Geochemistry of Hydrothermal Alteration Associated with Cenozoic Intrusion-Hosted Cu-Pb-Zn Mineralization at Tav¸Sanlıarea, Kütahya, NW Turkey

Article Geochemistry of Hydrothermal Alteration Associated with Cenozoic Intrusion-Hosted Cu-Pb-Zn Mineralization at Tav¸sanlıArea, Kütahya, NW Turkey

Mustafa Kumral 1,*, Amr Abdelnasser 1,2 and Murat Budakoglu 1

1 Department of Geological Engineering, Faculty of Mines, Istanbul Technical University, Istanbul 34469, Turkey; [email protected] (A.A.); [email protected] (M.B.) 2 Department of Geology, Faculty of Science, Benha University, Benha 13518, Egypt * Correspondence: [email protected]; Tel.: +90-212-285-6307

Academic Editor: Maria Economou-Eliopoulos Received: 18 December 2015; Accepted: 6 February 2016; Published: 17 February 2016

Abstract: The Miocene magmatic intrusion in the Tav¸sanlızone of the Kütahya-Bolkarda˘gBelt (KBB) in the northwestern region of Turkey is represented by the E˘grigözgranitoids. This paper studies the petrology and geochemistry of hydrothermal alterations associated with the vein-type Cu-Pb-Zn mineralization hosted by this pluton, focusing on the determination of the mass gains and losses of chemical components, which reflect the chemical exchanges between the host rocks and hydrothermal fluids. Vein-type Cu-Pb-Zn mineralization is closely associated with intense hydrothermal alterations within the brecciation, quartz stockwork veining, and brittle fracture zones that are controlled by NW-SE trending faults cutting through the E˘grigözgranitoids. Paragenetic relationships reveal three stages of mineralization: pre-ore, ore, and supergene. The ore mineralogy typically includes hypogene chalcopyrite, sphalerite, galena, and pyrite, with locally supergene covellite, malachite, and azurite. Wall-rock hypogene hydrothermal alterations include pervasive silicification, sulfidation, sericitization, and selective carbonatization and albitization. These are distributed in three main alteration zones (zone 1: silicified/iron carbonatized alterations ˘ albite, zone 2: argillic-silicic alterations, and zone 3: phyllic alterations). Based on the gains and losses of mass and volume (calculated by the GEOISO-Windows™ program), zone 1 has a higher mass and volume gain than zones 2 and 3. Non-systematic zonal distributions of alterations are observed in which the silicic-carbonate alterations +/´ albitization appeared in zone 1 in the center and the phyllic-argillic alterations appeared in zones 2 and 3, with an increase in base metals (Cu-Pb-Zn) in the zone from Cu, Cu-Pb, to Cu-Pb-Zn moving outwards.

Keywords: vein-type Cu-Pb-Zn mineralization; hydrothermal alteration geochemistry; mass-balance calculation; E˘grigözgranitoids; Kütahya; Turkey

1. Introduction The metallogenic belt in Turkey lies within the Anatolian tectonic belt which is a part of the larger Tethyan-Eurasian metallogenic belt (TEMB). TEMB was formed during Mesozoic and Early Cenozoic times [1]. In the western part of this belt, mineralization was controlled by extensional events that took place after the closure of the NeoTethys [1]. It is linked with the subduction of Neothyan oceanic crust remnants beneath the Anatolian plate along the Aegean-Cyprean Arc. This mineralization is also related to the Oligocene-Miocene/Pliocene calc-alkaline magmatic activity during post-collision continent-continent setting and includes Pb-Zn, Sb, As, and Au-Cu deposits [1]. Ku¸scu et al. [2] reported four different varieties of mineral deposits occurring in the western TEMB: (1) low and high

