(Simav-Kütahya) Cu-Pb-Zn-(Ag) Mineralization, NW TURKEY

Cent. Eur. J. Geosci. • 5(3) • 2013 • 435-449 DOI: 10.2478/s13533-012-0139-2

Central European Journal of Geosciences

Fluid Inclusion and Sulfur Isotope Thermometry of the Inkaya (Simav-Kütahya) Cu-Pb-Zn-(Ag) Mineralization, NW TURKEY

Research Article

Yeșim Özen∗ and Fetullah Arik†

Geological Engineering Department, Selçuk University, Konya, Turkey

Received 14 May 2013; accepted 18 August 2013

Abstract: The Inkaya Cu-Pb-Zn-(Ag) mineralization, located about 20 km west of the Simav (Kütahya-Turkey), is situated in the northern part of the Menderes Massif Metamorphics. The mineralization is located along an E-W trending fault in the Cambrian Simav metamorphics consisting of quartz-muscovite schist, quartz-biotite schist, muscovite schist, biotite schist and the Arıkayası formation composed of marbles. Mineralized veins are 30-35 cm in width. The primary mineralization is represented by abundant galena, sphalerite, chalcopyrite, pyrite, fahlore and minor amounts of cerussite, anglesite, digenite, enargite, chalcocite, covellite, bornite, limonite, hematite and goethite with gangue quartz. Fluid inclusion studies on the quartz samples collected from the mineralized veins indicate that the temperature range of the fluids is 235°C to 340°C and the salinities are 0.7 to 4.49 wt. % NaCl equivalent. The wide range of homogenization temperatures indicates that two different fluid generations were trapped in quartz. Sulfur isotope studies of the sulfide minerals showed that all of the δ S values are between − : and 2.6 per mil. These values are a typical range for hydrothermal sulfide minerals that have sulfur derived from a magmatic 34 source. 2 1 Pyrite-galena and pyrite-chalcopyrite sulfur isotope fractionation is consistent with an approach to isotopic equilibrium, and calculated temperatures are 254.6 and 277.4°C for pyrite-galena and 274.7°C for pyrite-chalcopyrite. The microthermometric data and sulfur isotope thermometry indicate the existence of a hydrothermal fluid that circulated along the fault crossing the Simav metamorphics and Arıkayası formation. Fluid inclusion and sulfur isotope thermometry can be used in combination with ore petrographical and geological information to provide site-specific targets for meso-hypothermal metal concentrations. Keywords: Fluid inclusion • sulfur isotope thermometry • Inkaya Cu-Pb-Zn-(Ag) mineralization • Simav • meso-hypothermal © Versita sp. z o.o.

1. Introduction

∗ † E-mail: [email protected] E-mail: [email protected] The study area is located in Ahmetli (Simav-Kütahya) in the Western Anatolia Region which is one of Turkey’s most important metallic provinces. The area is located in the western part of the Anatolian tectonic belt, in the southern part of the İzmir-Ankara zone, and in the northern 435 Fluid Inclusion and Sulfur Isotope Thermometry of the Inkaya (Simav-Kütahya) Cu-Pb-Zn-(Ag) Mineralization, NW TURKEY

