shoshonitic volcano-plutonic
Stibnite center in a mineral belt dominated by intrusion-related Cu-Au
-10 porphyry, skarn, and hydrothermal polymetallic deposits. It is
-8 -6 -4 -2 clearly zoned (proximal Au-Sb to distal As-Tl), has more dolo-
C a(H2S,aq) / log mol/L
mitization and sericitic alteration, has more introduced Fe, Mg,
Fig. 21. The solubility of realgar (eq. 4), orpiment (eq. 5), and stibnite (eq. K, and Tl and less Au in ore pyrite, and contains more Cu, Sn,
6) as a function of (A) temperature, (B) pH value, and (C) activity of H2S(aq) Te, and Se in stibnite, realgar, orpiment, and lorandite. It has
in hydrothermal solutions. The solubility curves were constructed after the
thermodynamic data published by Helgeson et al. (1978), Pokrovski et al.
lower-temperature and higher-salinity fluid inclusions and clear
(1996), Zotov et al. (2003), and Perfetti et al (2008) and using the SUPCRT isotopic evidence for magmatic water, CO2, and H2S, and most
model and database (Johnson et al., 1992). of the ore pyrite in carbonate rocks precipitated by fluid mix-
ing (e.g., Radtke et al., 1980; Holland et al., 1988; Groff, 1996;
Hofstra, 1997; Hofstra and Rye, 1998; Cline and Hofstra, 2000;
of Cu, Sn, Te, and Se in stibnite, orpiment, realgar, and loran- Emsbo et al., 2003; Lubben et al., 2012). These differences
dite suggests that these metalloids were derived from mag- suggest that it is the very shallow and/or distal manifestation
mas. The zonation from southern Au and Sb mineralization to of a concealed porphyry system and is best classified as a distal
northern As and Tl mineralization is perpendicular to the axis disseminated gold deposit.
of the volcanic field and, together with variations in the fluid
inclusion and isotopic data, suggests that fluid flow was from Conclusions
south to north. Mineralization appears to have occurred at the The evidence presented in this article confirm that Carlin-
interface between ascending magmatic fluids and convecting style gold deposits can form in the shallow/distal part of
intrusion-centered hydrothermal systems. Gold, Sb, As, and Claypool, G.E., Holser, W.T., Kaplan, I.R., Sakai, H., and Zak, I., 1980, The
Tl were introduced by hot (>200°C), saline (up to ~ 21 wt % age curves of sulfur and oxygen isotopes in marine sulfate and their mutual
interpretation: Chemical Geology, v. 28, p. 199–260.
NaCl equiv), moderately acidic (pH <5) fluids that carried Cline, J.S., and Hofstra, A.H., 2000, Ore-fluid evolution at the Getchell Car-
traces of magmatic H2S and CO2. The mineral and chemical lin-type gold deposit, Nevada, USA: European Journal of Mineralogy, v. 12,
zonation in the district is a result of different transport mecha- p. 195–212.
nisms of Au, Sb, As, and Tl under hydrothermal conditions Cline, J.S., Stuart, F.M., Hofstra, A.H., Premo, W., Riciputi, L., Tosdal, R.M.,
and may indicate a potential for additional gold mineralization and Tretbar, D.R., 2003, Multiple sources of ore-fluid components at the
Getchell Carlin-type gold deposit, Nevada, USA, in Eliopoulos D., et al.,
under cover at the southern end of the district. The evidence eds., Mineral exploration and sustainable development, v. 2: Rotterdam,
from Allchar also suggests that Tl mineralization may be pres- Millpress, p. 965–968.
ent in the most distal neutralized portions of other intrusion- Cline, J.S., Hofstra, A.H., Muntean, J.L., Tosdal, R.M., and Hickey, K.A.,
centered hydrothermal systems. 2005, Carlin-type gold deposits in Nevada: Critical geologic character-
istics and viable models: Economic Geology 100th Anniversary Volume,
Acknowledgments p. 451–484.
Cvetković, L., Boronikhin, V.A., Pavičević, M.K., Krajnović, D., Gržetić, I.,
The manuscript was substantially improved by the comments Libowitzky, E., Giester, G., and Tillmanns, E., 1995, Jankovićite, Tl5Sb9
of Panagiotis Voudouris and John Muntean. Also we would (As, Sb) 4S22, a new TI sulfosalt from Allchar, Macedonia: Mineralogy and
like to acknowledge John Muntean for all his support and Petrology, v. 53, p. 125–131.
patience in editing this manuscript. Cvetković, V., Knežević, V., and Pécskay, Z., 2000, Tertiary igneous formations
of the Dinarides, Vardar zone, and adjacent regions: From recognition to
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Comparison of the Allchar Au-As-Sb-Tl Deposit, Republic of Macedonia,