Minerals 2016, 6, 13; doi:10.3390/min6010013 www.mdpi.com/journal/minerals Minerals 2016, 6, 13 2 of 23 sulfidation epithermal deposits (Au and Au-Ag), (2) mesothermal (Cu-Pb-Zn), (3) skarn (Fe-Cu and Pb-Zn),Minerals and 2016 (4), 6 porphyry, 13 Cu deposits. 2 of 23 The E˘grigözgranitoid is located in western Anatolia (NW Turkey) and is a Cenozoic magmatic The Eğrigöz granitoid is located in western Anatolia (NW Turkey) and is a Cenozoic magmatic intrusion associated with the Hellenic subduction zones [3–6]. It represents the largest regionally intrusion associated with the Hellenic subduction zones [3–6]. It represents the largest regionally 2 exposedexposed NNE-trending NNE-trending pluton, pluton, covering covering ~400 ~400 km km2,, andand it it syn-tectonically syn-tectonically intrudes intrudes into into the the northern northern MenderesMenderes Massif Massif (foliated (foliated metagranites, metagranites, gneissicgneissic granites,granites, and and microgranites) microgranites) and and Tav Tavșanls, anlıı zone zone (blueschist/ultramafic(blueschist/ultramafic belt) belt) [ 7[7]] (Figure (Figure1 a,b).1a,b). ItsIts graniticgranitic rocks occur occur in in different different textural textural varieties, varieties, rangingranging from from microgranites microgranites chilled chilled along along the the peripheral peripheral contact with with Menderes Menderes Massif Massif into into a coarser a coarser holocrystallineholocrystalline character character moving moving inward [8]. [8]. They They are arealso alsoformed formed by partial by partialmelting meltingof mafic, oflower mafic, lowercrustal crustal rocks rocks during during post-collisional post-collisional extensional extensional tectonics tectonics in the in theregion region [9] [and9] and are arecoeval coeval to to Oligo-MioceneOligo-Miocene granitoids granitoids in thein centralthe central Aegean Aegean Sea region.Sea region. Altunkaynak Altunkaynaket al. [et6 ]al. reported [6] reported a SHRIMP a U-PbSHRIMP zircon ageU-Pb of emplacementzircon age of ofemplacement E˘grigözgranitoids of Eğrigöz at 19.48granitoids˘ 0.29 at Ma, 19.48 while ± 0.29 the 39Ma,Ar/ while40Ar datingthe 39 40 of biotiteAr/ andAr dating hornblende of biotite separated and hornblende from these rocksseparated is of 19.0from˘ these0.1 Ma rocks and is 18.9 of ˘19.00.1 ± Ma, 0.1 respectively.Ma and The18.9 mineralization ± 0.1 Ma, respectively. associated The with mineralization the E˘grigözgranitoids associated includeswith the FeEğrigöz skarn granitoids deposits [includes10,11], where Fe skarn deposits [10,11], where they are distributed along the border of this intrusion and within other they are distributed along the border of this intrusion and within other metamorphic rocks at the Çatak metamorphic rocks at the Çatak and Küreci area in the north, and the Kalkan and Karaağıl skarn in and Küreci area in the north, and the Kalkan and Karaa˘gılskarn in the south. the south.

Figure 1. (a) Map of Turkey [2,12]. (b) Area around Eğrigöz granitoids at the northern Menderes core Figure 1. (a) Map of Turkey [2,12]; (b) Area around E˘grigözgranitoids at the northern Menderes core complex (MCC) [13,14]. complex (MCC) [13,14].

2 Minerals 2016, 6, 13 3 of 23

This paper focuses on the vein-type Cu-Pb-Zn mineralization in E˘grigözgranitoids with special reference to the petrology and geochemistry of different hydrothermal alteration zones around the mineralized veins in the mine area by applying the mass and volume gains and losses of chemical components during the alteration process, which reﬂect chemical exchanges between wall rocks and hydrothermal ﬂuids [15–19]. The geological and petrographic studies determine the key features of host rocks, mineralogical changes and alteration zones related to the Cu-Pb-Zn mineralization.

2. Materials and Methods Field work was carried out during a number of field workings to collect rock samples representing the different rock units and mineralization types. Fifty thin-sections and polished sections were examined petrographically. Whole-rock major and trace element analyses were conducted for 23 rock samples in the Geochemistry Research Laboratories of Istanbul Technical University (ITU/JAL). The samples were pulverized using a Tungsten Carbide milling device. Major elements of the samples were analyzed by using a BRUKER S8 TIGER model X-ray Fluorescence spectrometer (XRF) (Istanbul Technical University, Istanbul, Turkey) with a wavelength range from 0.01–12 nm. Trace elements were analyzed by using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) ELAN DRC-e Perkin Elmer model (Istanbul Technical University). Approximately 100 mg powder sample was digested in two steps. The first step was completed with 6 mL 37% HCl, 2 mL 65% HNO3 and 1 mL 38%–40% HF in a pressure- and temperature-controlled Teflon beaker using Berghoff Microwave™ at an average temperature of 180 ˝C. The second step was completed with the addition of 6 mL 5% Boric acid solution. The remaining solution sample was analyzed by ICP-MS instrument. Normative mineral abundances were calculated from the major elements analyses and plots of elements were created using the igneous petrology software® Igpet (version 2.3) [20]. GEOISO-Windows™ program [21] was used for calculation and plotting of mass balance/volume change by determination of the absolute mobility of elements using equations from Gresens [15] and isocon diagrams of Grant [16,17].