part of the Menderes Massif and it is part of the Inner volcano-sedimentary sequence affected by HP/LT meta- West Anatolian of the Aegean Region. The Inkaya Cu- morphism, and this blueschist belt rests with a tectonic Pb-Zn-(Ag) mineralization is located about 20 km west of contact on the Afyon Zone at the south [12]. The Afyon the Simav (Kütahya-Turkey) (Fig. 1). The İnkaya Cu-Pb- zone was overthrusted by the Tavşanlı Zone and con- Zn-(Ag) mineralization is located along the E-W trending sists of shelf-type metasediments of Paleozoic-Mesozoic fault in the Simav metamorphics and the Arıkayası forma- age affected by low grade, regional, greenschist metamor- tion belonging to Menderes Massif Metamorfics, is vein phism [2, 4, 12, 13]. The Afyon Zone rests directly on the type mineralization (Fig. 2, Fig. 3). gneisses of the Menderes Massif [8]. [14] suggested that The WNW-ESE trending Simav Graben is located in the the Afyon zone of the Anatolides uncomformably overlies study area (Fig. 2). The Simav Graben was formed due to the Menderes Massif mentioned as a “core complex”. [15] the activation of the lateral component of the Simav Fault suggested that the north-south shortening of NW Turkey by N-S extension [1]. Several mineralizations (Arpaçukuru ceased at the end of the Oligocene and is replaced by N- Fe-Cu, Değirmenciler Sb, Gürkuyu Sb, Pınarbaşı Fe- S extension in the Lower Miocene. Thus, the extensional Cu-Pb-Zn mineralizations etc.), occur along the Simav regime formed the E-W extending graben systems in the Graben, and were formed in association with a tectono- region [16, 17] (Fig. 1 and Fig. 2). The Menderes Massif magmatic period. is interpreted as a “metamorphic core complex” formed on Geological studies on the metamorphic rocks of the region account of the listric faults, e.g. [14], [18–23] which consti- were carried out by [2–4]. [5, 6] studied the granitoids from tute the boundary of the graben. The development of the the petrogenetic point of view. [7] investigated the chem- magmatic activity in the western Anatolia is closely asso- ical composition and origin of volcanic rocks of Cenozoic ciated with the tectonic evolution of the region [12, 17, 24– age in the Simav region. [8] determined that mineraliza- 33]. As a result of the N-S compressional tectonic regime, tion is related to the faults of the Simav Graben. [9] stud- calc-alkaline volcanism closely associated with the gran- ied five mineralizations in the region that are products of itoids was developed in the region. syn-extensional magmatism related to the Menderes core The Simav Graben trending WNW-ESE is located in the complex. study area (Fig. 2). The alluvium is commonly shown in The present study was carried out in order to investigate the north part of the Simav Graben, whereas metamorphic the chemical-physical conditions and formation tempera- and plutonic rocks commonly crop out in the south part tures of the hydrothermal fluids and the mechanism of the (Fig. 2). The region is crossed by E-W trending faults İnkaya Cu-Pb-Zn-(Ag) mineralization using isotopic and which are nearly parallel to the Simav graben fault. The fluid inclusion data. In this study, fluid inclusion and sul- other fault system is a N-S trending set which cut the fur isotope thermometry data along with field observations former set of faults. and ore petrographical data were interpreted to constrain chemical and temperature conditions of the mineralizing Pre-Cambrian Menderes Massif Metamorphics (Kalkan fluids in the İnkaya Cu-Pb-Zn-(Ag) mineralization. The formation, Simav metamorphics, Sarıcasu formation, study of the İnkaya Cu-Pb-Zn-(Ag) mineralization and Arıkayası formation) form the basement in the region similar mineralizations along Simav Graben will poten- (Fig. 2). The massive is composed of a Precambrian tially be used to resolve problems regarding other similar “Gneiss core” and Paleozoic and Mesozoic “schist cover” mineralizations in the world. series [34–36]. According to [14] the “Gneiss core” con- 2. Geological settings stitutes the base of the lithological units within the studied area. It consists of the Kalkan formation represented 2.1. Regional geological setting by migmatite and biotite-bearing gneiss. The “schist cover” includes the Simav metamorphics, the Sarıcasu formation and the Arıkayası formation from bottom to top. Simav metamorphics which constitute the basal unit of The study area is located at the Menderes Massif (meta- the schist cover begin with muscovite schist, and con- morphic core complex) in the Western Turkey. In Western tinue with muscovite-biotite schist comprising metamafic- Turkey, the Pontides and the Anatolide-Tauride Block are metaultramafic levels in the middle part of the unit [8]. separated by an ophiolitic belt, known as the Izmir-Ankara The Sarıcasu Formation consists of quartz, albite, chlorite, suture zone, thrust southwards onto the Anatolides and muscovite bearing schists representing lower grade meta- Taurides [10] (Fig. 1). The region is within the Anatolides morphic facies than the Simav Metamorphics [8]. Arıkayası tectonic unit [11]. The Anatolides consist of the Tavşanlı formation has both lateral and vertical gradation to the zone, the Afyon zone and the Menderes Massif from north Sarıcasu Formation, the unit is composed of marble [8]. to south, respectively. The Tavşanlı zone consists of a The Budağan limestone unconformably overlies the meta- 436 Y. Özen, F. Arik

Figure 1. Geological and geotectonical maps of the Western Anatolia (after [45]).

