Mineralium Deposita (2002) 37: 587598 DOI 10.

1007/s00126-002-0275-6

A RT I C L E

Strashimir Strashimirov Rumen Petrunov Milko Kanazirski

Porphyry-copper mineralisation in the central Srednogorie zone, Bulgaria

Received: 10 January 2001 / Accepted: 30 January 2002 / Published online: 1 May 2002 Springer-Verlag 2002

Abstract The porphyry-copper systems in the central part of the Srednogorie zone (Bulgaria) are represented by three major deposits (Elatsite, Medet and Assarel) and several smaller deposits and occurrences, all of them within the Panagyurishte ore district. The hydrothermal systems are related to Late Cretaceous calc-alkaline igneous complexes. Ore mineralisation is developed predominantly in the apical parts of subvolcanic and intrusive bodies as well as within the volcanic and basement metamorphic rocks. Several of the porphyry systems are spatially associated with shallow-level intermediate and high-sulphidation volcanic-hosted epithermal deposits of economic importance, such as the major gold-copper mine at Chelopech located 10 km from the Elatsite porphyry-copper deposit. Mineralisation processes in the porphyry deposits start with intensive hydrothermal alteration of the wall rocks. K-silicate alteration is characteristic for pre-ore hydrothermal activity in all of them, and it is located mostly in their central parts. Propylitic alteration is prominent in the Medet and Assarel deposits. The Assarel deposit is located in the central part of a palaeovolcanic structure and shows a large spectrum of pre-ore alterations, including propylitic, sericitic, and advanced argillic assemblages. The initial stages of the hydrothermal systems are characterised by high temperatures (>550 500 C) and highly saline (5020 wt% NaCl equiv.) and vapour-rich uids of likely magmatic origin. The composition of the uids gradually changes from

S. Strashimirov (&) University of Mining and Geology St. Ivan Rilski, Soa 1700, Bulgaria E-mail: sbs@sta.mgu.bg R. Petrunov (&) M. Kanazirski (&) Institute of Geology, Bulgarian Academy of Sciences, Soa 1113, Bulgaria E-mail: petrunov@geology.bas.bg E-mail: milko@geology.bas.bg

H2ONaClFeCl2 to H2ONaClKCl and H2ONaCldominated as the uids cool, react with wall rocks, and may become diluted with meteoric water. Fe-Ti-oxide mineral associations were formed early in all deposits, later followed, in the Elatsite deposit, by an assemblage of bornite, chalcopyrite, platinum group element (PGE) phases, Co-Ni thiospinels, Ag- and Bi-tellurides, and selenides. The main ore stage in all deposits is dominated by chalcopyrite pyrite, associated with propylitic alteration at Medet, K-silcate-sericite alteration at Elatsite, and chlorite-sericite alteration at Assarel. Specic geochemical features of the ore systems are marked by precipitation of numerous ne-grained mineral inclusions in chalcopyrite and pyrite (palladoarsenide, Pd-rammelsbergite, Cu-Ni sulpharsenides in Elatsite; Co-and Ni-pyrite, carrolite, vaesite, sulvanite and colusite in Medet; enargite, As-sulvanite, colusite, goldeldite, wittichenite, calaverite and aikinite in Assarel). Native gold and electrum are observed as small grains, except in Elatsite where larger aggregates up to several millimetres are found. Molybdenite is present as small akes within chalcopyrite, or forms felted aggregates within thin quartz veinlets in the Elatsite and Medet deposits, and very rarely at Assarel. Thin veinlets of quartz-galena-sphalerite are found at the upper parts of the deposits. Supergene alteration of the primary sulphide minerals is developed in the Assarel deposit where a thick blanket of secondary copper mineralisation (chalcocite, covellite) has formed. In the other two deposits, secondary mineral associations (Cu and Fe oxides and hydroxides) are limited to near the surface. Dierences in the deposits studied suggest that Elatsite and Medet are formed probably at deeper levels of the porphyry systems, whereas Assarel is developed at rather shallower and lower-temperature conditions typical of the apical part of a subvolcanic body intruding its volcanic superstructure. Keywords Porphyry copper Balkan Bulgaria Srednegorie Panagyurishte Elatsite Medet Assarel

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Introduction
The Panagyurishte district is a part of the Central Srednogorie zone and includes three, relatively large porphyry-copper deposits (Assarel, Medet and Elatsite), several smaller ones (Tsar Assen, Vlaikov Vruh, Karlievo, and others) and numerous ore occurrences of the same type (Fig. 1). Individual porphyry-type deposits are closely associated with volcanic-hosted, medium- to high-sulphidation epithermal deposits mined for gold and copper, including Chelopech near Elatsite, and Elshitsa near Vlaikov Vruh (Bogdanov 1987; see Bonev et al. 2002, and Kouzmanov et al. 2002, this volume, for further references). Medet is Europes rst porphyrycopper producer. More than 460 million tonnes (Mt) of ore has been mined from the district at an average grade of 0.42% Cu, producing over 1.9 Mt copper and
Fig. 1 Geological map of the Panagyurishte ore district. All of Bulgarias major porphyry-copper and volcanic-hosted massive sulphide epithermal deposits are aligned along the NNW-SSEtrending Panagyurishte corridor cutting the Late Cretaceous Srednogorie magmatic zone of broadly EW orientation (modied after Bogdanov 1987)