3. Geology of the Study Area The study area is located about 50 km north of the Simav district (Kütahya-Turkey) (Figure1b) in the Tav¸sanlızone of the Kütahya-Bolkarda˘gBelt (KBB) at the northern margin of the Tauride-Anatolide platform (TAP). It represents parts of the northern Menderes core complex (MCC) in the Anatolian tectonic belt (Figure1b). This area is near Sudö¸se˘givillage at the southwest of Kütahya in the Korucuk region along the Da˘gardı district (Figure2). Detailed ﬁeld mapping reveals that it comprises Precambrian mylonitic biotite gneisses (Menderes massif), Paleozoic metamorphic rocks (mica schist, chlorite schist, calc-schist and marble), Jurassic limestone, and Cretaceous Da˘gardı ophiolite mélange. These rocks were intruded by the Miocene E˘grigözgranitoids (Figure2). Precambrian mylonitic biotite gneisses represent the oldest rocks formed in the base of the northern Menderes core complex (MCC) (Figure2). These rocks are intruded by the E˘grigözgranitoids and are highly mylonitized as a result of shearing (Figure3a). They are medium- to coarse-grained, whitish-grey in color, and show well-developed gneissic textures. They consist essentially of biotite and recrystallized quartz-feldspar aggregates with minor opaque minerals (Figure3a). K-feldspar is represented by microcline microperthite that formed large crystals surrounded by biotite lathes and quartz. Zircon occurs as an accessory mineral, forming high relief anhedral crystals (Figure3b). The Paleozoic metamorphic rocks that surround the E˘grigözgranitoids contain mica schist, chlorite schist, calc-silicate schist, and marble. They are affected by low-, moderate- and high-grade metamorphism [22]. The marble that appears in study area is ﬁne- to medium-grained, grayish in color, and composed essentially of carbonate (calcite and magnesite, ~80 vol. %), K-feldspar, and quartz (Figure3c). The marble is occasionally cut by small quartz veinlets that are either parallel or cross-cutting each other (Figure3d). Minerals 2016, 6, 13 4 of 23 Minerals 2016, 6, 13 4 of 23

Figure 2. Geologic map of the study area (simplified after [22,23]). Figure 2. Geologic map of the study area (simpliﬁed after [22,23]).

The Cretaceous Dağardı mélange represents the southernmost continuation of the Tavșanlı ZoneThe [24] Cretaceous occurring Da˘gardımélange in the northwesternrepresents part the southernmostof the study continuation area. It was of emplaced the Tavs, anlı onto Zone the [24 ] occurringTauride-Anatolide in the northwestern Platform during part ofthe the Late study Cretaceous area. It period was emplaced and formed onto a belt the of Tauride-Anatolide allochthonous Platformassemblages during sourced the Late from Cretaceous the Neotethyan period Izmir-Ankara-Erzincan and formed a belt of allochthonous Ocean [24]. Petrographically, assemblages sourced the fromDağ theard Neotethyanı mélange is represented Izmir-Ankara-Erzincan by tremolite-actinolite Ocean [24 schists]. Petrographically, in the Adnan Bahce the Da˘gardı area. These mélange rocks is representedare fine-grained, by tremolite-actinolite foliated and greenish-grey schists inin thecolor, Adnan and they Bahce consist area. of bundles These rocks of actinolite are ﬁne-grained, crystals foliatedembedded and greenish-greyin a schistose groundmass in color, and of they tremolite, consist actinolite, of bundles and of quartz actinolite with crystals pyroxene embedded relics and in a schistoseopaque groundmassminerals (Figure of tremolite, 3e). Tremolite actinolite, is the and dominant quartz with amphibole pyroxene group relics andmineral, opaque and minerals it is (Figurecommonly3e). Tremolite colorless, is forming the dominant subhedral amphibole fibrous groupcrysta mineral,ls with a andpreferred it is commonly orientation colorless, parallel formingto the subhedralmain foliation ﬁbrous trend. crystals Actinolite with a preferredis characterized orientation by a pale parallel green to thecolor main with foliation parallel trend.arrangement Actinolite of is 4 Minerals 2016, 6, 13 5 of 23 Minerals 2016, 6, 13 5 of 23 characterizedelongated small by prisms. a pale green These color rocks with are parallelcut by quartz arrangement and carbonate of elongated veinlets small that prisms. are parallel These to rocks the aremain cut foliation by quartz trend and (Figure carbonate 3e,f). veinlets that are parallel to the main foliation trend (Figure3e,f).

Figure 3. (a) Streaks of highly deformed and recrystallized quartz and feldspar with biotite as a result Figure 3. (a) Streaks of highly deformed and recrystallized quartz and feldspar with biotite as a result of mylonitization in biotite gneiss. (b) K-feldspar, plagioclase and biotite with zircon in biotite gneiss. of mylonitization in biotite gneiss; (b) K-feldspar, plagioclase and biotite with zircon in biotite gneiss; (c) Carbonate (calcite and magnesite) with lesser amounts of K-feldspar, and quartz in marble of (c) Carbonate (calcite and magnesite) with lesser amounts of K-feldspar, and quartz in marble of Paleozoic metamorphic rocks. (d) Small quartz veinlets cross-cut each other in marble. (e) Bundles of Paleozoic metamorphic rocks; (d) Small quartz veinlets cross-cut each other in marble; (e) Bundles of actinolite crystals embedded in a schistose groundmass of tremolite, and quartz in actinolite crystals embedded in a schistose groundmass of tremolite, and quartz in tremolite-actinolite tremolite-actinolite schist of Dağardı mélange. (f) Quartz and carbonate veinlets are parallel to the schist of Da˘gardı mélange; (f) Quartz and carbonate veinlets are parallel to the main foliation trend of

tremolite-actinolitemain foliation trend schist. of tremolite-actinolite Abbreviations: actinolite schist. Abbreviations: (Act), biotite (Bt),actinolite calcite (Act), (Cal), biotite K-feldspar (Bt), calcite (Kfs), magnesite(Cal), K-feldspar (Mgs), (Kfs), opaque magnesite mineral (Opq),(Mgs), plagioclase opaque mineral (Plag), (Opq), pyroxene plagioclase (Px), quartz (Plag), (Qz), pyroxene sericite (Ser),(Px), tremolitequartz (Qz), (Tr), sericite and zircon (Ser), (Zr).tremolite (Tr), and zircon (Zr).