morphics, starting with a conglomerate level including replacement-type kaolinite and alunite deposits related abundant and quartz pebbles. Granitoids crop out in the to the Simav Graben [8, 9, 37–44]. The İnkaya Cu-Pb-Zn- northern part of the studied area to the north of the Simav (Ag) mineralization, the Arpaçukuru Fe-Cu mineralization Graben. According to modal compositions of the Eğrigöz and the Değirmenciler Sb mineralization are shown along Granitoid, the pluton comprises granite, monzogranite and 2.2.the Simav Local Graben geological in Figure setting2. - ˙Inkaya deposit granodiorite, and is calc-alkaline in compositon [8,9]. The Kızılbük formation, uncomformably overlying the granitoids, is composed of the alternation of sandstone, clay- stone, marl and clayey limestone, all of dirty yellow to Mesothermal base-metal (Cu-Pb-Zn) veins are located in beige colours [8]. The Kızılbük formation grades to the the northern block of the Simav Graben [46–49]. These Civanadağ tuffs and is related to the Akdağ volcanites. mineralizations occur in the Eğrigöz granitoids and in the The Civanadağ tuffs consist of white and gray coloured gneisses of the Menderes Massif. The İnkaya Cu-Pb- tuffs with agglomerates in the upper levels. The tuffs are Zn-(Ag) mineralization is a similar Cu-Pb-Zn vein in the rhyolitic, andesitic and dasitic in composition. The Ak- southern block of the Simav Graben. The mineralization dağ volcanites consist of andesite, rhyolite, rhyodacite and occurs in the “schist cover” of the Menderes Massif as a dacite [8,9] (Fig.2). vein type [8, 9, 37–41]. There are a number of vein-type and stratiform base-metal The Inkaya Cu-Pb-Zn-(Ag) mineralization is located in mineralizations, epithermal precious metal, stibnite de- the western part of the study area, approximately 2 km posits, porphyry-type Cu-Mo deposit, and hydrothermal south of the town of Ahmetli (Fig. 3). The İnkaya Cu-Pb- 437 Fluid Inclusion and Sulfur Isotope Thermometry of the Inkaya (Simav-Kütahya) Cu-Pb-Zn-(Ag) Mineralization, NW TURKEY

Figure 2. Geological map of the region (after [9]).

Figure 3. Geological map of the study area (modiﬁed after [8, 9]).

Zn-(Ag) mineralization is confined by the Tahtacı Ridge through it. The other gallery was opened in the mineral- in the north, the Karantılı Ridge in the west, Küçükalan ization zone throughout an E-W fault (Fig. 3, Fig. 4). Place in the south and the Kocakulak Stream in the east. The Inkaya Cu-Pb-Zn-(Ag) vein-type mineralization is lo- In the mineralization area, there are two different galleries cated in mica-schist of the Simav metamorphics and mar- opened in previous years. Now, these two galleries are bles of the Arıkayası formation along the E-W trending filled with water (Fig. 4d). The first gallery was aban- fault (Fig. 3). The Simav metamorphics are represented by doned because the mineralization could not be reached the mica-schists that consist of metamafic-metaultramafic levels in the central part. The Arıkayası formation is rep- 438 Y. Özen, F. Arik

Figure 4. Photographs from gallery of the ˙Inkaya Cu-Pb-Zn-(Ag) vein type mineralization

resented by white, pinkish, light gray marble that is hard, veins in the Environmental Isotope Laboratory at the Uni- fragile and has irregular structure. Granoblastic textured versity of Arizona using an elemental analyzer (Costech) marbles consist mainly of carbonates and minor amounts coupled to the mass spectrometer. Precision is estimated of quartz and tridymite. The gray marbles of the Arıkayası to be ±0.15 or better (1s). formation cover the schists particularly on the top of the hills. 3. Materials and Methods Textural and microthermometric studies were carried out on the fluid inclusions from the İnkaya Cu-Pb-Zn-(Ag) mineralization. All fluid inclusions studied are hosted by quartz crystals associated with oxides and sulfides. The microthermometric studies were done in the Fluid Identification and characterization of the mineral assem- Inclusion Laboratory of Istanbul University. Microther- blages were carried out by means of ore microscopy anal- mometric analyses were done on polished thin sections yses for 16 samples at the Geological Engineering depart- using Linkam equipment (THMSG 600 freezing–heating ment of Selçuk University and ore petrography laboratory stage). In order to record the phase changes a coupled of the General Directorate of Mineral Research and Ex- image analysis system (magnetoscope− and videoprinter) ploration (MTA). A Nikon LV100 Pol microscope equipped was used. A total of 17 fluid inclusions were analyzed with Nikon (12 MP) digital camera at Niğde University by cycles of freezing down to 140°C and heating up (Niğde) was used to determine ore minerals, paragenetic to the appropriate temperature of total homogenization to successions and distinct textures. Two of the 16 samples ensure stability of the inclusions and representatively of were used in fluid inclusion studies, all of them were used the observations. These cycles were generally repeated in sulfur isotope analysis and three of them were used in several times in order to avoid problems with nucleation sulfur isotope thermometry. during freezing runs. Salinities were expressed as wt. % The sulfur isotope analysis was performed on pyrite, NaCl equivalent, using the melting temperature of the last galena and chalcopyrite for 17 samples collected from ore crystal of ice for two-phase fluid inclusions [50]. 439 Fluid Inclusion and Sulfur Isotope Thermometry of the Inkaya (Simav-Kütahya) Cu-Pb-Zn-(Ag) Mineralization, NW TURKEY

