Geochemical/isotopic evolution of Pb–Zn deposits in the Central and Eastern Taurides, Turkey

International Geology ReviewVol. 53, No. 13, November 2011, 1478–1507

ISSN 0020-6814 print/ISSN 1938-2839 online© 2010 Taylor & FrancisDOI: 10.1080/00206811003680008http://www.informaworld.com

TIGR0020-68141938-2839International Geology Review, Vol. 0, No. 0, Feb 2010: pp. 0–0International Geology ReviewGeochemical/isotopic evolution of Pb–Zn deposits in the Central and Eastern Taurides, Turkey

International Geology ReviewN. Hanilçi and H. Öztürk Nurullah Hanilçi* and Hüseyin Öztürk

Department of Geological Engineering, Avc0lar Campus, Istanbul University, Avc0lar, Istanbul, Turkey

(Accepted 11 December 2009)

The Central and Eastern Taurides contain numerous carbonate-hosted Pb–Zn deposits,mainly in Devonian and Permian dolomitized reefal–stramatolitic limestones, and inmassive Jurassic limestones. We present and compare new fluid inclusion and isotopicdata from these ore deposits, and propose for the first time a Mississippi Valley-type(MVT) mode of origin for them.

Fluid inclusion studies reveal that the ore fluids were highly saline (13–26% NaClequiv.), chloride-rich (CaCl2) brines, and have average homogenization temperaturesof 112°C, 174.5°C, and 211°C for the Celal Dag, Delikkaya, and Ayrakl0 deposits,respectively. Furthermore, the d34S values of carbonate-hosted Pb–Zn deposits in theCentral and Eastern Taurides vary between –5.4‰ and +13.70‰. This indicates a pos-sible source of sulphur from both organic compounds and crustal materials. In contrast,stable sulphur isotope data (average d34S –0.15‰) for the Çad0rkaya deposit, which isrelated to a late Eocene–Oligocene (?) granodioritic intrusion, indicates a magmaticsource. The lead isotope ratios of galena for all investigated deposits are heterogeneous.In particular, with the exception of the Suçat0 district, all deposits in the Eastern (Delikkaya,Ayrakl0, Denizovas0, Çad0rkaya) and Central (Katranbas0, Küçüksu) Taurides havehigh radiogenic lead isotope values (206Pb/204Pb between 19.058 and 18.622; 207Pb/204Pbbetween 16.058 and 15.568; and 208Pb/204Pb between 39.869 and 38.748), typical ofthe upper continental crust and orogenic belts.

Fluid inclusion, stable sulphur, and radiogenic lead isotope studies indicate thatcarbonate-hosted metal deposits in the Eastern (except for the Çad0rkaya deposit) andthe Central Taurides are similar to MVT Pb–Zn deposits described elsewhere. Theprimary MVT deposits are associated with the Late Cretaceous–Palaeocene closure ofthe Tethyan Ocean, and formed during the transition from an extensional to a compres-sional regime. Palaeogene nappes that typically limit the exposure of ore bodies indic-ate a pre-Palaeocene age of ore formation. Host rock lithology, ore mineralogy, fluidinclusion, and sulphur+ lead isotope data indicate that the metals were most probablyleached from a crustal source such as clastic rocks or a crystalline massif, and trans-ported by chloride-rich hydrothermal solutions to the site of deposition. Localization ofthe ore deposits on autochthonous basement highs indicates long-term basinal fluidmigration, characteristic of MVT depositional processes. The primary MVT ores wereoxidized in the Miocene, resulting in deposition of Zn-carbonate and Pb-sulphate–carbonate during karstification. The ores underwent multiple cycles of oxidation and,in places, were re-deposited to form clastic deposits. Modified deposits resemble the‘wall-rock replacement’ and the ‘residual and karst fill’ of non-sulphide zinc depositsand are predominantly composed of smithsonite.

*Corresponding author. Email: [email protected]

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mailto:[email protected]

http://www.informaworld.com

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International Geology Review 1479

Keywords: Mississippi Valley-type (MVT) Pb–Zn deposits; fluid inclusions; stablelight isotopes; lead isotopes; Central and Eastern Taurides; Turkey

IntroductionThe Tauride Mountains of southern Turkey consist mainly of passive margin carbonaticand clastic sedimentary rocks, and include Fe, Mn, Pb–Zn, and bauxite deposits (Figure 1).While there are published accounts of the bauxite and Mn deposits of the Tauride Mountains(Öztürk 1997; Öztürk and Hein 1997; Öztürk et al. 2002), there are no published studies on theformation of the Pb–Zn deposits on a regional scale in the international literature.

The Pb–Zn deposits of the Central Taurides occur in difficult geographic locations andwith limited reserves; thus mining of these deposits has often been interrupted. Currently,there is no active Pb–Zn mining in the Central Taurides. On the other hand, their lateralequivalents in the Eastern Taurides form the most important economic Pb–Zn depositsof Turkey. According to mining company data (collected from, e.g. ÇINKUR, DedemanComp., Oreks Comp., Havadan Comp., amongst others), until 2008, approximately 6.3 Mtof Zn + Pb ore with average 30% Zn grade was mined in this region (unpublished com-pany reports), and there are still 3.5 Mt of measured ore reserves left in the region. Activemining is still present in Eastern Tauride deposits, i.e. Delikkaya, Ayrakl0, Suçat0, andÇad0rkaya deposits, with an average 40,000–50,000, 25,000, 5000, and 15,000 t annualproduction, respectively.

There are three main models of ore formation proposed by previous studies for thePb–Zn deposits of the region. These are (1) hydrothermal vein fill associated with mag-matic intrusion (Imreh 1965; Petrascheck 1967; Metag and Stolberg 1971; Ayhan 1983,Ayhan and Lengeranl0 1986; Kusçu and Cengiz 2001); (2) leaching of the metals from theophiolitic rocks and primary ore-bearing Permian limestones, and precipitation in karsticsystems (Çevrim 1984; Çevrim et al. 1986); and (3) syn-sedimentary origin of the miner-alization associated with rifting in an early stage of the opening of the Neo-Tethyan Ocean(Koptagel et al. 2001).

The carbonate-hosted Pb–Zn deposits of the Eastern and the Central Taurides (Hanilçi2003; Hanilçi and Öztürk 2003, 2005, 2008) reveal similarities to the Mississippi Valley-type

Figure 1. The location of the carbonate-hosted Pb–Zn deposits in Tauride carbonate platform.

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1480 N. Hanilçi and H. Öztürk

(MVT) Pb–Zn deposits, particularly in terms of host rocks, geological setting, and thenature of ores. Both the Central and Eastern Taurides consist of the same tectono-strati-graphic units and both have undergone rapid uplifting and karstification processes thatdestroyed the primary sulphidic ore nature. On the other hand, the presence of the uniqueCu-bearing Pb–Zn deposit in the Eastern Tauride region, associated with a granodioriticintrusion of Eocene age, offers an opportunity for comparison of the isotopic, mineralogical,and geochemical characteristics with the more common type Pb–Zn deposits of the region.

The main purpose of this article is the study of ore formation and correlation of Pb–Zndeposits of the Central and Eastern Tauride belts, and to provide some clues for ore explorationstrategy in the Tauride belt. The studied deposits were selected for detailed investigationfor the following reasons: (1) in general, the geological features of the deposits are charac-teristic of the MVT deposits; (2) these deposits provide the opportunity to undertakedetailed investigations in different levels of the ore; (3) there is a typical example of thekarstification of the MVT deposits in Eastern Tauride. In this study, the Pb–Zn deposits ofthe Central and Eastern Tauride regions are examined in terms of field relations, lithologicassociations, petrography, mineralogy, fluid inclusions, and sulphur and lead isotopes. Onthe basis of this evidence, we provide a new model for the formation of the carbonate-hosted Pb–Zn deposits of the Tauride Mountains on a regional scale, and discuss the sub-sequent karstification and re-deposition processes that have modified these deposits. Acomparison of these Pb–Zn deposits with those found elsewhere in the same orogenic belt(e.g. Angouran and Mehdiabad deposits, Iran; Tréves deposit, France), as well as withthose in the Alpine–Himalayan range, will contribute to the global correlation of some ofthe events of the Tethyan region.

MethodsThe Pb–Zn deposits in the Eastern Tauride belt have been studied by a few scientists (e.g.Imreh 1965; Ayhan 1983, 1984; Çevrim 1984; Demir 1998), but most of these studiesfocused on a few deposits. Even though they have the same geological setting as the EasternTauride deposits, there are no data about Pb–Zn deposits in the Central Taurides. In thisstudy, we revised the geological maps of all deposits, produced the cross sections, andcorrelated the stratigraphical position of the Pb–Zn deposits of both the Eastern andCentral Taurides. Because of the intense karstification processes, samples for fluid inclu-sion and isotope studies were specifically collected in the primary ore zones, where theywere preserved from karstification.

Fluid inclusion studies were carried out on doubly polished thin sections of thesphalerite minerals. The measurements were made with a Linkham THM600 (at Univer-sität Göttingen, Germany) and THMG600 (at Istanbul University, Department of Geol-ogy, Turkey) heating–freezing stage mounted on an Olympus optical microscope fittedwith video camera and monitor. Heating and freezing measurements were undertakenusing standard techniques as described by Roedder (1984) and Shepherd et al. (1985).Accuracy was ±0.4°C for the heating stage and ±0.2°C for the freezing stage.