The Eğrigöz granitoid is the largest exposed pluton in western Anatolia that intruded into the rocks of the northern Menderes Massif (Figure 1b). The northern part of this pluton covers a wide area of the study area at the eastern and southern sides (Figure 2). Based on the modal analyses, 5 Minerals 2016, 6, 13 6 of 23

The E˘grigözgranitoid is the largest exposed pluton in western Anatolia that intruded into the

Mineralsrocks of 2016 the, 6 northern, 13 Menderes Massif (Figure1b). The northern part of this pluton covers a wide6 of 23 area of the study area at the eastern and southern sides (Figure2). Based on the modal analyses, these rocks areare inin monzograniticmonzogranitic andand quartzquartz monzoniticmonzonitic compositionscompositions (Figure(Figure4 ).4). MonzograniticMonzogranitic rocks consist of quartz (~25(~25 vol. %) and K-feldspar (orthoclase and microperthite, ~45~45 vol. %) with a minor amount ofof plagioclaseplagioclase (~35(~35 vol. %), biotite (~5(~5 vol. %), and minor sericite,sericite, zircon and opaques ((~1~1 vol. %) %) (Figure 55a).a). PlagioclasePlagioclase (albite(albite toto oligoclase)oligoclase) formsforms colorless,colorless, subidiomorphic,subidiomorphic, elongatedelongated and tabular crystals, with distinct lamellar twinning and sometimes zoning. Sericite is an alteration mineral occurring after K-feldspar and oligoclaseoligoclase (Figure(Figure5 b).5b). QuartzQuartz monzoniticmonzonitic rocksrocks containcontain quartz ((~15~15 vol. %%)) and are accompaniedaccompanied by K-feldspar (orthoclase- and microcline-microperthite; ((~35~35 vol.vol. %%)),)), oligoclaseoligoclase (~35 (~35 vol. vol. %), %), and and biotite biotite with with some some opaque opaque minerals minerals (Figure 5(Figurec). Some 5c). samples Some samplescontain minorcontain clinopyroxene minor clinopyroxene (Figure5 (Figured), hornblende 5d), hornblende (Figure5 (Figuree) andzircon 5e) and enclosed zircon enclosed in the biotite in the biotitecrystal crystal (Figure (Figure5f). 5f).

Figure 4. ClassificationClassiﬁcation of E E˘grigözgranitoids,ğrigöz granitoids, based on modal mineralogymineralogy [[25],25], QQ == quartz; A = Alkali feldspar; P = Plagioclase. Plagioclase.

4. Results Results and and Discussion Discussion

4.1. Cu-Pb-Zn Mineralization and A Associatedssociated Hydrothermal Alterations Cu-Pb-Zn mineralization hosted by the E E˘grigözgranitoidsğrigöz granitoids is closely associated with an intense hydrothermal alteration that was controlled by NW-SE-trending faults within brecciation, quartz stockwork veining, and brittle fracturefracture zones (Figure2 2).). TheThe normalnormal faultsfaults cutcut throughthrough thisthis plutonpluton atat the southernsouthern part part of of the the study study area area and areand nearly are parallelnearly parallel to the direction to the ofdirection Simav graben of Simav (NWN-ESE). graben (NWN-ESE).In addition, theseIn addition, faults werethese consideredfaults were considered to be conduits to be for conduits the transport for the transport of ore-bearing of ore-bearing ﬂuids to fluidsstructurally to structurally favorable sitesfavorable for the sites deposition for the ofdeposi ore mineralstion of ore [26 ].minerals The mine [26] area. The extends mine approximately area extends approximately600 m along this 600 fault m along zone this in the fault valley zone (NW-SE in the valley direction). (NW-SE Oyman direction).et al. [10Oyman] and et U˘gurcan al. [10] and UOymanğurcan [ 11and] stated Oyman that [11] Fe-skarn stated depositsthat Fe-skarn were formeddeposits along were the formed contact along of E˘grigözgranitoids the contact of Eğrigöz with granitoidsPaleozoic metamorphicwith Paleozoic rocks metamorphic (mica schist, rocks chlorite (mica schist, schist, calc-silicate chlorite schist, schist, calc-silicate and marble) schist, along and its marble) along its northern and southern borders. The studied Cu-Pb-Zn mineralization is found locally as vein-type deposits near these skarn deposits, and is controlled by faulting which post-dates the intrusion. It is characterized by a retrograde alteration forming K-silicate and sericitic alterations (sericite + chlorite + kaolinite ± tremolite ± calcite).