2.5 million oz. of gold since 1950 (Table 1). Assarel, Elatsite and Chelopech are currently in production. The Panagyurishte ore district in Bulgaria follows a distinct NNW-SSE-trending structural corridor crossing the broadly E-W-trending Srednegorie zone, which is part of the Alpine-Carpathian-Balkan orogenic system of eastern central Europe. The Panagyurishte district (Bogdanov 1987; Popov et al. 1996) and the Timok complex, hosting the world-class porphyry-copper and epithermal deposits at Majdanpek and Bor in Yugoslavia (Ciobanu et al. 2002, this volume), are the only two major economic porphyry-copper districts along a much more extensive belt of Late Cretaceous calc-alkaline magmatism, known as the Apuseni-Banat-Timok-Srednegorie belt (after Popov et al. 2000d) or the Banatitic Magmatic and Metallogenic Belt (Berza et al. 1998). The porphyry-copper deposits in the Panagyurishte district were objects of intensive investigations during the last decades, and numerous studies provide data about their hydrothermal systems and mineral composition. Metallogenic features of the district are discussed by, among others, Bogdanov (1984, 1987) and Popov et al. (1996). Ore mineralogy studies were carried out by Dimitrov (1988), Petrunov et al. (1992), Petrunov and

589 Table 1 Copper deposits in the Panagyurishte ore district and their production and resources (data provided by the Bulgarian Ministry of Environment and Water) Deposit Porphyry copper Assarel Elatsite Medet Vlaikov Vruh Tsar Assen Volcanic-hosted sulphide Chelopech Elshitsa Radka Krassen Remaining resources 254 Mt @ 0.41% Cu In production since 1976 154 Mt @ 0.33% Cu In production since 1981 Mined out (19641993) Mined out (19621979) Mined out (19801995) 31 Mt @ 1.39% Cu, 3.5 g/t Au In production since 1954 Mined out (19471996) (1.5 Mt @ 1.27% Cu) Mined out (19421997) (2.5 Mt @ 0.6% Cu) Mined out (19621973) Past production 100 Mt @ 0.53% Cu, trace Au 165 Mt @ 0.38% Cu, 0.21 g/t Au 163 Mt @ 0.32% Cu, 0.1 g/t Au 9.8 Mt @ 0.46% Cu 6.6 Mt @ 0.47% Cu 11.5 Mt @ 1.0% Cu, 3.0 g/t Au 2.5 Mt @ 1.0% Cu 6.4 Mt @ 1.0% Cu 0.30 Mt @ 0.76% Cu

Dragov (1993), Dragov and Petrunov (1996), and Popov et al. (2000a) in the Elatsite deposit, by Ushev et al. (1962), Strashimirov (1982, 1992) and Popov et al. (2000b) at Medet, and by Bogdanov (1987), Petrunov et al. (1991), Strashimirov (1993) and Popov et al. (2000b) at Assarel. Ushev et al. (1962), Arnaudova et al. (1991), and Kanazirski et al. (1995, 2002) provided observations about alteration distributions and their thermodynamic interpretation. Fluid-inclusion studies of the systems in porphyry deposits were carried out by Bogdanov (1987) and Strashimirov and Kovachev (1992). The aim of the present paper is to summarise the common and distinctive features of the three major porphyry-copper systems (Elatsite, Medet and Assarel), with a focus on their unusually complex element and ore mineral associations and the associated hydrothermal alteration of the diverse host rocks. In combination with a reconnaissance uid-inclusion study, these observations are used to interpret the evolution of the hydrothermal systems and the temperature conditions of ore formation.

Geological setting
The Panagyurishte ore district is a prominent structural lineament within the Banat-Srednogorie tectonic and metallogenic zone, which is one of the main magmatic and metallogenic structures of the Alpine BalkanoCarpathian-Dinaride system. The Panagyurishte ore district hosts all major Cu-Au deposits of Bulgaria and covers about 1,500 km2 of central Srednogorie. It includes a part of the Stara Planina (Balkan) mountain belt, which extends EW across the breadth of Bulgaria (Fig. 1). The geology of the region is dominated by extensive Late Cretaceous calc-alkaline magmatism, including intrusive and extrusive volcanic rocks with interbedded sedimentary rocks, developed over a basement of Precambrian and Riphean-Cambrian metamorphic rocks, Middle and Late Palaeozoic intrusions, and StephanianPermian and Triassic sedimentary rocks.

Precambrian metamorphic rocks of the basement are present as various (mainly granitic) gneisses, schists, and amphibolite (Fig. 1). The Riphean-Cambrian metamorphites include greenschist phyllites, diabase and diabase tus (Katskov and Iliev 1993; Cheschitev et al. 1995). Palaeozoic intrusive rocks include the Vejen Pluton of granodiorite to granitic composition located in the northernmost part of the map area (Fig. 1), and several small intrusive bodies of peridotite, gabbrodiorite, granodiorite to quartzdiorite and tonalite in the central and southern parts (Dabovski et al. 1972). Stephanian-Permian sediments have very restricted development in the region, and occur as isolated relicts (not included in Fig. 1) of red-bed conglomerates to coarse sandstones south of the Elatsite deposit. Triassic sediments are represented mainly by limestone and sandstone in the north, and sandstone in the southern part of the region. Late Cretaceous rocks have a wide distribution in the area. They have been classied into four complexes according to composition and stratigraphic position, and they are timed with variable precision by Moev and Antonov (1978) and limited K-Ar dating by Lilov and Chipcakova (1999). The Turronian terrigenous complex (9188 Ma) includes coal and sandstones. The Lower Senonian volcanogenic (8886 Ma) complex includes dominant eusive and lesser volcano-sedimentary and rarely sedimentary rocks formed as a result of extrusive activity of numerous volcanoes and accompanying submarine sedimentary processes. Lava sheets and agglomerates of block tu are characteristic for the central parts of the palaeovolcanic structures, whereas lapilliagglomerates, tu, tute, sandstone, limestone, argillite and tephroid ysch are most often found distally. Andesitic composition of the volcanic rocks dominates, but dacitic lithologies are more widespread in the southern part of the district, passing to latite-andesite, latite and eventually to trachyte in the northern area near Chelopech. The Early Senonian subvolcanic-hypabyssal complex involves numerous intrusive stock-like to elongate dykelike bodies and dykes which are co-magmatic with the