Stable sulphur isotope studies were carried out on four samples from the Central Tauridesand 22 samples from the Eastern Taurides Pb–Zn deposits (total 26 samples: 6 sphalerite, 18galena, and 2 pyrite). Isotope analyses were measured at Universität Göttingen, Institute fürGeochemie-Isotopengeologie (IGI). Sphalerite, galena, and pyrite grains were picked fromcrushed ore pieces, and powdered (5 g) samples were reacted with CuO to produce SO2 gas.Stable isotope ratios were determined from SO2 gas extracted using a Finnigan MAT 251mass spectrometer. The data were normalized to the Canyon Diablo meteorite (CDT).

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Mineral fractions of galena for mass spectrometry analysis were separated from theore samples by hand-picking. The isotopic compositions of galena from the Aladaglarregion (nine samples) and Hadim–Bozk0r region (one sample) were measured with aFinnigan MAT 262 mass spectrometer in the static mode at Universität Göttingen,Institute für Geochemie-Isotopengeologie (IGI), in Germany. Galena samples were dis-solved in 6 N HCl, dried, then dissolved again in 6 N HCl. For purification of Pb, columnchemistry was carried out following the method of Krog (1973) using small (500 μL)anion exchange columns. Pb-samples were loaded with Si-gel and phosphoric acid ontosingle Re-filaments. The thermal mass fractionation correction is 0.12%/amu (atomicmass unit).

X-ray diffraction (XRD) was carried out using a Philips diffractometer with CuK alpharadiation, a graphite monochromator, 40 kV, 30 mA, at 10 counts/min over a 2θ rangeof 4–60°C. The geochemical data reported in this paper were taken from earlier studies by theauthors and other published and unpublished company sources.

Geological settingTectono-stratigraphic units of the TauridesThe study region is located in the Central and Eastern Tauride mountains, which com-prise major allochthonous and autochthonous tectono-stratigraphic units. The sedimentaryunits, which mainly consist of carbonates, were deposited in shallow marine environmentsof the Anatolian microplate. The Anatolian microplate is composed of high-grade meta-morphic bodies such as, from W-E, the Menderes, K0rsehir, and Bitlis massifs (Figure 1).This microplate is delimited by the North Anatolian Suture Zone (NASZ) in the north,which is also known as the Izmir–Ankara–Erzincan Suture Zone, and the South AnatolianSuture Zone in the south (SASZ), which is also known as Bitlis–Zagros Suture. The Anato-lian micro-plate represents fragments of the African Plate or Gondwana. After the rifting inthe Late Triassic (e.g. Robertson and Dixon 1984; Robertson 2000), the Anatolian frag-ments were separated from the African Plate and accreted to the Eurasian Plate via theconsumption of the Neo-Tethyan Ocean in pre-Eocene time (e.g. Sengör and Y0lmaz1981) through the NASZ. The ophiolitic rocks of the studied area belong to the Neo-Teth-yan Oceanic crust, which were over-thrusted hundreds of kilometres to the south after theclosure of the ocean. The tectono-stratigraphic nappe units were emplaced into the regionfrom the Late Cretaceous until the Eocene and underwent greenschist facies metamor-phism. Small granodioritic stocks intruded the region after the nappe emplacement, possiblyin the late Eocene. The Miocene deposits unconformably overlay the tectono-strati-graphic units.

The Taurides are divided into six different nappe units, namely the Geyik Dag0 (auto-chthonous), Antalya, Alanya, Bolkar Dag0, Siyah Aladag, and Bozk0r nappes (Figure 2),in the Central Taurides (Özgül 1976), and six nappe units, namely the Yahyal0, SiyahAladag, Çataloturan, Beyaz Aladag, Ophiolitic melange, and Aladag Ophiolite, and oneautochthonous as Tufanbeyli (Figure 3) in the Eastern Taurides (Tekeli et al. 1983). Therock associations of each nappe unit indicate different depositional and basinal conditions(Özgül 1976).

Carbonate-hosted Pb–Zn deposits in the Taurides occur only within the Siyah Aladagand Yahyal0 units (Figures 2 and 3). These two units mainly consist of carbonatesdeposited on the northern slope of the passive margin of the Anatolian micro-plate.Despite some similarities between these two tectono-stratigraphic units, the Yahyal0

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Unit was metamorphosed to a low-grade greenschist facies. According to recent studies, theYahyal0 Unit is a metamorphic equivalent of the Siyah Aladag Unit (SAU; Tok et al. 2004).

The Yahyal0 UnitThe Yahyal0 Unit is defined as the ‘South Central Anatolian Unit’ by Özgül (1971) in theCentral Taurides and the ‘Yahyal0 Unit’ in the Eastern Taurides by Blumenthal (1952) and

Figure 2. Tectonostratigraphic units of the Central Taurides (modified after Özgül 1976).

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Tekeli et al. (1983). The unit consists of associations of a low-grade greenschist metamor-phic sequence in the Aladaglar–Zamant0 region of the Eastern Taurides (Figure 3).

The base of the unit begins with Silurian(?)–Early Devonian rock associations: sericiteschist, quartz-sericite schist, chlorite-sericite schist, chlorite-calc schist, recrystallizedlimestone, and quartzite (Figure 4). The Middle–Upper Devonian succession includesintercalations of recrystallized limestone, calc schist, dolomite, and some bituminouslimestone zones. The Carboniferous is represented by sericite-chlorite schist, quartz-sericiteschist, and phyllite and intercalated with quartzite, and conformably overlies the UpperDevonian. The Permian rocks consist of recrystallized limestone, quartzite, and calc-schist intercalations. The lower part of the Permian begins with recrystallized limestoneincluding bio- and litho-zones such as Girvanella zones, with an average 15–30 m ofthickness (Tok et al. 2004). The Girvanella bio-zone (Figure 4) consists of spherical towell-rounded cyanobacterial algae concretions, between 5 and 30 mm in size. Thebedding thickness ranges from 0.5 to 1.5 m and includes chalcedony as vuggy fillingsgiving hardness to the rock. Black stylolites are typical in this zone with dense veinlets ofiron oxide, dolomite, and calcite. The limestones pass into grey quartzites. The upper-most part of the Permian consists of dark grey-black-coloured, thin- to moderately

Figure 3. Tectonostratigraphic units of the Eastern Taurides (simplified after Tekeli et al. 1983)and location of the carbonate-hosted Pb–Zn deposits in the region.

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thick-bedded, Mizzia-bearing recrystallized limestones. The Triassic is represented bymarl–mudstone–limestone inter-layers and dolomites.

The Siyah Aladag Unit (SAU)The SAU occurs in the Central Taurides and is referred to as the ‘Hadim nappe’ (Blumenthal1944), ‘Central Taurides Unit’ (Özgül 1971), and ‘Aladag Unit’ (Özgül 1976) in theCentral Tauride region, and ‘Siyah Aladag sequence’ (Blumenthal 1941), ‘Palaeozoic ofBelemedik’ (Blumenthal 1947), and ‘Siyah Aladag Nappe’ (Blumenthal 1952) in the EasternTauride region. The carbonate-hosted Pb–Zn deposits such as Katranbas0–K0z0lgeris andKüçüksu–Asar Tepe Pb–Zn deposits (Figure 2) in the Central Taurides, and Delikkaya,Denizovas0 (Celal Dag, Uzunkol Tepe) and Suçat0 Pb–Zn deposits (Figure 3) in the EasternTaurides are located within the SAU. This unit is composed of Late Devonian to LateCretaceous carbonates and clastic rocks (Figure 4) and is allocthonous.

The lowest sequence of the SAU, Late Devonian, is mainly composed of alternatingsiltstones and reefal limestones, gradually passing into quartz sandstone with limestone

Figure 4. Stratigraphic columnar section of the Siyah Aladag Unit and Yahyal0 Unit in the Centraland Eastern Taurides and position of the carbonate-hosted Pb–Zn deposits.

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intercalations. The Carboniferous is made of limestone with quartzite, sandy limestone,and occasional siltstone layers, and thick-bedded, light-grey limestones.

The Lower Permian is defined by Girvanella-bearing limestone, which was describedin detail in the Yahyal0 Unit, and which points out the marker horizon for Carboniferous–Lower Permian transition in the Taurides (e.g. Okuyucu 2002; Tok et al. 2004; Figure 4).This zone passes to Pseudoschwagerina-bearing limestone, which includes the strata-bound-type Pb–Zn-rich layers (Figure 4). The subsequent quartzites, which form the uppermostlevel of the Lower Permian, are medium- to thick-bedded. The Lower Permian’s thicknessis between 10 and 250 m and is deposited in shallow water, in reef, and near reef deposi-tional environments. The Upper Permian is characterized by Mizzia-bearing limestone,which indicates a lagoon-reefal environment in shallow and warm conditions on the car-bonate platform (Eren et al. 1993).