6 Minerals 2016, 6, 13 7 of 23 northern and southern borders. The studied Cu-Pb-Zn mineralization is found locally as vein-type deposits near these skarn deposits, and is controlled by faulting which post-dates the intrusion. It is characterized by a retrograde alteration forming K-silicate and sericitic alterations (sericite + chlorite + ˘ ˘ kaoliniteMinerals 2016tremolite, 6, 13 calcite). 7 of 23

FigureFigure 5. Photomicrographs 5. Photomicrographs of of E˘grigözgranitoids: Eğrigöz granitoids: (a ()a Quartz,) Quartz, K-feldspar, K-feldspar, plagioclase plagioclase with biotite with in biotite in E˘grigözmonzogranite;Eğrigöz monzogranite. ((bb)) SericiticSericitic alteration alteration after after K-feldspar K-feldspar and and plagioclase plagioclase in monzogranite. in monzogranite; (c) Zoned(c) Zoned plagioclase plagioclase with with quartz, quartz, K-feldspar K-feldspar andand biotite in in E E˘grigözquartzğrigöz quartz monzonite. monzonite; (d) and (d) ( ande) (e) MinorMinor clinopyroxene clinopyroxene and hornblendeand hornblende with with containing containi biotiteng biotite and zirconand zircon in quartz in quartz monzonite; monzonite. (f) Zircon enclosed(f) Zircon in biotite enclosed in quartz in biotite monzonite. in quartz Abbreviations:monzonite. Abbreviations: biotite (Bt), biotite clinopyroxene (Bt), clinopyroxene (Cpx), hornblende (Cpx), (Hbl),hornblende K-feldspar (Hbl), (Kfs), K-feldspar opaque (Kfs mineral), opaque (Opq), mineral plagioclase (Opq), plagioclase (Plag), quartz (Plag), (Qz), quartz sericite (Qz), sericite (Ser), and zircon(Ser), (Zr). and zircon (Zr).

4.1.1. Hydrothermal Alterations 4.1.1. Hydrothermal Alterations VariableVariable types types and and styles styles of hydrothermalof hydrothermal alterations alterations are are observed observed around the the fault/shear fault/shear zone zone in in the Eğrigöz granitoids. Three main alteration zones with gradual boundaries are distinguished the E˘grigözgranitoids. Three main alteration zones with gradual boundaries are distinguished based based on the field relationships, and geological and petrographic data. Zone 1: silicified/iron on the ﬁeld relationships, and geological and petrographic data. Zone 1: siliciﬁed/iron carbonatized carbonatized alterations (quartz-sulfide-carbonate ± albite) occurred around ore veins and shear zones; zone 2: argillic-silicic alterations (quartz-sulfide ± kaolinite ± sericite ± chlorite), and zone 3: phyllic alterations (sericite/muscovite-quartz-sulfide ± carbonate ± tremolite). 7 Minerals 2016, 6, 13 8 of 23

MineralsThe2016 silicified/iron, 6, 13 carbonatized alteration zone (zone 1) envelops ore veins and/or shear zones in8 of the 23 mine area and is characterized by yellowish/brownish or reddish colors (Figure 6a,b). As this zone is near the fault zone, it is highly affected by brecciation (Figure 6c). Based on ore mineralogical studies,alterations it has (quartz-sulfide-carbonate a high amount of chalcopyrite˘ albite) and occurred pyrite with around the alteration ore veins minerals and shear (Figure zones; 6d). zone 2: argillic-silicicThe argillic-silicic alterations alteration (quartz-sulfide zone (zone˘ 2)kaolinite is in contact˘ sericite between˘ chlorite), the northern and zone border 3: phyllic of zone alterations 1 and the(sericite/muscovite-quartz-sulfide Eğrigöz granitoids. It is represented˘ carbonate by rocks˘ tremolite). enriched in quartz and sulfide minerals with kaolinite,The silicified/iron sericite, and carbonatized chlorite (Figure alteration 6e,f). zone Qu (zoneartz 1)veinsenvelops are characterized ore veins and/or by the shear comb-textured zones in the infillingmine area of andquartz is characterized crystals growing by yellowish/brownish out from a wall rock or (Figure reddish 6e). colors The (Figure mineralization6a,b). As in this this zone zone is isnear situated the fault within zone, the it is contact highly affectedwith quartz by brecciation veins and (Figure alteration6c). Based minerals on ore (Figure mineralogical 7a) enriched studies, in chalcopyriteit has a high amountand sphalerite of chalcopyrite with pyrite. and pyrite with the alteration minerals (Figure6d).