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eusive rocks. Their composition ranges from monzonite porphyry to granodiorite, quartzmonzodiorite, and rarely quartzgabbro. The volcanic-intrusive structures are indicated by lateral variations in the volcano-sedimentary deposits, and by radial and circular fracture patterns interpreted from aerial photographs and detailed mapping (Popov 1987, 1996; Popov and Popov 2000). They include, in a possible sequence of decreasing age based on lithostratigraphic relations, major centres near Celopech Elatsite, Medet Assarel, Elshitsa Vlaikov Vruh, and Pesovets (Popov 1996). The Late Senonian (Maastrichtian) ysch complex is represented by limestones and sandstones. Volcanism and ysch sedimentation was immediately followed in the Late Cretaceous by a folding and faulting event, leading to several partly fault-bounded E-W to WNWESE grabens or synclines where the volcanics are preserved (near Chelopech, Panagyurishte), separated by uplifted blocks exposing the crystalline basement (Fig. 1; Popov 1996). As a result, the major part of preLate Cretaceous rocks was eroded during uplift. Palaeogene, Pliocene and Quaternary sediments overlap transgressively the deformed Late Cretaceous stratigraphy, and lie directly upon the basement rocks in some areas.

Geology, wall-rock alteration and ore mineralisation of the porphyry-copper deposits

Elatsite The Elatsite deposit is located in the northern part of the Elatsite-Chelopech ore eld about 10 km NW of the Chelopech volcanic centre (Popov et al. 2000a). It is associated with Late Cretaceous dykes (quartz syenodiorite and granodiorite porphyries) in the Precambrian to Early Palaeozoic phyllites, and a Late Palaeozoic granodiorite (Fig. 2). The phyllites are contact-metamor-

phosed to hornfels adjacent to the dykes and Palaeozoic granodiorite. The dykes dip south in the direction of an inferred magma chamber of the volcano-intrusive structure. Porphyry-copper mineralisation occurs with an ellipsoidal shape (800350 m, elongated SWNE) dipping south and developed in the porphyry dykes, the basement granodiorite, and less in the metamorphic rocks. K-silicate alteration (K-feldspar, biotite and quartz, Table 2) in the Elatsite deposit is established in the granodiorites, the dykes and in their metamorphic country rocks along the contacts with the porphyry dykes, and is characterised by metasomatic replacement of the primary minerals. Metasomatic K-feldspar and biotite replace the primary K-feldspar and plagioclase. Amphibole is replaced by biotite and biotitic metablasts with inclusions of quartz, feldspar and ore minerals. Igneous biotite is partly replaced by chlorite, and plagioclase by calcite and illite. The propylitic alteration in the Elatsite deposit includes chloritisation, epidotisation, sericitisation and actinolitisation of the Palaeozoic granodiorite and the Late Cretaceous hypabyssal intrusions, as described by Bogdanov (1987). Local epidote-chlorite-quartz-carbonate alteration is contemporary with the magnetitebornite-chalcopyrite assemblage (according to Dragov and Petrunov 1996), and is grouped with the propylitic alteration. Sericitic alteration is developed in the upper levels of the deposit and is represented by a quartz-illite-pyrite assemblage and short veinlets of ne to coarse-grained, euhedral pyrite and minor carbonate. The term sericitic is used in this work in the sense of alteration consisting of a mica-type mineral (e.g. illite) + quartz + pyrite, including mixed-layer illite-smectite in which illite layers are predominant (following Hayba et al. 1985). These assemblages were formed during the epithermal sericitisation as a reaction of the uid with K-silicatealtered rocks. The transitional zone (K-silicate-sericitic)

Fig. 2 Geological map (left) and section (right) of the Elatsite porphyry Cu (-Au-PGE) deposit. Chalcopyrite bornite mineralisation is almost exclusively associated with K-silicate alteration in and around Cretaceous porphyries which intrude the Palaeozoic Vejen Granodiorite and earlier metasediments (after Kalaidjiev et al. 1984)