The Lower–Middle Triassic sequence begins with oolitic limestones, which in turnpass upwards to a yellow-, green-, brown-, and purple-coloured, laminated to thinly beddedmudstone–marl–siltstone succession.

The Jurassic of the SAU is dominated by a thick sedimentary succession of limestoneand dolomitic limestone. The important Pb–Zn deposits in the Eastern Taurides (Delikkaya,Uzunkol Tepe, and Suçat0 deposits) occur within these Jurassic limestones, which can bedivided into three levels as thinly bedded limestone, massive limestones, and bituminouslimestones (Figure 4). The lowermost Jurassic sequence mainly consists of laminated tothin-bedded bituminous-rich limestones inter-layered with dolomitic limestones. Thissequence is conformably overlain by thick-bedded massive limestones of Dogger andMalm, which contains Pb–Zn deposits (Ayhan et al. 1984). This level is especially affec-ted by nappe tectonics and displays intense karstification, making a consistent definitionfor the whole succession. The third level of the Jurassic is represented by bituminous-richlimestones.

Pb–Zn DepositsCentral TauridesThe Pb–Zn deposits of the SAU are hosted within the carbonates in the Hadim–Bozk0r(Konya) region of the Central Taurides (Figures 4 and 5a). The Katranbas0, K0z0lgeris, andKüçüksu–Asar Tepe Pb–Zn deposits were chosen for investigations among the minerali-zations in the region (Figure 5a). All the deposits will be discussed in two groups as theKatranbas0–K0z0lgeris and Küçüksu–Asar Tepe deposits, because the reserves are small,are close to each other, and have similar geological features. In total, approximately100,000 t of Zn + Pb ore with 35% grade has been mined from these deposits between1965 and 1990; the quantity of ore mined before 1965 is unknown.

The Katranbas0–K0z0lgeris and Küçüksu–Asar Tepe DepositsThe Katranbas0–K0z0lgeris deposit is located between the Katranbas0 and K0z0lgeris hills(Figure 5a). The Küçüksu deposit is located on the south-eastern and north-eastern slopesof the Küçüksu Hill, and the Asar Tepe deposit is north-west of the Asar Hill (Figure 5b).All the deposits of the region occur in the Pseudoschwagerina-bearing Lower Permianlimestones, which overlie the Girvanella-bearing limestones and belong to the SAU, arethe host unit of the deposits. The Katranbas0–K0z0lgeris deposit strikes N40°–50°W anddips 40°–45°NE; the Küçüksu deposit strikes N30°–40°W and dips 30°–35°SE.

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The ore bodies are all of the strata-bound type and generally occur as concordantlenses to the strike of the host carbonates, which are typically thick-bedded and highlyfractured (Figure 5b). However, they may also be associated with faults parallel to thebedding. Some slickensides are indicators of such structures, which commonly develop par-allel to the bedding. The ore thickness varies from 0.5 to 3 m, and the zone extends at least800 m in length in the Katranbas0 and Küçüksu regions.

The ore bodies are highly porous, soft, and brownish due to surface oxidation of theiron sulphides. The ore bodies were oxidized into carbonate Pb–Zn minerals, mainlysmithsonite and cerussite, but some sulphidic ore minerals, such as galena and sphalerite,were also preserved at some localities. N–S trending faults cut the Katranbas0 ore body,and N35°E trending fractures are filled with the carbonate ore. Dolomitization is a wide-spread alteration type in the limestones, and such zones contain disseminated sulphur min-erals such as pyrite, sphalerite, and galena.

Mineralogy and geochemistryThe ore microscopy and XRD results show that the ore at Katranbas0–K0z0lgeris andKüçüksu–Asar Tepe is predominantly cerussite, smithsonite, galena, sphalerite, and haematite-limonite with minor dolomite, calcite, quartz, and barite (Table 1). Where sulphides are

Figure 5. (a) Geological map and (b) cross section of the Katranbas0–K0z0lgeris and Küçüksu–AsarTepe Pb–Zn depoists in the Central Taurides.

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present, the ore also includes pyrite and marcasite. Haematite-limonite occurs as pseudo-morphs after pyrite in the low-grade brownish ore. The high background value in the XRDpatterns indicates the presence of amorphous iron oxides and hydroxide minerals. The ironoxi-hydroxides cause a brownish yellow colour on the ore bodies. Sphalerite is very rare,and occurs as small crystals with good internal reflections as a primary mineral. Galena islargely altered to cerussite. Some disseminated galena crystals were identified in the dolo-mitic wall rocks.

White kidney-type zincite and the hydrozincite are present as oxidation products ofsphalerite, both in the fissures of the dolomites and in dissolution cavities in the smith-sonites. The Pb–Zn deposits in the Hadim–Bozk0r region are largely changed into smith-sonite and cerussite by carbonatization of primary sulphide minerals. Some vuggy andcolloform structures developed in the carbonated ore bodies. Chemical analyses under-taken in the region (Alp 1976) indicate that Pb-values (2.75%) of the Katranbas0 depositare higher than the those of the others (average 0.3%, n = 3). While Zn-content of theKücüksu deposit is 36%, the others have 27% on average (n = 13). Furthermore, Ag andCu are scarce in the K0z0lgeris and Küçüksu–Asar Tepe deposits (average 0.002%). Also,the deposits in the region have similarities in terms of Cd values (average 0.14%, n = 18),according to available data (Alp 1976).

Eastern TauridesThe most economically important carbonatic Pb–Zn deposits of Turkey are in the EasternTauride region, commonly known as the Aladaglar–Zamant0 Pb–Zn province (Figure 3) inthe Turkish literature (e.g. Metag and Stolberg 1971; Ayhan et al. 1984; Çevrim 1984;Hanilçi and Öztürk 2003). In this region, mining activities extend back to the Bronze Age,by Hittites (Ayhan et al. 1984), followed by the Roman Empire, Seljuks, and Ottomans.There are more than 50 mines known in the region; however, only eight are in operation atpresent. This study was carried out on six of those eight deposits: the Ayrakl0, Çad0rkaya,Uzunkol Tepe, Celal Dag, Suçat0, and Delikkaya Pb–Zn deposits (Table 1).

The Ayrakl0 depositThe Ayrakl0 Pb–Zn deposit is located 17 km SE of Yahyal0 (Kayseri) (Figure 3). From1962 to 2006, approximately 500,000 t of ore with 25 wt.% Zn and 10 wt.% Pb weremined. Annual ore production from the deposit is up to 25,000 t with 35–38 wt.% Pb + Znfrom underground mining in 2008 (unpublished company report).

The Ayrakl0 Pb–Zn deposits occur both in Devonian thickly bedded, crystalline car-bonates of the Yahyal0 nappe (Figures 4 and 6a) and at the contact between crystalline car-bonates with the calc-schists. The field studies indicate two types of deposit: hard, strata-bound-type, high-grade ore; and soft, karstic-type, low-grade ore. The strata-bound-typemineralization occurs at three different levels in the Middle Devonian succession. Thefirst level entirely comprises a white, dense, 25–60 cm-thick compact smithsonite layerconcordant to the bedding of recrystallized carbonates. The second and third mineraliza-tion levels are lens-shaped with N50E, 40°SE orientation within the calc schists and at thecalc schist–bituminous schist black crystalline limestone contacts. This type of hard, high-grade smithsonite ore, which is parallel to layering/bedding, has not been observed inother deposits of the region. The strata-bound-type mineralization is important because itgives some clues as to the origin of the Tauride belt primary carbonate–hosted Pb–Zndeposit.

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Tabl

e 1.

Com

paris

on o

f the

car

bona

te-h

oste

d Pb

–Zn

depo

sits

in th

e Ea

ster

n an

d C

entra

l Tau

rides

.

Reg

ion

Nam

e of

dep

osit

Hos

t roc

kA

ge o

f hos

t roc

kO

re m

iner

als

Alte

ratio

nO

re ty

pe

Tect

ono-

stra

tigra

phic

unit

East

ern

Taur

ides

Ayr

akl0

Rec

ryst

alliz

ed

limes

tone

, cal

c sc

hist

Mid

dle

Dev

onia

npy

-mar

, gln

, sp,

an

gl, c

er, s

m,

hyc-

zc, h

m-lm

–St

rata

-bou

nd, v

ein,

kars

ticY

ahya

li

Çad

0rkay

aR

ecry

stal

lized

lim

esto

neU

pper

Per

mia

nap

y, p

y-m

ar, g

ln, s

p,

cpy,

angl

, cer

, sm

, hm

-lm

Kao

liniti

zatio

nR

epla

cem

ent t

ype

and

vein

Del

ikka

yaM

assi

ve li

mes

tone

Mid

dle

Jura

ssic

py-m

ar, g

ln, s

p, cp

y,

angl

, cer

, beu

, sm

, hy

c-zc

, hm

-lm

Dol

omiti

zatio

nR

epla

cem

ent, v

ein,

ka

rstic

Siya

h A

lada

g

Suça

t0M

assi

ve li

mes

tone

py-m

ar, g

ln, s

p,

angl

, cer

, sm

, hyc

-zc

, hm

-lm

–R

epla

cem

ent,

kars

tic

Den

izov

as0

Uzu

nkol

tepe

–V

ein,

kar

stic

Cel

al D

agM

izzi

a-be

arin

g lim

esto

neU

pper

Per

mia

nD

olom

itiza

tion

Stra

ta-b

ound

, ka

rstic

Cen

tral T

aurid

esK

atra

nbas

0Ps

eudo

schw

ager

ina-

bear

ing

limes

tone

Low

er P

erm

ian

py-m

ar, g

ln, s

p,

angl

, cer

, sm

, hy

c-zc

, hm

-lm, b

a

Dol

omiti

zatio

nSt

rata

-bou

nd,

kars

ticK

üçük

su–

Asa

r Tep

eK

0z0lg

eris

Abb

revi

atio

ns: a

py, a

rsen

opyr

ite; c

py, c

alco

pyrit

e; sp

, sph

aler

ite; g

ln, g

alen

a; p

y, p

yrite

; mar

, mar

casit

e; c

er, c

erru

site;

ang

l, an

gles

ite; s

m, s

mith

soni

te; h

yc, h

ydro

zinc

ite; z

c, z

inci

te; h

m-lm

,ha

emat

ite-li

mon

ite; b

eu, b

euda

ntite

; ba,

bar

ite.