Figure 6. (a) Silicified/ironSilicified/iron carbonatized alterationalteration˘ ± albite;albite. ((bb)) Reflected Reflected light, light, centimeter-scale centimeter-scale view view of ofcarbonatization carbonatization alteration alteration with with quartz quartz in zone in zone 1; (c )1. Brecciation (c) Brecciation of quartz of quartz filled byfilled carbonate by carbonate and sulfide and sulfide(pyrite) (pyrite) in zone in 1; zone (d) Carbonate, 1. (d) Carbonate, quartz andquartz sulfide and sulfide (pyrite (pyrit and chalcopyrite)e and chalcopyrite) with sericite with sericite in zone in 1; zone(e) Reflected 1. (e) Reflected light, centimeter-scale light, centimeter-scale view of comb-textured view of comb-textured quartz crystals quartz within crystals wall within rock (sericitized, wall rock (sericitized,kaolinitized kaolinitized and silicic) in and zone silicic) 2; (f) in Quartz zone and2. (f sulfide) Quartz minerals and sulfide with minerals sericite in with zone sericite 2. Abbreviations: in zone 2. Abbreviations:carbonate (Car), carbonate chalcopyrite (Car), (ccp), chalcopyrite hematite (hem), (ccp), pyrite hematite (py), (hem), quartz pyrite (Qz),and (py), sericite quartz (Ser). (Qz), and sericite (Ser). 8 Minerals 2016, 6, 13 9 of 23

MineralsThe argillic-silicic 2016, 6, 13 alteration zone (zone 2) is in contact between the northern border of zone 1 and9 of 23 the E˘grigözgranitoids. It is represented by rocks enriched in quartz and sulﬁde minerals with kaolinite, The phyllic alteration zone (zone 3) is the outer zone and is characterized by preferential sericite, and chlorite (Figure6e,f). Quartz veins are characterized by the comb-textured inﬁlling of replacement of the original K-feldspar and/or plagioclase-biotite by quartz crystals growing out from a wall rock (Figure6e). The mineralization in this zone is situated sericite/muscovite-kaolinite-carbonate (Figure 7b,c). Some samples have tremolite (Figure 7d), within the contact with quartz veins and alteration minerals (Figure7a) enriched in chalcopyrite and traversed by a few carbonate veinlets (Figure 7e). This zone has a high amount of chalcopyrite, sphalerite with pyrite. sphalerite, and galena with pyrite (Figure 7b,f).

Figure 7. (a) Enriched mineralization at contact with quartz veins and sericitic alteration in zone 2; Figure 7. (a) Enriched mineralization at contact with quartz veins and sericitic alteration in zone 2. (b) Reflected light, centimeter-scale view shows phyllic alteration with sulfide in zone 3; (c) Kaolinite (b) Reflected light, centimeter-scale view shows phyllic alteration with sulfide in zone 3. (c) Kaolinite and sericite/muscovite with quartz in zone 3; (d) Tremolite and sericite alteration in zone 3; and sericite/muscovite with quartz in zone 3. (d) Tremolite and sericite alteration in zone 3. (e) Carbonate veinlets traversed the altered rocks; (f) Reflected light, centimeter-scale view of pyrite, (e) Carbonate veinlets traversed the altered rocks. (f) Reflected light, centimeter-scale view of pyrite, chalcopyrite, sphalerite, and hematite in zone 3. Abbreviations: azurite (Azu), carbonate (Car), chalcopyrite, sphalerite, and hematite in zone 3. Abbreviations: azurite (Azu), carbonate (Car), chalcopyritechalcopyrite (Ccp), (Ccp), covellite covellite (Cv), (Cv), hematite hematite (hem),(hem), K-feldspar (Kfs), (Kfs), kaolinit kaolinitee (Kao), (Kao), malachite malachite (Mlc), (Mlc), muscovitemuscovite (Ms), (Ms), plagioclase plagioclase (Plag), (Plag), pyrite pyrite (Py),(Py), quartzquartz (Qz), sericite (Ser), (Ser), and and sphalerite sphalerite (Sp). (Sp).

9 Minerals 2016, 6, 13 10 of 23

The phyllic alteration zone (zone 3) is the outer zone and is characterized by preferential replacement of the original K-feldspar and/or plagioclase-biotite by sericite/muscovite-kaolinite-carbonate (Figure7b,c). Some samples have tremolite (Figure7d), traversed by a few carbonate veinlets (Figure7e). This zone has a high amount of chalcopyrite, sphalerite, and galena with pyrite (Figure7b,f).