591 Table 2 Wall-rock alteration types and mineral assemblages. Ab Albite, act actinolite, alu alunite, bi biotite, calc calcite, chl chlorite, ep epidote, ksp K-feldspar, kl kaolinite, hem hematite, il illite, prl pyrophyllite, py pyrite, qtz quartz Wall-rock alteration types Mineral assemblages Medet Propylitic Ep+chl+calc Elatsite Ep+act+ab+bi+qtz+calc Ep+chl+ab+bi+qtz Assarel Ep+chl+ab+ksp+il+qtz+py Chl+ab+ksp+il+qtz+py Chl+ab+il+qtz+py Chl+kl+ab+il+qtz+pyepksp Kl+ab+il+qtz+py Chl+il+qtz+py Ksp+bi+qtz Ksp+bi+qtz+il+pl+calc Ksp+chl+qtz+il+ab Chl+ab+qtz+il+py Chl+qtz+il+py Il+qtz+py Il+qtz+py Il+qtz+py Il+qtz+py+prl Il+qtz+py+kl Prl+qtz+py Kl+qtz+py Alu+qtzprlpyhem Alu+qtzklpyhem

Propylitic argillic Propylitic-sericitic K-silikate K-silicate-sericitic Sericitic Sericitic advanced-argillic Advanced argillic (acid-chloride subtype) Advanced argillic (acid sulphate subtype)

between the K-silicate alteration and sericitic alteration is characterised by the presence of chlorite, sericite, quartz, pyrite and chalcopyrite. A particular characteristic of Elatsite is an early magnetite-bornite-chalcopyrite association containing platinum group elements (PGE), Co, Ni, Te, Se, Bi, Au,
Table 3 Ore mineral associations and geochemical assemblages. Aikin Aikinite, brnt bornite, bcz bohdanowiczite, brvt bravoite, cal calaverite, calc calcite, car carrollite, chal chalcocite, chpy chalcopyrite, cls clausthalite, colus colusite, cov covellite, en enargite, euc eucairite, gal galena, Au native gold, gldf goldeldite, hem hematite, hs hessite, ilm ilmenite, kz kawazulite, ln linnaeite, mgt Ore mineral association Mgt-hem brnt, chpy Location and mineralisation style Central parts; veinlets, aggregates, lenses Whole ore body; veinlets, short veins, disseminated, aggregates Specic geochemical assemblages 1. FeTi 2. CuPGEFe CoNiTeBiSe AuAg 3. AgSeTe, Bi 1. 2. 3. 4. 5. 6. 7. FeCuMo, Au CoNi NiPdAs CuAs (Te) CuSnV CuPbBi BiAgTe Mo-Re

and Ag in minerals such as merenskyite, carrolite, nickeliferous linnaeite, pyrrhotite, hessite, clausthalite, kawazulite, naumannite, eucairite, bohdanowiczite, weissite, native Au, Te and Bi, and unnamed phases (Pd, Ag)3Te4 and PdNiTe (Table 3; Petrunov et al. 1992; Petrunov and Dragov 1993; Dragov and Petrunov 1996).
magnetite, mch michenerite, mer merenskyite, mol molybdenite, nm naumannite, Bi native Bi, Te native Te, Pd-ars Pd-arsenide, Pdramm Pd-rammelsbergite, py pyrite, pyrrh pyrrhotite, qtz quartz, rut rutile, sph sphalerite, sulv sulvanite, tetr tetradymite, vaes vaesite, ws weissite, wittch wittichenite Typomorphic minerals Elatsite Assarel Medet Mgt, hem, ilm, rut Py, chpy, mol, gld Colus, sulv, hs, tetr Car, vaes, Co-Ni-pyr qtz, mol Qtz, pyr, calc Qtz, gal, sph Cov, chal, brnt

Mgt, hem, rut, ilm Mgt, hem, ilm Brnt, chpy, mer, ln, car, ws, mch, Au Hs, cls, kz, nm, euc, bcz, Te, Bi Py, chpy, mol, gld Car, vaes Pd-ars, Pd-ramm qtz, mol Qtz, pyr, calc, gld Qtz, gal, sph Cov, chal, brnt Py, chpy, gld En, gldfd, cal Colus, sulv, As-sulv Aikin, wittch qtz, mol Qtz, pyr, gld Qtz, gal, sph Cov, chal, brnt

Qtz-py-chpy

Qtz-mol

Inner parts; thin veinlets Qtz-py calc Medium and outer parts; short veins Qtz-gal-sph Marginal and upper levels; short veins Cov-chal (sec) Upper levels (zone of secondary enrichment in Assarel)