Petrographic and microthermometric analyses were con- galena was altered to cerussite and anglesite through- ducted on the fluid inclusions trapped in the quartz, calcite out its fractures and fissures under atmospheric condi- and sphalerite using doubly polished sections and wafers tions (Fig. 6d,g). As well as cerussite and anglesite, chal- of thickness variable from 80 to 140 µm using a Linkam cocite and covellite are observed throughout its fissures THMSG-600 heating–freezing stage and Olympus BX51 (Fig. 6g). Galena usually occurs in massive and irregu- 2 microscope. The stage was calibrated using pure CO lar grains containing typical triangular cleavage fissures standards, and, according to replicate measurements, the due to polishing (Fig. 6a,c-g). Galena commonly contains accuracy is estimated to be in the order of ±2°C for heat- fahlore (Fig. 6c,d), that is abundant in the mineralization

ing and ±0.2°C for freezing measurements.ice The tempera- and shows allotriomorphic forms. tures of homogenization (Th), eutectic phase change (Te) Enargite, occurring as inclusions within hypidiomorphic and final meltingice of ice (Tm ) were measured at least pyrite, is the earliest formed metallic mineral (Fig. 6d). twice on each inclusion. Fluid inclusion salinity was cal- Chalcopyrite continued to form during and after pyrite culated from Tm [51]. crystallization. Chalcopyrite-I which is observed rarely 4. Results in sphalerite (Fig. 6e) has very small sizes. Idiomor- phic sphalerite is observed as inclusions within allotri- 4.1. Ore petrography omorphic chalcopyrite-II. Idiomorphic and hypidiomorphic sphalerite has brown-reddish internal reflections indicating high Fe contents and high formation temperature, according to [52, 53]. The dominant sulphide minerals in the İnkaya Cu-Pb-Zn- Fahlore can be observed in some samples as inclusions (Ag) mineralization are pyrite, sphalerite, galena, chal- within galena. Fahlore is replaced by galena which of- copyrite, fahlore and minor enargite, associated with ten contains from small to large inclusions of sphalerite, gangue quartz accompanied by secondary ore minerals as pyrite and chalcopyrite (Fig. 6c-g). Pyrite and chalcopy- covellite, chalcocite, digenite, cerussite, anglesite, mala- rite were observed in fissures and fractures of the Simav chite, orpiment, realgar, hematite, goethite and limonite. metamorphics (wall rock), also (Fig. 7). Some of these minerals may be shown in ore body as macroscopical (Fig. 5). Based on ore petrography of the studied samples, it is Ore minerals are found in mica-schist (Simav metamor- possible to establish a paragenetic sequence which in- phics) and marbles (Arıkayası formation). The ore miner- cludes at least two stages (according to chalcopyrite) of als in 16 polished sections listed in relative abundance ore mineral deposition. Therefore, in the Inkaya Cu-Pb- from most abundant to least are: pyrite, chalcopyrite, Zn-(Ag) mineralization, the sequence is enargite, pyrite, galena, sphalerite, fahlore and enargite (Fig. 6). Pyrite chalcopyrite-I, sphalerite, chalcopyrite-II, fahlore, galena. is also shown along to fractures and fissures of wall rocks Based on the microscopic studies the mineralization was (Fig. [7]). formed during the hydrothermal phase of magmatic ore Pyrite is the most abundant ore mineral and occurs in deposition. According to mineral paragenesis (enargite all of the polished sections. Pyrite grains are sub- to etc.) [54], this mineralization type is a high sulfidation de- euhedral with cubic forms and show a large variety of 4.2.posit. Fluid inclusions textures and grain sizes (Fig. [6]). Some pyrite grains appear coarse grained, cataclastic structured, idiomorphic and allotriomorphic showing spongy texture. Chalcopyrite is observed frequently in the polished sec- Fluid inclusion studies were carried out for microthermom- tions and is the second ore mineral in abundanceµ etry measurements on quartz related with primary miner- (Fig. [6]a-h). Chalcopyrite generally occurs as massive alization. Typically, the quartz is associated with galena aggregates ranging in size from few hundredths of a m and sphalerite. Quartz grains hosting fluid inclusions are to various cm. Chalcopyrite crystals are opticallyµ homoge- either clear phenocrysts in, or sample with, metallic miner- neous. There are 2 generations: Earlier chalcopyrite (Cpy als in veins, such as galena and sphalerite. Based on [55]’s I) appears as small rounded blebs (5 to 25 m) included criteria, all investigated fluid inclusions are identified as in sphalerite crystals (Fig. 6e). Later chalcopyrite (Cpy II) primary. The primary, secondary and psuedosecondary is widely distributed, and occurred later than sphalerite criteria suggested by [55] were used as a standard for dis- and pyrite (Fig. 6a-d,f-h). tinguishing the origin of inclusions but microthermometric Deformation traces are commonly observed on galena measurements were mainly carried out on inclusions with in the mineralization (Fig. 6a,c-g). Galena has some a primary or most likely primary origin. In terms of the pyrite, chalcopyrite, sphalerite and fahlore inclusions. The number and the volumetric proportions of phases present 440 Y. Özen, F. Arik