4.1.2. Ore Mineralogy The ore mineralogy includes chalcopyrite, sphalerite, galena, pyrite, covellite, malachite, and azurite. These ore minerals are disseminated in the alteration zones, as well as at the contact between quartz veins and highly altered granite. Gangue minerals include quartz, mica, and calcite. Chalcopyrite is characterized by a brassy yellow color in air with high reflectance, weak bireflectance and weak anisotropy. It occurs as fine- to medium-grained, anhedral to subhedral crystals (up to 4 mm in grain size) disseminated in gangue quartz and altered zones within quartz veins and host rocks. It is associated with pyrite, sphalerite, and galena (Figure8a) and occurs as inclusions in sphalerite as chalcopyrite exsolution (Figure8b). Also, it is partly replaced by sphalerite and poikilitically trapped within massive pyrite. Chalcopyrite crystals are slightly corroded along their cracks replaced by covellite (Figure8c). They often display various oxidation products with covellite and goethite in the weathered areas. Sphalerite is the second-most abundant sulfide mineral. It is characterized by grey color with low reflectance and isotropism and occurs as coarse anhedral grains (up to several centimeters in size) in the main vein as well as in the altered host rocks associated with copper minerals. It is always found close to chalcopyrite and covellite (Figure8d) with ragged edges and fractures. Galena occurs disseminated in quartz-veined altered rocks either as subhedral to anhedral grains and massive, or as inclusions within sphalerite. It is characterized by white to whitish-grey colored grains with triangular cleavage pits and it sharply cuts across chalcopyrite and sphalerite (Figure8e). Inclusions of chalcopyrite are found within galena as irregular veinlets. Pyrite shows a whitish-yellow color with high reflectivity and forms idiomorphic crystals associated with chalcopyrite, sphalerite, and galena. It occurs as irregular and corroded massive aggregates scattered in quartz veins of the host rock. Pyrite displays progressive stages of alteration to goethite (Figure8f). Covellite is characterized by strong blue color with orange to reddish-brown anisotropism and is derived from the alteration of chalcopyrite along their fractures or partial and/or complete alteration (Figure9a,b). Malachite occurs as aggregates in association with chalcopyrite, sphalerite, and azurite and appears green in color in cross-polarized light and grey in color with low reflectance in plane-polarized light (Figure9c,d). Azurite, like malachite, is associated with chalcopyrite and sphalerite and occurs in supergene weathered deposits, and it has a blue color (Figure9c,d). Fe-oxides and hydroxides that are represented by hematite and goethite occur mainly as alteration products replacing the Fe-bearing sulfide minerals in quartz veins and alteration zones. They occur as porous colloform bands with radiating fine fibers and/or massive crystal aggregates associated with pyrite (Figure8f). Paragenetic relationships appear in three stages of mineralization: pre-ore, ore, and supergene. Each stage is characterized by unique mineral assemblages (Figure 10). The pre-ore stage has disseminated euhedral pyrite and quartz, observed as a large anhedral crystal matrix. The main hydrothermal stage has sphalerite predated by galena and chalcopyrite. During this stage, a second type of quartz was deposited as small crystals forming thin veinlets. The supergene post-ore assemblage consists of covellite, malachite, azurite, and Fe-oxides and -hydroxides. Minerals 2016, 6, 13 11 of 23 Minerals 2016, 6, 13 11 of 23

Figure 8. Photomicrographs of reﬂected light microscopy: (a) Chalcopyrite associated with pyrite and galenaFigure in8. aPhotomicrographs quartz vein; (b) Inclusions of reflected of chalcopyrite light microscopy: in sphalerite (a) Chalcopyrite as chalcopyrite associated disease; with (c) Slightly pyrite corrodedand galena along in chalcopyritea quartz vein. cracks (b) replacedInclusions by of covellite; chalcopyrite (d) Sphalerite in sphalerite with chalcopyrite, as chalcopyrite covellite disease. and pyrite;(c) Slightly (e) Galena corroded with along triangular chalcopyrite cleavage cracks pits associated replaced withby covellite. chalcopyrite (d) Sphalerite in quartz vein;with (chalcopyrite,f) Alteration ofcovellite pyrite and to goethite pyrite. ( withe) Galena azurite. with Abbreviations: triangular cleavage azurite pits (Azu), associated chalcopyrite with chal (Ccp),copyrite covellite in quartz (Cv), galenavein. (f (Gn),) Alteration goethite of (Gth), pyrite pyrite to goethite (Py), sphalerite with azuri (Sp),te. and Abbreviations: quartz (Qz). azurite (Azu), chalcopyrite (Ccp), covellite (Cv), galena (Gn), goethite (Gth), pyrite (Py), sphalerite (Sp), and quartz (Qz).

11 Minerals 2016, 6, 13 12 of 23

Minerals 2016, 6, 13 12 of 23 Minerals 2016, 6, 13 12 of 23

FigureFigure 9. Photomicrographs 9. Photomicrographs of of reflected reﬂected light light microscopy: ( a(a)) Covellite Covellite is anis an alteration alteration product product after after Figure 9. Photomicrographs of reflected light microscopy: (a) Covellite is an alteration product after chalcopyrite.chalcopyrite; (b) (Theb) The same same as asFigure Figure 7a7a but but in cross-polarized light light (XPL); (XPL). ( c) ( Aggregatesc) Aggregates of malachite of malachite chalcopyrite. (b) The same as Figure 7a but in cross-polarized light (XPL). (c) Aggregates of malachite (green)(green) and and azurite azurite (blue) (blue) associated associated with with sphalerite. sphalerite; ((dd)) TheThe cross-polarized cross-polarized light light (XPL) (XPL) of Figure of Figure7c. 7c. (green) and azurite (blue) associated with sphalerite. (d) The cross-polarized light (XPL) of Figure 7c. Abbreviations:Abbreviations: azurite azurite (Azu), (Azu), chalcopyrite chalcopyrite (Ccp), (Ccp), covellite (Cv), (Cv), malachite malachite (Mlc), (Mlc), pyrite pyrite (Py), (Py), quartz quartz Abbreviations: azurite (Azu), chalcopyrite (Ccp), covellite (Cv), malachite (Mlc), pyrite (Py), quartz (Qz),(Qz), and andsphalerite sphalerite (Sp). (Sp). (Qz), and sphalerite (Sp).