FeAu PbZnAg Se CuFe

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This mineral association is spread irregularly throughout the deposit, forming lenses dominated by magnetite (partly replaced by hematite) with K-feldspar and biotite. Sulphur activity was relatively low, as indicated by the local precipitation of pyrrhotite in this association, and also by the presence of Co-Ni thiospinels, tellurides and selenides. The presence of bornite and Pt-Pd phases, tellurides and selenides associated with magnetite is not found in the other deposits from the central Srednogorie zone, but is known from other porphyry-copper systems in the Carpatho-Balkan belt, including the Majdanpek (NE Serbia; data of Pavichevich in Jankovic 1990) and Buchim deposits (Macedonia; Petrunov et al. 2001). Similar associations have been described from the Santo Tomas II deposit in the Philippines (Tarkian and Koopmann 1995). Coarse-grained native gold occurs in thin veinlets cutting the magnetite-bornite-chalcopyrite association, and individual gold crystals up to several mm are found in small cavities within bornite. The main association of economic importance is the quartz-pyrite-chalcopyrite association as veinlets, aggregates or disseminations. Rare minerals such as Pdrammelsbergite, palladoarsenide, Co-Ni sulphoarsenide of the gersdorte-cobaltite group as well as unidentied Pd-Ni arsenides are found as inclusions mainly within chalcopyrite (Dragov and Petrunov 1996). Gold is present as tiny inclusions of electrum (2429 wt% Ag) in chalcopyrite (Strashimirov and Kovachev 1994). This association contains also some molybdenite in small, well-dened quartz-molybdenite veinlets. The main sulphide association is accompanied by a K-silicate-sericitic type of alteration. A quartz-pyritechalcopyritecalcite association is developed mainly at the marginal and upper parts of the deposit as veins and veinlets. A quartz-galena-sphalerite association has a very limited distribution in the marginal parts of the deposit. Late-stage stockwork inll consists of quartz-calcite-zeolite. Supergene alteration is very subordinate and is characterised by tenorite, claudetite, chalcophyllite, libetenite, thenardite, and chalcocite (Tokmakchieva 1994). Medet The Medet deposit is located in the apical part of the Medet intrusive body of quartz monzodiorite and granodiorite porphyries which intruded in the N-NE part of the Assarel-Medet ore eld (Fig. 3). The basement includes Palaeozoic granitic and metamorphic rocks, mainly gneisses. The most intensive jointing and faulting is developed in the central and eastern parts of the intrusive body. These are the sites of high permeability and locate copper mineralisation. The orebody is an extensive stockwork of pipe-like shape, elongated in a NW-SE direction, and drilling has conrmed the mineralisation over 1,000 m in depth. The wall-rock alteration in the Medet deposit has been studied by Ushev et al. (1962). Ushev et al. (1962)

Fig. 3 Geological overview of the location of the mined-out porphyry-copper deposit of Medet and associated minor ore occurrences, located in and above the roof of a large porphyritic granodiorite to quartz-monzodioritic intrusion. The Medet intrusive body is emplaced near the intersection of a NNW-oriented and probably deep-seated fault zone with fault slices developed along the contact between Paleozoic granitoids and metamorphic basement rocks (after Popov and Popov 2000)

established mineral-specic alteration zones which can be combined into two main types: K-silicate alteration (metasomatic K-feldspar and biotite, quartz and apatite) and propylitic alteration (chlorite, epidote and carbonate). Epidotisation, chloritisation and subordinate sericitisation accompany the sulphide precipitation in the Medet deposit. Sericititic alteration has a limited distribution mainly around the zone of K-silicate alteration (S. Chipchakova, personal communication 2000). The earliest ore mineral association is quartz-magnetite-hematite associated with K-silicate propylitic alteration, containing Ti-bearing minerals such as rutile, ilmenite, Mn-ilmenite, pseudobrookite and davidite (Strashimirov 1992). The pervasive main quartz-pyrite-

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chalcopyrite association contains mineral inclusions which form specic assemblages. The Co-Ni assemblage is represented by carrollite, vaesite, Co- and Ni-bearing pyrite (with a content of cobalt up to 17 wt%). Cu-Sn-V (colusite and sulvanite) and Bi-Ag-Te (hessite and tetradimite) assemblages are rarely found as micron-sized inclusions in chalcopyrite (Table 3; Strashimirov 1982). Native gold is found mainly as ne inclusions in chalcopyrite, rarely in pyrite. The Ag content of gold varies within the range of 8 to 32 wt% (Strashimirov and Kovachev 1994). Molybdenite occurs as rare single akes, but generally it forms discrete veinlets together with quartz. Molybdenite is determined as 2H and rarely 3R polymorphic modications, and the latter is characterised by a higher Re content. The quartz-pyrite association forms well-dened veins and veinlets in the central part of the deposit. The quartz-galena-sphalerite association is observed rarely as small veins in the upper and marginal parts of the deposit. Secondary copper minerals are rarely found in the deposit, mainly in its upper part or along faults at depth. Assarel The Assarel deposit, unlike the previous two deposits, is associated with and partly hosted by coeval volcanic rocks. It is located in the central part of the Assarel volcano, in an area of intensive radial and concentric faulting and jointing (Fig. 1). The central part of the volcano is predominantly composed of massive and brecciated lava sheets, and pyroclastics of dominantly andesite and latite-andesite composition. The Assarel granodiorite porphyry is located in the centre of the former stratovolcano and consists of two apophyses which join at depth. The eastern part of the structure is

uplifted due to post-ore faulting, such that weakly altered basement metamorphic rocks are now exposed at the same structural level as the volcanic rocks with advanced argillic alteration. The ore mineralisation forms a cone whose top is inclined by 8085 towards the south or south-west. The horizontal cross section of the deposit, therefore, has an ellipsoidal shape with a long axis oriented in a N-S direction. Mineralogical observations of the upper levels of the Assarel deposit revealed the following pre-ore hydrothermal alteration within the subvolcanic-hypabyssal bodies, volcanic rocks and Palaeozoic granitoides: propylitic, propylitic-argillic, propylitic-sericitic, sericitic, sericitic-advanced argillic and advanced argillic acidchloride and acid-sulphate subtypes (Kanazirski 1994, 1998, 2000, 2002). A typical cross section in the central part of the deposit shown on Fig. 4 illustrates the spatial distribution of the alteration pattern. K-feldspar-biotite metasomatites, as relics in some areas of propylitised granodiorite porphyries and Paleozoic granitoides, are reported by Arnaudova et al. (1991) and demonstrate early K-silicate and K-silicatepropylitic alteration, the latter one sporadically found in the upper levels of the Assarel deposit (Kanazirski 2000, 2002). Epithermal sericitisation and advanced argillisation in the lithocap are seen to overprint propylitic and K-silicate alterations. The propylitic alteration is best developed within the Late Cretaceous volcanic rocks, subvolcanic hypabyssal bodies, and partly within the Paleozoic granitoides. Propylitic-argillic and propylitic-sericitic alterations are distinguished in the transition zone toward the propylitic alteration (Kanazirski 2000). Mineral assemblages including illite + quartz + pyrite + pyrophyllite (kaolinite) dene a transitional sericitic-advanced argillic type of alteration (Kanazirski et al. 1995; Kanazirski 2000, 2002).