Figure 5. Photographs showing ore minerals as macroscopical from the Inkaya Cu-Pb-Zn-(Ag) mineralization (a) photograph showing mainly pyrite (py), galena (gn), sphalerite (sph), chalcopyrite (cpy) and malachite (mh) in the ore vein (b) galena (gn) and sphalerite (sph) (c) pyrite (py), chalcopyrite (cpy) and quartz (q) as gangue mineral (d) galena (gn) and chalcopyrite (cpy).

· − − 2 2 in the fluid inclusions at room temperature, only one type CaCl 6H O) during freezing first melt within 3°C of pre- of inclusions can be recognized. The fluid inclusions are dicted eutectic temperatures ( 37·°and 52°C).· Such low predominantly two-phase liquid vapour (L+V), primary in- first melt· temperatures indicate the presence of metastable 2 2 2 2 clusions. In the inclusions, the vapor phase typically oc- salt hydrates (presumably MgCl 8H O, MgCl 6H O or 2 2 cupies 10-15 vol % of the total inclusion volume.µ The mor- CaCl 4H O). The formation of metastable phases during phology of the inclusions vary from tabular to ellipsoidal, freezing of fluid inclusions can lead to misinterpretation and sizes usually range from < 5 to 10 m (Fig. 8). of the chemical composition of− fluid inclusions in natural The fluid inclusions from quartz in veins containing galena samples. This is especially true for fluid inclusions with first melt temperatures below 37°C which may be erro- and sphalerite (ore-stage quartz) homogenize at temper- 2 atures varying from 235 to 340°C (Table 1, Fig. 9). The neously interpreted as being rich in CaCl [56]. Eutectic wide range of homogenization temperature indicates that temperatures data of the fluid inclusions in Inkaya Cu- Pb-Zn-(Ag) mineralization indicate more complex brines two fluid generations were trapped in quartz. The homog- 2 within a polycomponent salt system, probably a H O- enization temperatures (Th) of the first fluid are in the 2 2 NaCl-KCl-CaCl -MgCl system [57]. ice range of 295 – 340°C, the second fluid is in the range of − − 235 – 270°C (Fig. −10). − The range of ice melting temperatures (Tm ) is wide, from The inclusions in quartz show a eutectic temperature (Te) 2.7 to 0.4°C. The salinities are varying between 0.7 – with a range from 49.6 to 32.9°C (Table 1·). Fluid in- 4.49 wt. NaCl eq. (Table 1 and Fig. 9). To summarize, 2 2 2 2 clusions in the NaCl-MgCl -H O and NaCl-CaCl -H O the microthermometric data is centered on two ranges, as 2 2 systems that form stable salt hydrates (MgCl 12H O and shown in the Th vs. salinity plot (Fig. 10). 441 Fluid Inclusion and Sulfur Isotope Thermometry of the Inkaya (Simav-Kütahya) Cu-Pb-Zn-(Ag) Mineralization, NW TURKEY