Introduction submicron gold in association with pyrite and marcasite; and

The Allchar Au-As-Sb-Tl deposit is situated in the western

part of the Vardar zone, in close proximity to its contact with

the Adriatic and the Eurasian plate with elements of both

continental and oceanic rock types (Karamata et al., 2000;

na Dimitrijević, 2001; Zelić et al., 2010; Robertson et al., 2013).

It extends from northwest to southeast across the central part

en of the Balkan Peninsula and is situated between the Dina-

be rides, Drina-Ivanjica terrain, Korab-Western Macedonian

42°N Macedonian massif. Rifting was followed by the development

of a subsiding carbonate platform and formation of oceanic

crust during Late Triassic-Early Jurassic time (Sharp and

N Robertson, 2006; Dilek et al., 2007; Robertson et al., 2013).

Allchar The western (external) Vardar zone represents a complex zone

that comprises ophiolites and ophiolitic mélange (Karamata

posed of spinel lherzolite, harzburgite, and dunite, preserve

evidence of metamorphic soles at their base. The K/Ar age

Argillic alteration Stibnite-bearing jasperoid

N Stage 1 Stage 2 Stage 3 Stage 4

Triassic marble and dolomite Sulfidation

Triassic schist Supergene alteration

Mineralogy Host rock/mineralization Locality Age (Ma) Method Reference

Abbreviations: Qtz = quartz

Sample Mineralogy δ13C (‰ V-PDB) δ18O (‰ V-SMOW) Reference

1 Calcite 2.4 14.9 Volkov et al. (2006)

Marc Marcasite –4.7 Jankovic (1993) B1 Botryoidal

Abbreviations: V-CDT = Vienna-Canyon Diablo Troilite

Ultrabasic Basic Intermediate Acid

Phono- andesite High-K calc-alkaline

Unaltered Pliocene tuff

Concentration in altered rock

Concentration in altered rock

1,000 Te125 Sb121 Sb121 As75

1,000 Au197 Te125 1,000 Cs133 Sb121

1,000 Te125 Sb121 Cs133 Sb121

1,000 Te125 Au197

Hg202 1,000 Cs133

Tl205 Hg202 1,000

1,000 Hg202 Hg202

Fig. 11. (Cont.)

2.6‰, reflecting a strong input of magmatic H2S during the

Sample Mineralogy δDH2O (‰ V-SMOW) δ18Omineral (‰ V-SMOW) δ18OH2O (‰ V-SMOW) Reference

AD-2 Fluid inclusions, realgar –99 This study

Abbreviations: V-SMOW = Vienna-standard mean ocean water

Homogenization into liquid phase occurred from 120° to

Calcite, Volkov et al., 2006

Orpiment, fluid inclusion

15 Barite, fluid inclusion

50µm 15µm 20µm 10µm

100 200 300

15 groundwater on the northern side of the system. The localiza-

a(H2S,aq) = 10-6 mol/L

T = 250°C (auriferous arsenian pyrite and marcasite, stibnite, realgar, orpi-

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