Fig. 4 Geological section through the central part of the Assarel deposit. Economic chalcocite-covellite mineralisation is associated with an irregular subhorizontal zone of supergene enrichment overprinting sericitic and advanced argillic alteration, above earlier propylitic alteration with hypogene pyrite-chalcopyrite mineralisation. The southern limit of the orebody (cut-o grade 0.15% Cu) is to the left of the depicted section (after Popov et al. 1996)

594

Advanced argillic alteration is represented by two subtypes. The porphyritic textures are overprinted and obscured in the acid-chloride subtype of alteration, with a mineral assemblage of pyrophyllite, quartz and pyrite diaspore, corundum, zunyite and kaolinite. The assemblage kaolinite + quartz + pyrite is rare. The acidsulphate subtype, including the precipitation of alunite + kaolinite, suggests changes from HCl-rich uids to H2SO4-rich ones with time. Similar mineral assemblages typical of advanced argillic alteration are described in high-sulphidation epithermal deposits by Silberman and Berger (1985), Sillitoe (1991, 1995), Eaton and Settereld (1993), Arribas (1995) and others. The ore mineralogy and alteration at Assarel is particularly complex compared to the other deposits. The early quartz-magnetite-hematite association, which is typical of the other porphyry copper deposits in the region, occurs only in a very limited extent in the Assarel deposit. The late quartz-molybdenite association is very rare. Quartz + chalcopyrite pyrite as the main hypogene ore stage is temporally associated with sericitic and transitional sericitic-propylitic alteration. Quartzpyrite with minor chalcopyrite is prominent in the central and marginal parts of the deposit. The quartzgalena-sphalerite association is rarely developed and found mainly in the upper part of the deposit. Galena and sphalerite are found in well-dened veins with chalcopyrite at depth. Several mineral assemblages representative of high-sulphidation style are established in the upper levels (Table 3; Petrunov et al. 1991). These include enargite, goldeldite (Cu-AsTe assemblage), colusite, As-sulvanite and sulvanite (Cu-Sn-V assemblage), aikinite and wittichenite (Cu-Bi assemblage), hessite and tetradymite (Bi-Ag-Te assemblage) found as ne mineral inclusions in chalcopyrite. They are spatially related to sericitic and advanced argillic alterations of the volcanic rocks in the highest parts of the deposit. Thus, Assarel combines typical features of porphyry copper at depth with an overprint of high-sulphidation style of mineralisation in the upper parts of the system. Assarel is the only major deposit in the district with a well-developed supergene enrichment blanket of chalcocite and covellite, which is of major importance for the economics of the deposit. In contrast to the other deposits in the region, native gold is rare in the hypogene ore but assays show elevated Au concentrations near the contact between the zone of oxidation and the zone of secondary enrichment (Strashimirov 1993). The zone of supergene enrichment is 6070 m thick above primary quartz-pyrite-chalcopyrite ore, and below a zone of complete oxidation which usually comprises the rst 1015 m below the present-day land surface. Minor porphyry copper deposits The Tsar Assen deposit is situated in the SE part of the Radka ore eld in the easternmost part of the Panagyurishte ore district (Fig. 1, Kouzmanov 2002, this vol-

ume). The area is composed of andesitic eusive rocks derived from the northern part of the Elshitsa volcano-plutonic structure. Dominant rocks are lapilliagglomerate tu and lava ows and lesser ash tus and lava breccias. Subvolcanic dacite and granodiorite porphyries cut the eusive rocks. Ore mineralisation is related to two larger, stock-like granodiorite porphyry bodies dipping steeply SSW. The western orebody (Tsar Assen 1) is located in the apical part of the granodiorite porphyry and was mined by an open pit. A zone of oxidation and leaching is developed at the upper levels, followed by secondary copper mineralisation overlying a zone of primary sulphides at depth. The main ore associations and their spatial distribution are similar to those established in the Assarel deposit. A specic feature of this deposit is the minor quantity of molybdenite, and the presence of mineral inclusions of cobaltite, linneite and millerite in the quartz-pyrite-chalcopyrite association. The Vlaikov Vruh deposit is located close to the southern border of the Elshitsa graben within the broader Elshitsa ore eld, covering the easternmost part of the Panguyrishte ore district (Fig. 1). The geology of the area is composed of Precambrian gneiss and overlying eusive andesites which are intersected by a subvolcanic, E-W-trending, dyke-like dacite body. The ore mineralisation is spatially related to a small intrusion of granodiorite porphyry (dacite in its marginal parts), extending in E-W direction. The intrusion has irregular contacts with many apophyses, and it includes numerous wall-rock xenoliths (metamorphic rocks, andesites and Palaeozoic granites; Popov et al. 2000c). The ore mineralisation is most intensive along the faults and at brecciated contacts adjacent to large xenoliths. The main orebody is located at the intersection of two fault zones of SSW and ENE strike. The mineralogical composition of the ore associations has not been studied in detail because the deposit was closed more than 20 years ago, but published data suggest that all typical associations of the other porphyry-copper deposits in the region are present at Vlaikov Vruh (Bogdanov et al. 1971).