Figure 6. Mineral assemblages of the ˙Inkaya Cu-Pb-Zn-(Ag) mineralization. (a), (c) sphalerite (sph), chalcopyrite (cpy-II) and pyrite (py) inclusions in galena (gn); gangue (g) (b) idiomorphic sphalerite (sph) and pyrite (py) inclusions in chalcopyrite-II (cpy-II); (d) sphalerite (sph), chalcopyrite (cpy-II), pyrite (py) and fahlore (fh) inclusions in galena (gn), cerussite (cs) are observed throughout fissures of galena (gn) and enargite (eg) inclusion in cataclastic pyrite (e) small sized chalcopyrite-I (cpy-I) inclusions in sphalerite (sph) (f) galena (gn) containing typical triangular cleavage fissure (g) chalcopyrite (cpy-II) replaced by galena (gn), cerussite (cs) are observed throughout fissures of galena (gn) and chalcocite (chc) formation throughout fissures; gangue (g) (h) hypidiomorphic pyrite (py) inclusions in sphalerite (sph). 442 Y. Özen, F. Arik

Figure 7. Pyrite (py) and chalcopyrite (cpy) in ﬁssures and fractures of Simav metamorphics; gangue (g).

Figure 8. Photomicrographs showing ﬂuid inclusions in quartz.

4.3. Sulfur isotopes n − : n n n copyrite and pyrite have ranges between 0.1 and 0.3‰ n CDT ( = 3, mean = 0.2) and 1δ5 and 2.6‰ CDT ( = 10, mean = 1.5), respectively. Seventeen samples of galena ( = 4), chalcopyrite ( = 34 δ 3) and pyrite ( = 10) from the İnkaya Cu-Pb-Zn-(Ag) Sulﬁdes show a wide range of S values34 between – mineralization were analyzed for sulfur isotopes. The iso- 2.1 (galena) and +2.6‰ (pyrite). The S values of −topic: results− : on galena,n pyrite and chalcopyrite− : samples chalcopyrite34 vary between +0.1 and +0.3‰. The order are reported in Table 2. The galena has ranges between of S enrichment obeys the equilibrium sequence, i.e., 1 7 and 2 1‰ CDT ( = 4, mean = 2 0). The chal- pyrite > chalcopyrite > galena [59]. 443 Fluid Inclusion and Sulfur Isotope Thermometry of the Inkaya (Simav-Kütahya) Cu-Pb-Zn-(Ag) Mineralization, NW TURKEY

Figure 9. (a) Homogenization temperatures and (b) salinities of ﬂuid inclusions in quartz crystals of the ˙Inkaya Cu-Pb-Zn-(Ag) mineralization.

Table 1. Homogenization temperature (Th), eutectic temperature (Te), final ice melting temperature (Tmice and salinities of fluid inclusions in quartz crystals of the Inkaya Cu-Pb-Zn- (Ag) mineralization, Simav-Kütahya (NW Turkey)) Temperatures Salinity Mineral Te (°C) Tmice (°C) Th (°C) (wt. % NaCl eq.) − − − − quartz −47.6 −1.8 300 3.06 quartz −49.6 −1.8 295 3.06 quartz −46.6 −1.8 305 3.06 quartz −41.7 −1.8 320 3.06 quartz −35.0 −2.7 245 4.49 quartz 35.9 −2.7 315 4.49 quartz 32.9 2.7 235 4.49 Figure 10. Fluid inclusion data of quartz on homogenization − temperature–salinity diagram illustrating typical ranges quartz - −2.7 - 4.49 for fluid inclusions from different deposit types (modified quartz - −1.6 336 2.74 after [58]). quartz - 1.6 336 2.74 quartz - −1.6 300 2.74 quartz -− - 0.4 - 0.70 quartz - −1.6 - 2.74 quartz - 0.4 270 0.70 quartz - 1.6 - 2.74 quartz - - 300 - The most reliable thermometric estimates are obtained quartz - - 340 - from sulfur isotopic fractionation of pyrite-galena and pyrite-chalcopyrite pairs obtained by combining the analyzed minerals (Table 3). Pyrite-galena and pyrite- δ δ chalcopyrite mineral pairs are cogenetic according to ore 34 34 petrography and sulfur isotope studies. Pyrite-galena The S value of the fluid was calculated from their S and pyrite-chalcopyrite mineral fractionation is consistent 2 value of sulfide minerals and the mineral–H S fractiona- with an approach to isotopic equilibrium, and calculated 2 tion factor of [59], assuming H S as the main sulfur species temperatures are 254.6 and 277.4°C for pyrite-galena and in the fluid (Table 2). 274.7°C for pyrite-chalcopyrite pairs. 444 Y. Özen, F. Arik