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The karstic deposits are generally situated in the NE–SW fractures and karstic halos.The main karstic-type ore vein strikes N40–60E, and dips 40°–80°SE. The karstic-typemineralization occurs in the Middle Devonian recrystallized limestones, bituminous lime-stones, and the calc-schists. The calc-schists are interbedded with 5–10 cm-thick bitumi-nous schists with disseminated galena and sphalerite. In the zones where the crystallinelimestones are the country rocks, galena is partially preserved; however, the sphaleritegrains were entirely changed to smithsonite.

The karstic-type open space filling ore formation develops along the fault zones, andgenerally shows regular geometry similar to vein ores. In the Ayrakl0 deposit, the oreextends a few hundred metres in length with regular thickness averaging 2 m. Big open-ings represent the fault intersections and are filled with ore up to 20 m thick and of pocketform.

The ore body of the Ayrakl0 deposit shows chemical zonation from bottom to top. Thesoft brownish grey level consisting of zinc carbonates at the bottom of the ore zone passesupwards into bluish grey Pb-oxides and iron oxides. Such kinds of chemical fractionation

Figure 6. Cross sections of the carbonate-hosted Pb–Zn deposits in the Eastern Taurides: (a)Ayrakl0, (b) Çad0rkaya, (c) Uzunkol Tepe and Celal Dag, (d) Delikkaya, and (f) Suçat0 deposits.

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or zonation throughout the ore bed can be explained in two ways. They are formed eitherby in situ reorganization of the Zn–Pb- and Fe-constituents by supergene fluids or period-ical changing of the concentrations of lead and zinc ions in a descending solution resultingin the formation of banded ore formation, depending on the width of open space. Thesezones exhibit a laminated structure of microcrystalline galena and limonite-enrichedsmithsonite, interbedded with clay. On a large scale, galena changes into cerussite andanglesite, and sphalerite to smithsonite, due to oxidation. Sphalerite is entirely altered tocarbonatic zinc; however, unaltered galena is partially preserved within the cerussites.Some smithsonite and zincite-hydrozincite zones formed by country rock replacement dis-play multiple styles of framework: vuggy, massive, and stiff and colloform structures.

The Çad0rkaya depositThe Çad0rkaya Pb–Zn deposit is located approximately 14 km NW of Yahyal0 settlement.It reveals completely different mineralogical and chemical features from those of the otherPb–Zn deposits in the Eastern Tauride region (Figure 3). The deposit occurs in recrystal-lized limestones of the Yahyal0 nappe unit (Figure 4) and is structurally controlled, whichnearly parallels the dikes of Karamadaz0 granodiorite of the late Eocene–Oligocene(?)(Oygür 1986). Although there are large mineralized zones, the mining is focused on thewestern side of the S0ps0kkaya Hill (Figure 6b). The Pb–Zn deposit developed within theNNE–SSW striking fracture zones of the grey to dark grey, moderately to thickly beddedrecrystallized Permian limestones. Alteration is represented by quartz, pyrite, and kaolinite.

The main ore vein is elongated in a N10E direction and is composed of sulphide min-erals. The iron oxide cap with the zinc carbonate minerals has been mined in the last 10years, and currently the primary sulphidic Pb–Zn ore zone is being mined. The sulphideminerals of the ore consist of galena, sphalerite (dark brown–black), pyrite, chalcopyrite,and arsenopyrite in a decreasing abundance. The gangue consists of quartz, calcite, epi-dote, and chlorite.

The Uzunkol Tepe depositThe Uzunkol Tepe and Celal Dag deposits are also known as the Denizovas0 region deposits(Figure 3). Several artefacts such as ancient galleries, wooden shovels, and some smeltingremnants indicate that mining goes back possibly to Roman times. To date, more than 1 Mt ofPb–Zn ore has been mined from the Uzunkol Tepe and the Celal Dag deposits.

The host rock of the deposit is dolomitized Jurassic limestones, which are thick-bedded,highly fractured, and light grey, belonging to SAU. The Uzunkol Tepe deposit follows alonga N45–60E striking 75°NW dipping fault zone for 750 m (Figure 6c). Post-mineralizationfaults cross-cut and offset the ore body. The ore body is mainly vein type; however,karstic pockets formed through the fault zones are generally stock type. The thickness ofthe ore veins varies between 1 and 5 m with an average of 2 m.

The Celal Dag depositThe deposit is located approximately 900 m SE of the Uzunkol Tepe deposit and hostedby Mizzia-bearing Upper Permian limestones (Figure 6c). It is divided into two ore zones.The first zone, also known as the Celal Dag Desandri ore zone, is located on the southernslopes of Celal Hill. The second occurs in the sub-surface fracture zones and karstic voids,and does not expose to the surface.

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The first ore zone is parallel to the N45E and 45°NW striking bedding of the Mizzia-bearing Upper Permian limestone. Although it reaches up to 1.5 m thickness, it is notbeing mined due to presence of abundant iron oxide-hydroxide minerals. In addition,700 m NW of this ore zone, within the Mizzia-bearing limestones, there are 15–30 cm-thick and 1.5–2 m-long, N25–30E striking, both concordant and cross-cutting, ore zonespresent. These ore zones include primarily galena and sphalerite minerals and were exam-ined by fluid inclusion studies.

The second ore zone is investigated in underground mining galleries along the three faultzones (N35W – 50°SW, N60E – 65°–70°SE and, N40E – 65°NW). The ore is re-activatedmultiple times after the formation and thus brecciated. This kind of ore is vein type andthickness varies between 1.5 and 5 m.

The Delikkaya depositThe Delikkaya (meaning vuggy rock in Turkish) deposit has the biggest reserve in theAladaglar–Zamant0 Pb–Zn metallogenic province, and is at ∼3000 m elevation in the Tau-ride Mountains (Figure 3). Mining has been carried out since Roman times and it is esti-mated that about 2,500,000 t of ore with total grade between 35% and 40% Zn + Pb(Zn ≥ 30%) has been mined within the last 40 years. At present, about 40,000–50,000 t ofPb–Zn ore is being mined annually.

The host rocks of the Delikkaya Pb–Zn deposit are thick-bedded, massive Jurassiclimestones (Figures 4 and 6d). The main ore occurs in a N55–65E striking, SE dipping faultzone. The known dimension of the deposit is approximately 130 m (depth) by 500 m (length).Mining began as an open pit at the surface and then changed to underground mining due toincreasing thickness of overburden. The ore body has vein geometry and is discordant tothe country rocks. However, there are some karstic cavity-filling deposits, which showstock-lens geometry approximately 30 × 50 × 5 m in dimension (Figure 7). Dolomitization isthe widespread alteration and replaced by sphalerite.

Figure 7. Chemical zonation of the Delikkaya Pb–Zn deposit in the Eastern Taurides (see text fordetail).

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The Delikkaya deposit shows a typical example of the supergene enrichment andkarstification processes with well-developed intra-karstic sedimentation, similar tothe Ayrakl0 deposit. The ore body shows a chemically fractionated nature with ironoxides at the top, lead sulphides and oxides in the middle, and zinc carbonates at thebottom as shown in Figure 7. The vuggy skeleton and brecciated ore bodies supportthe interpretation that the karstification and the tectonic activities had continued afterthe formation of the ore. The breccias are mainly composed of galena particles, whoseouter parts turned into anglesite and cerussite due to oxidation. The colloform struc-ture, as seen both in the karstic caves and above the oxide–carbonate zinc bodies, likea crust, indicates re-mobilization of the zinc via meteoric waters and then precipita-tion as zincite and hydrozincite under low-temperature conditions in the supergeneenvironment.

The Suçat0 depositThe deposit formed in thick-bedded and fractured, massive Jurassic limestone of the SAU(Figures 3, 4, and 6e). The ore mainly occurs within two tectonic features: N15–20E-oriented, 80°SE dipping faults and their karstic cavities, and N15–30W oriented, 50–70°SWdipping fracture zones. In addition, N45–65E oriented, 65–85°NW dipping faults and theirrelated karst features mainly consist of zinc carbonate minerals, and the N10W oriented75–85°NE dipping fracture fillings comprise galena and sphalerite. The cross-cuttingmain tectonic features cause karstic cavities to develop horizontally; thus, the ore bodiesform in pipe geometry with average 5 m width and 25 m depth. There are also some vein-type ore bodies, which vary in widths from centimetres to metres, average 40 m in length,and are related to the fractures.