Data from uid-inclusion studies

Reconnaissance uid-inclusion studies have been performed on quartz samples from dierent ore associations of the three major porphyry deposits in the region (Tables 4 and 5). The majority of uid inclusions contain liquid + vapour (type A) whereas uid inclusions with liquid + vapour + solid (type B) have been observed less frequently (Fig. 5). They are subdivided into six subtypes according to their petrographic features (Table 4). Halite, sylvite, hematite and rarely sulphide minerals are found as daughter minerals in type B inclusions (Fig. 5a, b, d). The chemistry of the hydrothermal uids has been inferred from the presence of daughter crystals and from measurements of eutectic temperatures, mostly in B type inclusions. An evolution

595 Table 4 Fluid-inclusion types and their characteristic features Type A1 Composition L+V Characteristics Large gas bubble (1:3 to 1:5), isometric shape (or negative crystal), presence of CO2 and CH4, extremely high temperature of homogenisation (>500 C), quartz-feldspar association A very large, dark gas bubble (1:3 to 1:2), isometric shape, often homogenisation in the gas phase, Th<(?)400500 C, quartz associated with pyrite, chalcopyrite, pyrrhotite The most abundant inclusion type. Ratio between gas and liquid varies in large range (1:6 to 1:20); quartz associated with sulphide minerals, or carbonates formed during late stages of hydrothermal processes, Th 420 to 120 C Large inclusions (up to 50 lm) with dark gas bubble, isometric or of irregular shape, daughter minerals are hematite (S1) and halite (S2) (rarely tiny opaque mineral present), high salinity of liquid, Th 400575 C Large inclusions with dark gas bubble, isometric or irregular shape, daughter minerals S2 S1 S3 (sylvine), high salinity of liquid, Th 380490 C, quartz associated with magnetite, hematite, rutile, bornite Very large inclusions (up to 100 lm), S2 and S3 present, hematite is found often, and opaque minerals are rarely present Elatsite ++ Medet + Assarel

A2

L+V

++

A3

L+V

++

++

B1

L + V + S1 + S2

+++

B2

L + V + S1 + S2 S3

++

B3

L + V S1 + S2 + S3 S4

++

Table 5 Homogenisation temperatures, composition and salinity of uid inclusions in the porphyry copper deposits of Elatsite, Medet and Assarel (n.d. No data) Mineral association Th (C) Elatsite Quartz-K-feldspar Quartz-magnetite-hematite ( born, chlpy, pyrrh) Quartz-pyrite-chalcopyrite Quartz-molybdenite Quartz-pyrite Quartz-galena-sphalerite >500 n.d. 575450 H2ONaClFeCl2 50 wt% NaCl equiv 450330 H2ONaClKCl to H2ONaCl 360310 300260 240230 Medet >500 n.d. 400380 H2ONaClFeCl2 2012 wt% NaCl equiv 390320 H2ONaClKCl to H2ONaCl 330300 310280 280240 Assarel n.d. n.d. n.d. n.d. 310290 n.d. Not found 230215 195150

of the uid composition from H2ONaCl FeCl2 to H2ONaClKCl and H2ONaCl is indicated by the brine inclusions, from type B2 through type B3 to the aqueous inclusions of type A3. The uid inclusions are distributed very irregularly within the quartz from dierent associations and deposits. Overall, the abundance of visible-size inclusions is greater in quartz from ore mineral associations which formed in the earlier stages of the mineralisation process, and is practically unavailable for the late and probably low-temperature argillic alteration assemblages. Quartz from the Elatsite deposit contains the whole spectrum of inclusions observed in the district, whereas quartz from the Assarel deposit contains relatively few inclusions of type A3 only. Large-bubbled two-phase

inclusions (type A1) in quartz associated with K-feldspar indicate a temperature above 500 C for the earliest recorded uids. Well-shaped three-phase inclusions (type B) are found in quartz associated with the rst ore mineral assemblages including magnetite bornite hematite pyrrhotite and Ti-bearing minerals at Elatsite. The temperatures of homogenisation and the salinity measured from the inclusions of type B are higher in the Elatsite deposit than at Medet (Table 5). Eects of high-temperature boiling in the Elatsite and Medet deposits is indicated by type A2 vapour inclusions coexisting with brine inclusions (type B1) which have higher salinity than the pre-ore inclusions of type A1. Three-phase inclusions are not found in quartz associated with the later formed ore

596 Fig. 5ad Fluid inclusions in quartz associated with porphyry-copper ores in the Panagyurishte region. a Inclusion type-B1 (left side of the photo) containing a cubic halite crystal (hl) together with hematite (hem). Inclusion type-B2 on the right side contains several transparent daughter minerals halite (hl) and sylvite (slv), Elatsite deposit. b Inclusion of B2-type, negative crystal shape, containing hematite (hem), halite (hl) and sylvite (slv), Elatsite deposit. c Two-phase inclusions (type-A1) in quartz associated with K-feldspar, Medet deposit. d Large threephase inclusion (type-B3) containing halite (hl), sylvite (slv), pyrite (py) and an unidentied opaque ore mineral (ore min), Elatside deposit

minerals, and the number of primary two-phase inclusions suitable for measurements signicantly decreases. Chalcopyrite deposition occurred at similar temperatures between 450 and 320 C at Elatsite and Medet, but at clearly lower temperatures near 300 C at Assarel. Halite-saturated brine inclusions were never found in quartz associated with the later ore minerals including molybdenite, pyrite, galena and spalerite. The number of primary two-phase inclusions suitable for measurement signicantly decreases in such samples, and nearly all inclusions are too small for cryometric measurements. However, a gradual decrease in temperature from >300 C (molybdenite) through 310 260 C (quartz-pyrite) to 280150 C (galena-spalerite) is a common feature for all three deposits.