Table 2. Sulfur isotope data of galena, chalcopyrite and pyrite and H S of the Inkaya Cu-Pb-Zn-(Ag) mineralization, Simav-Kütahya (NW Turkey) (H S were calculated by using equations of [59]. 1000 ln α 0.40(10 /T for pyrite; 1000 ln α −0.05(10 /T for chalcopyrite; 1000 ln 2 α −0.63(10 /T for galena. 6 2 6 2 2 6 2 = ) = ) 34 34 34 = ) Sample Mineral δ S(‰)mineral δ S(‰)H2S δ S(‰) interval − − IN-GI2 Galena −2.0 − − IN-G4I-16 Galena Galena −1.72.0 −0.02 0.02 − − ( 1.7) – (-2.1) 0.30 I-1 Galena 2.1 0.10 IN-G5I-7 Chalcopyrite Chalcopyrite 0.3 0.1 0.26 (0.1) – (0.3) I-12 Chalcopyrite 0.1− 0.26 IN-G4 Pyrite 2.0 0.46 IN-G4-2IN-G5 Pyrite 1.8 1.2 0.07 0.73 0.53 − IN-GI2IN-G6 Pyrite 1.4 2.2 0.93 IN-G7 Pyrite 1.3 0.03 ( 1.5) – (2.6) 0.13 I-7 Pyrite 2.1 0.83 I-10 Pyrite− 2.6 −1.33 I-15Bold: Pyrite 2.3 1.03 I-1 Pyrite 1.5 2.77 The samples were used for sulfur isotope geothermometry

Table 3. Sulfur isotope geothermometry of the Inkaya mineralization, Simav-Kütahya (NW Turkey) (1000 ln α 1,03(10 /T for pyrite-galena;

1000 ln α 0,45(10 /T for pyrite-chalcopyrite [59, 60] 6 2 6 2 = ) δ34S(‰) Pyrite-Galena Pyrite- Chalcopyrite = Sample) Galena Pyrite Chalcopyrite T °C* T °C* 277.4 ∆ ∆ 254.6 IN-GI2 -2.0 1.4 - 3.4 --274.7 IN-G4 -1.7 2.0 - 3.7 -- IN-G5 - 1.8 0.3 - - 1.5 5. Discussion

eastern part of the Central Rhodopes and are absent in the western part of the Central Rhodopes, which are characterized by few small Pb–Zn and Sb deposits [65, 66]. A most relevant modern analogue to the Menderes Mas- Ore fields include Madan, Laki, Davidkovo, Eniovche and sif core complexes is the Eastern Rhodope in Bulgaria. Ardino in Bulgaria, and Thermes as a continuation of the The first is a large, metamorphic core complex [61]. The Madan ore field in Greece [61, 67]. The deposits comprise protracted extension and magmatism show surprising sim- hydrothermal Pb–Zn veins, disseminated vein stockworks, ilarity with the Eastern Rhodope in Bulgaria. Both the and metasomatic replacements, which are the economi- Eastern Rhodopes and the Menderes core complexes ex- cally most important orebodies. All ore fields are spa- hibit exhumation histories of surprisingly similar duration tially associated with the inferred detachment fault [68]. (about 35–45 Ma) and evolution of the mafic magmatism, In a recent study of the Petrovitsa vein of the Madan ore and similar mechanisms likely explain these processes in field, [69] showed that precipitation within the vein struc- the two regions [61]. ture was mainly the result of cooling from about 310 to The Rhodope Massif, like the Menderes Massif, is charac- 285°C over the assumed 400 m vertical interval. [70] es- terized by numerous small to moderate-sized polymetallic tablished a similar temperature interval from fluid inclu- ore deposits of variable composition and ore type, some sion studies in quartz from the Laki ore field but [71] noted of which are grouped into ore districts of global signif- much lower minimal temperatures. The largest tempera- icance [62–64]. Major ore deposits are localized at the 445 Fluid Inclusion and Sulfur Isotope Thermometry of the Inkaya (Simav-Kütahya) Cu-Pb-Zn-(Ag) Mineralization, NW TURKEY

δ − :