Although this deposit displays similarities with the Ayrakl0 and Delikkaya deposits interms of intra-karstic features, there is an obvious difference; it contains well-roundedquartz–barite-bearing galena pebbles up to 10 cm in diameter. These pebbles are exogenicto the system because quartz and barite do not occur in the ore body. Therefore, these peb-bles were probably transported into the karstic holes as a clastic material and rounded bywater energy in holes of the cave.

Mineralogy of the Eastern Tauride Pb–Zn depositsThe XRD and ore microscopy studies show that all of the the Pb–Zn deposits in theAladaglar–Zamant0 region except for the Çad0rkaya deposit have similar paragenesis(Table 2). The mineralogical associations consist of arsenopyrite (in the Çad0rkayadeposit), chalcopyrite (in the Çad0rkaya and Delikkaya deposits), sphalerite, galena,pyrite, and marcasite as the primary sulphides; anglesite, cerrusite, beudantite, smith-sonite, hydrozincite, zincite, siderite, haematite, and limonite as the secondary oxides; andquartz, calcite, dolomite, and kaolinite as the gangue minerals, which together constitutethe paragenesis.

In the paragenesis Ayrakl0, Çad0rkaya, Denizovas0, and Delikkaya deposits, there aretwo different sphalerite formations. The first (sph-I) is seen in shades of grey and displayslight orange internal reflection. The zonations and cleavages are fairly clear. The crystalsare generally coarse and anhedral. The sphalerite is altered to smithsonite along the crystalrims and in micro-fractures. The second sphalerite (sph-II) is dark-grey-coloured and ispresent in the vugs of the galena particles.

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The sph-I displays replacement and brecciated textures in general. In contrast to theother deposits, sph-I in the Çad0rkaya deposit is dark brown to dark grey-black in colour,which indicates a high Fe content, includes chalcopyrite inclusions, and displays red intra-reflection colour.

Chalcopyrite is observed in the Çad0rkaya and Delikkaya Pb–Zn deposits in theregion. Chalcopyrite mostly occurs as inclusions in sphalerite minerals and disseminatedcrystals in gangue quartz in the Çad0rkaya deposit, and also as small individual crystals inboth deposits. The Dündarl0 deposit, which is close to the Çad0rkaya deposit and outsidethe scope of this study (Figure 2), also displays Cu-enrichment similar to Çad0rkaya andindicates a magmatic hydrothermal system of relatively high temperature. Chalcopyrite min-erals are rarely observed in the Delikkaya deposit, and not observed at the other deposits inthe region.

Pyrite occurs at the Ayrakl0, Çad0rkaya, and Delikkaya deposits at two stages.Pyrite (I) is mostly anhedral to subhedral and is replaced by sphalerite in the Çad0rkayadeposit. Framboidal-type pyrite grains of the Ayrakl0 deposit probably formed by bac-terial activity at low temperature. Pyrite (II) is seen as late-stage idiomorphic grains.Marcasite, which occurs in all deposits, is especially abundant in the Çad0rkaya depositas large grains.

Galena occurs in all the deposits and is usually oxidized to cerrusite, especially alongthe cleavages. Granular features such as sandy material seen at the Çad0rkaya deposit areassociated with the dissolving and removal of the zinc and iron constituents. Cerrusite andanglesite occur in a colloform texture along the edge of the galena grains. Galena is coatedby anglesite, as it has been detected by XRD in the galena-rich samples.

Beudantite [PbFe3(AsO4)(SO4)(OH)6] has been detected at the Delikkaya deposit asthe soft and earthy textured materials of brownish yellow colour. Its abundance may reachup to 15% in some samples and forms within the oxidation zone of the primary sulphidicore. This zone is generally related to karst channel-filling processes during or after the oxi-dation and contains cerrusite, limonite, and clay.

Smithsonite in hand specimens is grey, brownish grey, and greyish blue due to someimpurities. Smithsonite reveals a colloform skeletal structure. Bluish-grey-coloured

Table 2. Relative succession and mineral paragenesis of the carbonate-hosted Pb–Zn deposits inthe Central and Eastern Taurides.

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smithsonite samples are hard and the iron content of the smithsonite defines their colours.Although they have been seen as replacing sphalerite, they generally are associated withreplacement of the calcitic materials.

Zincite and hydrozincite occur as coatings or vuggy infillings in the carbonatic ore.Haematite and limonite are found in all deposits, but siderite was detected only in theÇad0rkaya deposit.

Chemical zonationA chemical and/or mineralogical zoning develops in almost all ore deposits in the region.However, the chemical and/or mineralogical zoning is particularly evident in theDelikkaya (Figure 7) and Ayrakl0 deposits. The three main chemical sub-zones distin-guished in the deposits are (I) an iron cap zone at the top; (II) a high-grade ore zone in themiddle, which is composed of (IIa) Pb-rich and (IIb) Zn-rich sub-zones; and (III) a zinccarbonate zone at the bottom.

The typical zoning is well developed in the Delikkaya deposit. Zone I, at the top,forms a well-developed iron cap zone, dominated by iron oxides-hydroxides and clay min-erals (Figure 7). The chemical analyses of the 50 ore samples, taken from the 2785 level,indicate a high Fe content with 29.5% Fe, 9% Zn, and 8% Pb in average composition.Zone II occupies a larger area and is divided into two subzones (IIa and IIb). Zone IIa con-tains mainly Zn–Pb carbonate minerals such as smithsonite and cerrusite. It developedbetween 2785 and 2765 m and has a grade of 25–30% Zn and 2% Pb (IIa). On the otherhand, Zone IIb is between 2765 and 2715 m and mainly contains galena, sphalerite, andanglesite with 35–40% Pb and 3–5% Zn (Figure 7). Zone III is made of zinc oxide-carbon-ate minerals such as smithsonite, zincite, and hydrozincite, and occurs at the contact of thefootwall limestone and also in deeper sections through the ore body.

The development of chemical zoning of the ore body can be related to both primaryand secondary ore formation processes. Chemical zonation in the whole deposits is typicalof where in situ supergene oxidation has taken place after the intra-karstic sedimentation.In this environment the hydromechanically transported ore materials, which consist of amixture of Zn–Pb–Fe minerals, undergo multi-cyclic oxidation and hence separation ofelements. Zone I, the iron cap zone, is formed by oxidation of the pyrite and sphalerite(Fe, Zn)S to iron oxides and trapping of the ferric and ferrous iron compounds in this zonebecause of their low mobility in the oxidation zone. Galena and its oxidation products arelocalized in the upper section of the ore body due to their relatively low mobility com-pared to Zn.

Zone II has two sub-zones: IIa and IIb. This zonation (IIa and IIb) should beformed via a different hydrological regime within Zone II. The high Pb-content ofZone IIa indicates that Zn was totally mobilized downwards from this zone via anintense hydrological regime and placed into the limestones at the bottom. On the otherhand, because of the low hydrological regime, Zn did not mobilize in zone IIb andoxidation occurred in situ. The different thickness of Zone III, beneath Zones IIa andIIb, also indicates the different hydrological regime within the ore zone. Owing to itshigh geochemical mobility, Zn infiltrated to the bottom (Zone III) and re-deposited infootwall limestone via a replacement process. Formation of hydrozincite and zincitealso reflects actual depositions and is marked by coatings up to 3 mm thick on woodymaterials of the ancient galleries at the Tekneli deposit (Demir 1998). Such a chemicalzonation – iron at the top, lead in the middle, and zinc at the bottom – was also detected atthe Ayrakl0 deposit.

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Fluid inclusion and isotope studiesFluid inclusionsFluid inclusion studies are suitable for micro-thermometry and an analysis is available insphalerite samples from the Ayrakl0, Celal Dag, and Delikkaya deposits. The host miner-als are the first-stage sphalerite in ore paragenesis. The primary, secondary, and pseudo-secondary criteria suggested by Roedder (1984), Shepherd et al. (1985), and Van DenKerkhof and Hein (2001) were used as a standard for distinguishing the origin of inclu-sions. Fluid inclusions are classified as aqueous two-phase (L–V) inclusions. At roomtemperature, a relatively low vapour-to-liquid ratio can be seen, and vapour ranges from10 to 15 vol.%.

Measurements were made in primary and pseudo-secondary inclusions. In general,inclusions are relatively small (5–17 μm), rarely exceed 30 μm in diameter, and havemainly irregular shapes, but inclusions parallel to the growth zones of the sphalerite arerectangular.

Micro-thermometric features of the fluid inclusionsEutectic temperatures (Te) and last ice-melting temperatures (Tm-ice) could be observedin some inclusions. Te, Tm-ice, and homogenization temperature (Th) results obtainedfrom the primary and pseudo-secondary inclusions are shown in Table 3 for differentdeposits. Te and Tm-ice data have been interpreted by using the tables of Roedder (1979)and Shepherd et al. (1985).