Summary and discussion

Similarities and dierences in mineral associations and uid inclusions from the hydrothermal systems in porphyry-copper deposits from the Panagyurishte region of the central Srednogorie zone reect the geologic position of the ore mineralisation within the framework of Late Cretaceous volcanic-intrusive complexes. Although depths and uid pressures have not been quantied at this stage, the deposits may together represent a continuum from relatively deep, basement-hosted deposits centred on intrusive stocks (Elatsite, Medet) to rather shallow and lower-temperature hydrothermal systems associated with subvolcanic stocks intruding their own volcanic

superstructure (Assarel), with a likely transition to highsulphidation epithermal deposits (Chelopech, Radka). Typical porphyry-style wall-rock alteration is represented by K-silicate and propylitic assemblages, at an early stage of the hydrothermal-metasomatic evolution. The outer parts of the deposits are generally aected by propylitic alteration developed proximally to a K-silicate zone (Medet), a sericitic zone (Elatsite), or a sericiteadvanced argillic zone (Assarel). The zone of K-silicate alteration in the upper levels of the Elatsite deposit is overprinted by sericitic alteration, where the main sulphide mineralisation and quartz-pyrite veins are developed. Sericitic and advanced argillic assemblages (acid-chloride and acid-sulphate subtypes) are developed in the upper levels, and are representatives of an epithermal style of alteration, notably at Assarel. This type of alteration overprints K-silicate and propylitic alteration in a second stage of wall-rock alteration. This stage is only weakly expressed in the Medet deposit, due to the deeper erosion level of this deposit. Apart from dierences of the erosion level, the dierences in type of wallrock alteration is probably due to variable proportions of vapour and brine uids derived from a magmatic source, and low-salinity uids of meteoric origin. However, more data are required for rigorous modelling of the development of these systems. The characteristic features of the ore mineralisation common in all three deposits are (1) early appearance of Fe-Ti-oxide minerals, (2) wide distribution of the pyritechalcopyrite association as the main ore stage, and (3) presence of late quartz-molybdenite, quartz-pyrite

597

and quartz-galena-sphalerite veins. The most signicant dierences among the deposits are the presence of PGE and gold mineralisation in the Elatsite deposit, as well as the occurrence of an epithermal style of mineralisation (with very rare molybdenite) in the Assarel deposit. These characteristics indicate dierences of the primary source of the ore elements. PGE mineralisation and CoNi assemblages found in the Elatsite deposit and Co-Ni assemblage in the Medet deposit may suggest participation of uids inuenced by mac/ultramac rocks. Enargite and numerous rare minerals including tellurides and selenides occur at Assarel, emphasising the transitional nature of this deposit to the high-sulphidation epithermal environment. Major pyrite-rich massive-sulphide epithermal Cu-Au deposits are spatially associated within a few kilometres from each of the large, and some of the smaller porphyry-copper deposits in the Panagyurishte ore district. They are of medium- to high-sulphidation style and have a similarly complex, element association with abundant arsenic, bismuth and other sulphides and tellurides (Bonev et al. 2002, and Kouzmanov et al. 2002, this volume). Heinrich et al. (1999) suggested that in some cases this could indicate a relation between magmatic vapour condensates from subjacent porphyry-copper deposits and epithermal uids forming high-sulphidation epithermal deposits. It is assumed that in the Medet and Elatsite deposits only limited participation of meteoric waters occurred in the initial stages. By contrast, the shallower volcanic level of the Assarel system facilitated intensive reworking of the host rocks, in an environment which was more open to the incursion of meteoric water. Interactions of lowand high-salinity magmatic uids with meteoric waters within a composite cross section, extending from basal intrusives up into the subvolcanic domain, might explain the close spatial relationship between porphyry copper and intermediate to high-sulphidation epithermal styles of mineralisation, which are a characteristic feature of the Panagyurishte district and the Late Cretaceous Balkan Carpathian magmatic hydrothermal belt in general.
Acknowledgements The authors would like to thank C. Heinrich sincerely for his precise review of the manuscript and fruitful suggestions, also T. Driesner and W. Halter for their support in nal polishing of the gures. We are also thankful to I. Queralt (Institute of Earth Sciences, Barcelone) and the Spanish Council for Scientic Research for the support in realising X-ray determinations of minerals in the hydrothermally altered rocks. Part of uid inclusion studies was performed at Free University (Amsterdam) and we acknowledge J.L.R. Touret and E.A.J. Burke for their support. We thank Geotechmin Consulting @ Engineering Co., Ltd and the colleagues from the Geological Departments of Assarel, Medet and Elatsite mines for their support during the eld work. The manuscript was revised according to helpful suggestions of T. Ulrich, C. Andrew and B. Lehmann, whom we would like to thank sincerely.

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