34 ture range for the productive paragenesis (200 to 345°C) The S variation of 2 1‰ and 2.6‰ of minerals falls was measured for the Davidkovo ore field [72]. The poly- within the range of magmatic sulfur, indicating a mag- metallic vein deposits from Madan and Luki precipitated matic origin. A temperature of approximately 270°C is from a slightly acidic fluid with a range of salinities from calculated by sulfur isotope geothermometry for the min- 0.5 to 5 eq. wt.% NaCl. These temperatures and salin- eralization. ities are similar with to those of the İnkaya Cu-Pb-Zn- Both sulfur isotope thermometry and fluid inclusion data (Ag) mineralization (235 – 340°C / 0.7 – 4.49 wt.% NaCl). provide evidence for presence of a hydrothermal system. The İnkaya Cu-Pb-Zn-(Ag) mineralization shows surpris- The fluid inclusion data suggest the same origin for the ing similarity to the vein type Pb-Zn mineralizations of fluid as indicated by the sulfur isotope data. Sulfur iso- the Rhodope Massif in formation, age, temperature and tope studies indicate that Inkaya Cu-Pb-Zn-(Ag) mineral- salinity. ization derived from a magmatic hydrothermal system that Available salinity data for the İnkaya Cu-Pb-Zn-(Ag) was probably part of a larger system at depth. Finally, mineralization is less than 4.5 eq. wt.% NaCl, but 2 to fluid inclusion studies may help define the mechanism of 3 eq. wt.% NaCl is adequate to transport ore-forming con- mineralization. centrations of Pb and Zn [69]. Ore petrography, sulfur isotope data, sulfur isotope ther- A mesothermal base-metal (Cu-Pb-Zn) vein is located in mometry and fluid inclusion data suggest the presence the northern block of the Simav Graben [1, 46–49]. These of magmatic-hydrothermal (meso-hypothermal) solution. mineralization occur in the Eğrigöz granitoids and in the Geochronological and radiogenic isotope studies of the gneisses of Menderes Massif. The Inkaya Cu-Pb-Zn-(Ag) İnkaya Cu-Pb-Zn-(Ag) mineralization and magmatism will mineralization is a similar Cu-Pb-Zn vein in the southern be clarified as soon as possible with a new study. block of the Simav Graben. The mineralization occurs in Acknowledgments the “schist cover” of the Menderes Massif as a vein type [8, 9]. While the İnkaya Cu-Pb-Zn-(Ag) mineralization is a Prof. Dr. İlkay KUŞÇU meso-hypothermal mineralization; the Arpaçukuru Fe-Cu mineralization is a porphyry type; the Değirmenciler Sb TheProf. authors Dr. Nilgün wish to GÜLEÇ thank mineralization is an epithermal type in the Simav Graben. (Muğla Sıtkı Koçman University-Muğla-TURKEY),Asst. Prof. The İnkaya Cu-Pb-Zn-(Ag) mineralization was first stud- Dr. Nurullah HANİLÇİ (Middle East Techni- ied by [8]. [8] focused on geological settings and ore min- cal University-METU-Ankara-TURKEY),Prof. Dr. İbrahim ÇOPUROĞLU eralogy of the İnkaya Cu-Pb-Zn-(Ag) mineralization. [8] (İstanbul University-İstanbul- made no mentions of fahlore and enargite. In this study, TURKEY) and (Niğde detailed ore petrography was carried out. Formation tem- University-Niğde-TURKEY) for their helpful discussions, perature of the mineralization was calculated by using advice and encouragement. The authors would like to fluid inclusion and sulfur isotope thermometry. thank reviewers for their careful readingScientific of the paper Research and 6. Conclusions theirProject helpful Coordination comments. of Selçuk This paper University that is part of the PhD research has been supported byTÜBİTAK-ÇAYDAG (BAP Project No: 09101029 and 09401059) and The İnkaya Cu-Pb-Zn-(Ag) vein type mineralization in the (Project No: 110Y355). Simav (Kütahya-Turkey) is related to the magmatic ac- References tivity that is closely associated with the tectonic evolution of the region. High sulfidation İnkaya mineralization, located in E-W oriented veins, have quite rich mineral assemblages. The metamorphic-hosted vein is mineral- [1] Oygür V., Erler A., Metallogeny of the Simav graben. ized with galena, sphalerite, chalcopyrite, pyrite, fahlore, Bulletin of the Geological Society of Turkey, 2000, quartz and accompanied by minor amounts of cerussite, 43, 7-19 (in Turkish with English summary) anglesite, digenite, enargite, chalcocite, covellite, bornite, [2] Akdeniz N., Konak N., The rock units of the Simav limonite, hematite and goethite. region of Menderes Massive and the situation of Fluid inclusions in quartz indicate that there were two metabazic and metaultramafic rocks. Bulletin of the ore forming stages characterized by hydrothermal fluids. Geological Society of Turkey, 1979, 22, 175 -184 (in These stages involved hydrothermal fluids of low (235 – Turkish with English summary) 270°C) - moderate (295 – 340°C) temperature and low- [3] Akdeniz N., Konak, N., Geology of Simav-Emet- moderate salinity (0.7 – 4.49 wt. % NaCl eq.). Tavşanlı-Dursunbey-Demirci regions. Bulletin of 446 Y. Özen, F. Arik

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