Upon cooling, complete solidification of the inclusions took place below –90°C for theDelikkaya and Ayrakl0 deposits and below –70°C for the Celal Dag deposit. During heating,first ice melting was demonstrated by the brightening of frozen phases, which was observedas a wide range: between –80°C and –21.2°C for the Ayrakl0 deposit, −62.2°C and −58°Cfor the Delikkaya deposit, and −52°C and −37°C for the Celal Dag deposit (Table 3).

There are two main interval eutectic temperatures for the Ayrakl0 deposit, which arebetween –55°C and –21.2°C (corresponding Th is between 180°C and 229°C) andbetween –80°C and –52.2°C (corresponding Th is between 51°C and 100°C). In contrast,the Delikkaya and Celal Dag deposits have a narrow range of Te data (Table 3).

The Te data (between −55°C and −21.2°C) of the Ayrakl0 deposit indicate that inclu-sion fluids are characterized by a CaCl2-rich aqueous solution (Crawford 1981; Roedder1984) during the first stage of mineralization. However, the slight depression of the eutec-tic below −52°C shows the presence of other solutes (e.g. MgCl2). In the later stage ofmineralization in the Ayrakl0 deposit, the Te data (between −80°C and −52.2°C) indicatethat Li, K, and Br should have been added to the solution besides the Ca and Mg, via long-time fluid−rock interactions. The Te data of the Delikkaya deposit (between −62.2°C and −58°C) indicate that the fluids as characterized dominantly by CaCl2. But, for the Celal Dagdeposit, the Te data (between −52°C and −37°C) indicate that the inclusion fluids are char-acterized by CaCl2, MgCl2, and FeCl2 (Crawford 1981; Roedder 1984) as the dominant saltcomponents during mineralization. The Te data of the deposits clearly indicate that the oresolutions are CaCl2-rich and metals should have been transported by chloride complexes.

Final ice melting temperature (Tm-ice) has been detected in all fluid inclusions. Salinityestimates were calculated from Tm-ice in all inclusions based on the method of Roedder(1979) and Crawford (1981) for inclusions assuming a simple NaCl + H2O (Tm-ice ≥ −20.8),and salinities of inclusions −20.8 ≥ Tm-ice were calculated based on the equation of Bodnar(1993) and computer program of Bakker (1999).

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Tabl

e 3.

Mic

ro-th

erm

omet

ric d

ata

of th

e A

yrak

l0, C

elal

Dag

, and

Del

ikka

ya P

b–Zn

dep

osits

in th

e Ea

ster

n Ta

urid

es.

Sam

ple

no.

Type

of

incl

usio

n

Eute

ctic

tem

p. T

e (°

C)

Last

ice-

mel

ting

tem

p.

Tm-ic

e (°

C)

Hom

ogen

izat

ion

tem

p.Th

(°C

)

Dep

osit

Inte

rval

nA

vera

geIn

terv

aln

Ave

rage

Inte

rval

nA

vera

ge

Ayr

akl0

901-

1P/

PS−8

0 to

−78

4−7

9−2

7 to

−19

4−2

350

to 9

44

7290

1-2

P−8

0 to

−78

1−7

9−2

21

−22

981

9890

1-2

P−7

5 to

−73

2−7

4−2

3 to

−21

2−2

289

to 9

3.4

291

.290

1-2

P/PS

−52.

2 to

−51

4−5

1.6

−29

to −

144

−21.

576

to 9

44

8590

2P

−55

to −

477

−51.

5−2

8.5

to −

217

−24.

7519

2 to

229

721

0.5

902

P/PS

−25

to −

233

−24

−17

to −

33

−10

224

to 2

293

226.

590

2PS

−21.

21

−21.

2−4

1−4

196

119

6C

elal

Dag

DN

Z-02

P−5

2 to

−51

.98

−51.

95−2

8.5

to −

218

−24.

7589

to 1

578

123

DN

Z-02

P−3

7.5

to −

3710

−37.

25−2

8 to

−22

10−2

586

to 1

6210

124

DN

Z-02

P−2

1.6

1−2

1.6

−15

1−1

590

190

Del

ikka

yaA

-10

P−6

2.2

to −

584

−60.

1−1

4 to

−11

.54

−12.

416

7 to

180

417

4.5

P, P

rimar

y; P

S, p

seud

osec

onda

ry.

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Salinities of fluid inclusions from the examined samples show variation rangingbetween 13.5 and 26 equivalent wt.% NaCl in the Ayrakl0 deposit (Figure 8a), between 23and 28 equivalent wt.% NaCl in the Celal Dag deposit, and between 15.4 and 17.3 equi-valent wt.% NaCl in the Delikkaya deposit (Figure 8a).

With some exceptions most of the Th of the Ayrakl0 deposit has two different rangesbetween (a) 50°C and 100°C, and (b) 200°C and 229°C (Figure 8b). The Th data of theCelal Dag deposit are between 86°C and 162°C (average 112°C; Figure 8b), and those ofDelikkaya deposit are between 167°C and 180°C (average 174.5°C; Figure 8b).

The Th has decreased from 229°C to 50°C in the Ayrakl0 deposit, from 180°C to167°C in the Delikkaya deposit, and from 162°C to 86°C in the Celal Dag deposit duringthe primary mineralization. While the Th drops, the salinities of the deposits do notdecrease, thus indicating that ore fluids did not mix with meteoric water, which has lowsalinity, during the mineralization (Figure 8c).

Sulphur isotopesStable sulphur isotopic studies were carried out on 4 samples in the Central Taurides and22 samples in the Eastern Taurides Pb–Zn deposits. The analyses were made from pyrite(2), sphalerite (6), and galena (18) samples.

The d34SCDT values of the Central Tauride deposits are between 3.43‰ and 13.70‰ ingalena (with average 8.97‰). The d34SCDT values of the Pb–Zn deposits in the Central Tau-rides are in the range of –0.59‰ to 0.34‰ in pyrite and galena for the Çad0rkayadeposit (with average –0.15‰), 6.25‰ to 10.64‰ in galena for the Suçat0 andDelikkaya deposits (with average 8.32‰), and –5.4‰ to –2.12‰ in galena and sphaleritefor the Ayrakl0 deposit (with average −3.35‰; Table 4; Figure 9).

Isotopic study results suggest both magmatic and crustal source for sulphide in themineralization. The d34SCDT values of the Çad0rkaya deposit fall in a narrow rangebetween −0.59‰ and 0.34‰ (average −0.15‰), which is interpreted as evidence of amagmatic source (Figure 9). The Ayrakl0 deposit has relatively light sulphur isotopic values,on average −3.35‰, among the investigated deposits (Figure 9). This weakly negative iso-topic feature of this deposit suggests some contribution of reduced sulphur species fromthe host rocks. Black and organic matter-rich host rocks are the usual source for the lightisotopes. The relative enrichment of the light isotopes within the galena (−5.4‰, –4.61‰)and slightly heavier sulphur isotopes by sphalerite (between –3.18 and –2.12‰) indicates

Figure 8. (a) Frequency versus wt.% NaCl equivalent salinity histogram, (b) homogenizationtemperature (Th) versus frequency histogram, and (c) homogenization temperature (Th) versus wt.%NaCl equivalent salinity diagram of fluid inclusions in sphalerite in the Celal Dag, Delikkaya, andAyrakl0 Pb–Zn deposits.

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a degree of sulphur isotope fractionation in relation to the changing temperature during themineralization.

Sulphides have a wide range of d34SCDT values: from 13.70‰ to 3.43‰ in theDelikkaya, Suçat0, and Denizovas0 deposits in the Eastern Taurides and the Katranbas0-K0z0lgeris, and the Küçüksu–Asar Tepe deposits in the Central Taurides (Figure 9) are

Table 4. d34SCDT (‰) values of the carbonate-hosted Pb–Zn deposits in the Eastern and CentralTaurides.

Sample no. Deposit Mineral d34SCDT (‰) Deposit average

Eastern TauridesAYR-01 Ayrakl0 Sphalerite −2.17 −3.35, n = 6AYR-02 Ayrakl0 Sphalerite −2.12AYR-03 Ayrakl0 Sphalerite −3.18AYR-04 Ayrakl0 Galena −5.4AYR-05 Ayrakl0 Galena −4.61AYR-06 Ayrakl0 Galena −2.66DK-01 Delikkaya Galena 9.67 8.32, n = 8DK-02 Delikkaya Galena 10.64DK-03 Delikkaya Galena 9.31DK-04 Delikkaya Galena 9.28DK-05 Delikkaya Galena 6.46DK-06 Delikkaya Galena 6.25DK-07 Delikkaya Galena 6.64SÇT-01 Suçat0 Galena 7.55DNZ-01 Denizovas0 Pyrite 12.19 10.53, n = 5DNZ-02 Denizovas0 Galena 9.77DNZ-02 Denizovas0 Sphalerite 10.15DNZ-03 Denizovas0 Sphalerite 12.01DNZ-04 Denizovas0 Sphalerite 8.53CK-01 Çad0rkaya Pyrite −0.21 −0.15, n = 3CK-02 Çad0rkaya Galena −0.59CK-03 Çad0rkaya Galena 0.34Central TauridesKB-01 Katranbas0 Galena 13.70 8.97, n = 4KB-02 Katranbas0 Galena 3.43KB-03 Katranbas0 Galena 7.85KS-01 Küçüksu Galena 10.90

Figure 9. The d34SCDT ‰ values of the carbonate-hosted Pb–Zn deposits in Central and EasternTaurides.

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slightly heavier than the Ayrakl0 and Çad0rkaya deposits. Even though the sulphur isotopiccomposition of the carbonate-hosted Pb–Zn deposits of the Eastern and Central Tauridesfall into the data of the MVT deposits, which have wide ranges between –30‰ and +40‰(Claypool et al. 1980; Rollinson 1993), it is difficult to determine the precise nature of thesource of sulphur according to these d34SCDT data alone. These values suggest an isotopicfractionation from heavy isotope sources such as seawater sulphates or pore fluid, or both.However, these wide-ranging values of sulphur isotopic composition clearly indicate themultiple sources different than the magmatic source as represented by the Çad0rkayadeposit (Figure 9). Earlier investigators have also presented similar sulphide isotopicresults and identified seawater sulphates as the main source of the sulphur (Çevrim 1984;Koptagel et al. 2005).

Lead isotopesThe lead isotope studies were carried out on nine galena samples in the Eastern Tauride(Aladaglar region) deposits and two galena samples from the Central Tauride (Hadim–Bozk0rregion) deposits (Table 5). The lead isotope ratios of galena for all deposits are heteroge-neous. In particular, except for the Suçat0 deposit, there are relatively high radiogenic leadisotope values (206Pb/204Pb between 19.143 and 18.622; 207Pb/204Pb between 16.058 and15.568; and 208Pb/204Pb between 39.869 and 38.748) typical of the upper continental crustand orogenic belts (Zartman and Doe 1981), indicating that significant radiogenic Pb wasgenerated in the source reservoir by the decay of U and Th prior to mineralization in theolder basement rocks (Figure 10). Lead isotope data of the Suçat0 deposit indicate that thelead source should be the lower crust or upper mantle, however; analytical contaminationshould be taken into account because this deposit shows only karstic-type features.

Discussion and conclusionsThe Pb–Zn deposits in the Eastern and the Central Taurides occur within the carbonaterocks of the Siyah Aladag Unit (SAU) and the Yahyal0 Unit, which is the metamorphicequivalent of the SAU. The age of the carbonate host rocks are Devonian, Permian, andJurassic. The ore types present in the deposits are highly diverse and can be divided intofour genetic types in relation to mineralogy, formation processes, zonation, and geometry.These are (1) mostly strata-bound-type primary Pb–Zn sulphides, (2) karstificated Pb–Znsulphides and wall-rock replacement-type carbonatic ore, (3) karst fill-type ore, and (4)intrusive related Pb–Zn ± Cu sulphides.

Table 5. Lead isotope values of the carbonate-hosted Pb–Zn deposit in the Eastern and CentralTaurides.

Sample no. Deposit 206Pb/204Pb 207Pb/204Pb 208Pb/204Pb

DK256 Delikkaya 18.623 15.569 38.749DK061 Delikkaya 18.790 15.780 39.165GGC-02 Delikkaya 18.864 15.793 39.200908 Suçat0 18.307 15.417 38.246DNZ-03 Denizovas0 19.058 16.059 39.869AYR-23 Ayrakl0 18.999 15.902 39.534CK-01 Çad0rkaya 19.144 15.874 39.584GYN90 Göynük 18.994 15.797 39.331897 Katranbas0 18.673 16.054 39.545KS-01 Küçüksu 18.554 15.986 39.387

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(1) The strata-bound-type Pb–Zn mineralization in both the Central and EasternTaurides occurs generally in Pseudoschwagerina-rich limestone at the top of thestromatolite zone, rich in Girvanella fossils of the Early Permian (Figure 4).Despite the long distance of over 300 km between the two regions, the presence ofmineralization in a special stratigraphic horizon is highly consistent. The hostlithology should have played an important role in the precipitation of the metalsulphides, either as a sulphate-reducing agent with its high organic matter contentor by providing space with its high porosity; or both. A vuggy filling-type chal-cedony formation was observed in this lithology throughout the section. The primarystrata-bound Pb–Zn sulphides of the Ayrakl0, Delikkaya, and Katranbas0 depositsare thinly bedded, are lenticular-shaped, and consist of sphalerite and galena.These kinds of formations are also seen as 25–60 cm-thick, hard and high-gradecarbonatic zinc ore, as the replacement of the primary sulphides by carbonates inthe Ayrakl0 deposit. Some of the sulphidic primary ores may have been completelyconsumed due to rapid uplifting and erosion, or altered to karstic channel fillings.

(2) The second type of ore dominantly consists of smithsonite (ZnCO3), anglesite(PbSO4), and a small amount of Zn- and Pb-sulphides (sphalerite and galena)representing the partly oxidation products of the primary sulphidic ore. This typeof ore body may represent in situ oxidation products of the wall droplets of theprimary sulphidic ore without long-term transportation. The wall rock of theprimary ore should have been partly or completely changed and thus the depositsmay be completely exogenic to the host lithology. Supergene oxidation processeswere probably triggered by a lowering of the groundwater table and oxidation ofthe sulphides and the subsequent increase in acidity due to release of hydrogenions. Dissolution of the carbonates is enhanced by sulphate generation in theopenings and the erosion of the primary ore with downward-moving groundwa-ter. Transportation of the Zn- and Pb-ions by descending supergene solution,infiltration into the deeper part of the section, and replacement of calcite by

Figure 10. (a) 206Pb/204Pb versus 208Pb/204Pb and (b) 206Pb/204Pb versus 207Pb/204Pb diagrams forgalenas from carbonate-hosted Pb–Zn deposits in the Central and Eastern Taurides in reference tolead evolution curves of Zartman and Doe (1981) for upper crust (UP), lower crust (LC), mantle(M), and orogene (O). (Deposits: 1, Suçat0; 2–4, Delikkaya; 5, Göynük; 6, Küçüksu; 7, katranbas0; 8,Ayrakl0; 9, Çad0rkaya; 10, Denizovas0.)

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smithsonite (ZnSO4 + CaCO3 → ZnCO3 + CaSO4) appear to be the main proc-esses of the carbonatic Zn ore formation. Some of the sulphides, mostly galena,may have formed in association with chemical sedimentation in karstic ponds withstagnant and anoxic water.

(3) The third type of ore deposits, the karstic ore, was formed at long distances awayfrom the primary ore body as a secondary formation. This type of ore consists com-pletely of secondary ore minerals and does not show any primary wall-rock rela-tions, such as dolomitization. It also includes rounded exogenic ore clasts of galena,barite, and quartz. No barite-bearing formations were detected at any of the sectionsof the ore deposits in the region. However, they were detected in the Suçat0 deposit,where the exogenic clasts of up to 5 cm occur in the sand-sized, uncemented galenaaccumulations. This kind of galena may have been transported by strong water flowin karstic holes and deposited in favourable places as clastic material.

(4) The Cu-bearing Çad0rkaya Pb–Zn deposit was formed in relation to the granodioriticintrusion in the late Eocene-Oligocene(?). The mineralogy, ore chemistry, and sta-ble sulphur isotope values of the deposit are completely different from those of theother deposits of the region. The presence of a shallow iron-rich oxidized zoneand carbonatic and/or karstic-type ore formation in this location suggests a rela-tively younger stage of the ore formation. Some workers postulate that all of thedeposits of the region were formed in association with this intrusion (Ayhan 1983;Ayhan et al. 1984); however, stratigraphic controls on the ore formation over awide area, the diversity of ore chemistry, and the age relations of the depositsclearly indicate that the Pb–Zn mineralizations of the region formed before intrusion,except in the case of the Çad0rkaya deposit.

Fluid inclusion data obtained from the primary sulphidic ore zone indicate that the fluidsresponsible for primary ore formation at the Celal Dag deposit had an average homogeni-zation temperature of 112°C and salinity between 23% and 28% NaCl equivalent; for theDelikkaya deposit, an average homogenization temperature of 174.5°C and average salinityof 16.2% NaCl equivalent; and for the Ayrakl0 deposit, a homogenization temperature of211°C (first stage of mineralization) and 86°C (late stage of mineralization), and a salinityof between 13.5% and 26% NaCl equivalent. In general, these data are similar to MVTdeposits (Figure 11) but Th of the first stage of the Ayrakl0 deposit is relatively higher thanthe average Th of the MVT deposits. The eutectic temperatures of the aqueous fluid inclu-sions range from −52 to −37°C for the Celal Dag deposit, suggesting that CaCl2, MgCl2,and FeCl2 (Crawford 1981; Roedder 1984) were present in the ore-forming fluids. For theDelikkaya deposit, the range between −62.2°C and −58°C indicates that the fluids werecharacterized dominantly by CaCl2. For the Ayrakl0 deposit, the range of −55°C to −21.2°C at the first stage of the mineralization suggests the presence of CaCl2-rich solu-tions, and that from −52.2°C to −80°C at the late stage of the mineralization suggests thatadditional components, such as Li, K, and Br, were added to the Ca- and Mg-bearing solu-tion system. The eutectic temperature of the inclusions shows that the ore-forming fluidswere enriched as chloride ions. Thus, it is assumed that Pb and Zn were possibly trans-ported as chlorine complexes ( , ) in ore-forming fluids with temperaturesranging from 50°C to 229°C and being moderately saline. Dissociation of chloride com-plexes with temperature decrease should have resulted in sulphide precipitation as

ZnCl24

− PbCl24

−

H S ZnCl (or PbCl ) ZnS(or PbS) 2H 4Cl2 42

42 ++ + +− − −→ .

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Precipitation of sulphide minerals yields hydrogen ion and results in pH decrease, whichcontributes to the wall-rock alteration or to the creation of open space into which oresimultaneously precipitated.

Sulphur isotope values (d34SCDT) of carbonate-hosted Pb–Zn deposits in the Centraland Eastern Taurides are from −5.4‰ to 13.70‰. It is very difficult to determine the pre-cise nature of the source of sulphur with such a wide range of d34SCDT data. One particularlocation amongst the deposits, the Çad0rkaya deposit, which is related to late Eocene–Oligocene(?) magmatic intrusion, has the average d34SCDT value of −0.15‰ (n = 3),clearly indicating a typical magmatic source for the sulphur. The slightly negative isotopevalues of the Ayrakl0 deposit (d34SCDT from −5.4‰ to −2.12‰) indicate that the sulphurmay have originated from a source related to organic compounds that is rich in 32S isotopevalues. Also, framboidal pyrite occurrence in the paragenesis of the Ayrakl0 deposit indicatesthat the bacteriogenic sulphur reduction processes have played an important role in low-temperature conditions (up to 110°C, Jørgensen et al. 1999). The Delikkaya, Denizovas0,and Suçat0 deposits in the Eastern Taurides and Katranbas0–K0z0lgeris–Küçüksu depositsin the Central Taurides are slightly rich in 34S (d34SCDT from 3.43‰ to 13.70‰, averageof 17 samples 9.07‰), which indicates a crustal source of the sulphur. Sulphur may haveoriginated from evaporates and/or formation water via organic matter oxidation, such as

Positive sulphur isotope values of the sulphides that fall into a narrow band may indicatean isotopically equilibrated sulphur source and thermochemical sulphate reduction.

It is well known that the metal source of most of the MVT deposits is crustal (e.g.Sverjensky 1981, 1986; Leach et al. 2006), and fluids leach the metals from the crust andtransport into the deposition site by laterally migrating during the closure of an ocean ororogenesis. On the other hand, metals can be leached from the crust via vertically circulating

Figure 11. Comparison of the homogenization temperature and salinity values of the Celal Dag,Delikkaya, and Ayrakl0 Pb–Zn deposits with the different deposit types (our data plotted on the figuretaken from Kontak 1995).

CH O SO H S HCO2 42

2 32+ → +− .

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hydrothermal fluids through the fault zone at the early stage of the opening an ocean. TheZn and Pb might be generated from oilfield brines, which include a high amount of Zn andPb, i.e. 700 and 200 ppm, respectively (Carpenter et al. 1974). Such highly saline hydro-thermal solutions could migrate on a large scale and pick up the metals from the pathwayrocks. The rock associations of the Taurides and sulphur and lead isotope data indicatethat the metals may have leached from clastic rocks such as quartzite and shales duringlong-term transportation from the deeper parts of the basin into the basinal highs. Both thisstudy and Pb-isotope analysis made by Çevrim (1984) suggest that Pb has a highly radio-genic character (Figure 10). This statement indicates the important rate of lead that hasoriginated from an older continental crust as related with the decay of U and Th. On theother hand, metamorphosed Pb–Zn-rich levels within the schist in the Akdagmadeni massif,the basal part of the Taurides, at the south of the studied area has been reported (Genç2001). Such a metamorphic massif with Pb–Zn-rich lithologies can be a source of the met-als scavenged by deep-seated faults.

The most recent studies suggest that MVT deposits in the world are generally relatedto the platform carbonates within orogenic belts (Garven 1985; Bethke and Marshak 1990;Leach et al. 2001, 2005). A number of studies reveal that the solutions responsible for theMVT deposits are the output of a large-scale hydrothermal system related to main oro-genic events. The Tauride belt, a fragment of the Alpine–Himalayan orogenic belt, standsout with considerable widespread carbonate-hosted Pb–Zn deposits, which display simi-larities with each other and distinguish the region as an important Pb–Zn province. In thisstudy, these Pb–Zn deposits of the Central and Eastern Taurides, which commonly takeplace within the Permian, Devonian, and Jurassic limestones, are compared with eachother for the first time, and this correlation provides a regional-scale determination andmodelling of the ore formations. The Pb–Zn deposits of the Taurides are highly similar toMVT Pb–Zn deposits, in terms of carbonate host rocks, tectonic setting, alteration type(dolomitization), fluid characters, simple ore mineralogy and chemistry, and sulphur andlead isotope data. On the other hand, the deposits in the Taurides have been oxidized,reworked, and re-deposited as in situ and/or transported to the karstic holes and re-accu-mulated as a clastic material. The geological nature of the region in which the Tauridedeposits occur is highly complex when compared to those MVT deposits elsewherebecause of the effects of the multi-phase orogenic deformations due to Alpine orogenesisand following the post-orogenic deformation stage (i.e. the neotectonic period).

In the light of this study we propose for the first time an MVT model on the formationand evolution of the Tauride Pb–Zn deposits in Turkey. According to our model, we couldcome up with the following conclusions.

In the Upper Cretaceous, the total consumption of Tethyan Ocean gave way to a com-pressional tectonic regime, which forced the fluids to migrate and form the MVT depositsin the region (Figure 12).

In the Palaeocene–Eocene, the region reached to maximum crustal thickening causedby overthrusts, and S-type small granitic (e.g. late Eocene–Oligocene(?) Karamadaz0granodiorite) stocks were intruded into the nappe complex, and related skarn-type Fe andPb–Zn mineralizations (Çad0rkaya deposit) formed (Figure 12).

During the Miocene–Present, the region underwent rapid uplift owing to compres-sional tectonics and formation of both strike-slip and normal faults. The study area wasuplifted from the Miocene to the Present by at least 1500 m and underwent extensivekarstification. The MVT deposits largely oxidized, carbonatized, and re-formed intokarstic-type deposits by both in situ karstic process and/or transporting in short distances,due to this main uplift (Figures 12 and 13).

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The MVT-type Pb–Zn deposits are oxidized and carbonatized due to rapid uplift in theMiocene (t2 and t3) period (Figure 13). Oxidation of the sulphur minerals caused the pHto decrease, so karstification accelerated. The common intra-karstic sedimentation fea-tures in the region indicate that the metals had been transported as ions during the re-dep-ositional period. However, some ore gravels observed in the Suçat0 deposit indicate thatmechanical transportation also occurred in some places. Furthermore, the present condi-tion of the deposits (t3) engenders chemical zoning (Figures 7 and 13), thickening, andenrichment in the deposits re-formed during the karstification process.

Primary sulphidic Pb–Zn ores formed between Late Cretaceous and Palaeocene time.The Late Cretaceous marks the beginning of the ophiolite obduction over the Anatolidesfrom north to south. Thrusting of the oceanic crust and compaction of the passive margin

Figure 12. Model for formation of the carbonate-hosted Pb–Zn deposits in the Taurides (see textfor detail).

Figure 13. Model for evolution of the carbonate-hosted Pb–Zn deposits in the Taurides (see textfor detail).

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sediments should have been the main mechanism of the fluid generation and migration.The primary sulphidic Pb–Zn deposits (MVT type), which were subsequently re-modified,resemble the ‘wall-rock replacement’ and ‘residual and karst fill’ sub-types of non-sulphidezinc deposits of Hitzman et al. (2003) and formed after the Miocene time.

AcknowledgementsThe authors are thankful to Professor J. Hoefs (Goettingen University, Germany) for stable sulphurisotope studies and to Dr A.M. Van den Kerkhof (Goettingen University, Germany) for fluid inclu-sion studies. The authors are grateful to Ismet Alan and Metin Yüksel (General Directorate of Min-eral Research and Exploration – Ankara) for valuable discussions and contributions on the geology ofthe Taurides belt. For their critical review and helpful comments on an earlier version of the manu-script, Professor Jean Cline (University of Nevada, USA) and Professor Dr Barrie R. Bolton(Monash University, Australia) are thanked. Authors are thankful to Professor Hayrettin Koral(Istanbul University, Turkey) and Dr Cem Okan Kilic (University of Texas at Austin) for valu-able comments and improving the English text of the manuscript. Finally, the authors appreci-ate the very useful and beneficial comments and suggestions of the Editor of the Journal. TheGeneral Directorate of Mineral Research and Exploration (MTA) of Turkey gave valuablelogistic support during the field studies. The present work was supported by the Research Fundof Istanbul University, Project No. T-1164/18062001, and was partly supported by the TinçelCultural Foundation.

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Geochemical/isotopic evolution of Pb–Zn deposits in the Central and Eastern Taurides, Turkey

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