Figure 10. Paragenetic sequence of quartz, sulfide minerals, and supergene minerals as Figure 10. Paragenetic sequence of quartz, sulﬁde minerals, and supergene minerals as deﬁned by Figuremineraldefined 10. assemblages. Parageneticby mineral assemblages. sequence of quartz, sulfide minerals, and supergene minerals as defined by mineral assemblages. 4.2. Geochemical Characteristics

4.2. GeochemicalThe granitoid Characteristics rocks are divided into least-altered and altered rocks. The altered rocks have spatially associated with Cu-Pb-Zn mineralization developed along NW-SE fault zones in the The granitoid rocks are divided into least-altered and altered rocks. The altered rocks have 12 spatially associated with Cu-Pb-Zn mineralization developed along NW-SE fault zones in the 12 Minerals 2016, 6, 13 13 of 23

4.2. Geochemical Characteristics The granitoid rocks are divided into least-altered and altered rocks. The altered rocks have spatially associated with Cu-Pb-Zn mineralization developed along NW-SE fault zones in the northern part of the E˘grigözgranitoids. Six representative samples were collected from the least-altered granitoid rocks and 17 representative samples were collected from the altered rocks. Each was analyzed for major and trace elements (Tables1 and2).

Table 1. Major and trace elements contents of E˘grigözgranitoids at the Tavs, anlı area.

Sample ID Detection Limit Eg-21 Eg-23 Eg-25 Eg-30 Eg-41 Eg-42 Major elements (wt %)

SiO2 0.016 67.2 66.8 66.0 65.0 65.9 68.8 Al2O3 0.026 15.0 15.1 15.7 15.1 15.2 15.4 Fe2O3 0.001 2.9 2.9 3.2 4.1 3.5 1.2 MgO 0.060 1.3 1.2 1.3 1.2 1.0 1.1 CaO 0.001 2.5 2.9 3.2 3.3 2.9 2.4 Na2O 0.120 3.6 3.5 3.6 3.5 3.3 3.9 K2O 0.001 5.4 5.3 4.7 5.3 5.7 5.2 TiO2 0.001 0.5 0.5 0.5 0.3 0.5 0.2 P2O5 0.012 0.2 0.2 0.2 0.2 0.3 0.1 MnO 0.001 0.05 0.08 0.07 0.02 0.05 0.03 CO2 - 0.04 0.35 0.24 0.33 0.13 0.19 SO2 0.002 0.01 0.01 0.01 0.10 0.11 0.02 LOI - 0.8 1.1 1.0 2.0 1.6 1.7 Trace elements (ppm) As 10 - - - 80 10 20 Ba 24 1260 1190 1200 1350 1030 300 Co 9 20 30 35 10 20 15 Cs - - 188 128 6 8 7 Cu 1 3 5 5 61 12 1 Ga 6 15 15 16 15 16 15 Nb 6 14 15 14 14 15 14 Ni 6 8 6 9 11 7 7 Pb 5 25 31 29 178 36 0.7 Rb 3 140 140 130 210 170 220 S 20 43 72 53 520 530 110 Sc 8 437 252 409 - 8 - Sr 3 230 220 270 140 220 100 W 8 214 274 357 - - - Y 3 24 27 29 17 16 28 Zn 9 24 36 38 68 37 46 Zr 6 140 150 160 140 220 90 Density - 2.7 2.7 2.7 2.7 2.7 2.7 Quartz - 20.3 20.9 20.3 17.8 19.1 20.9 Orthoclase - 32.8 31.8 28.5 32.5 34.5 31.3 Albite - 28.7 28.2 29.4 29.2 27.6 33.1 D.I. - 81.8 80.9 78.2 79.5 81.2 85.3 FeOt - 2.6 2.6 2.9 3.7 3.1 1.1 K2O/Na2O - 1.5 1.5 1.3 1.5 1.7 1.3 LIL/HFS - 7.8 6.9 6.6 9.4 4.8 3.8 CIA - 50.0 49.2 50.2 47.9 49.8 49.1 Minerals 2016, 6, 13 14 of 23

Table 2. Geochemical data of the altered rocks in the study area.

Detection Least Altered Zone-1 Zone-2 Zone-3 Sample ID Limit Mean Eg-2 Eg-6 Eg-11 Eg-14 Eg-19 Eg-1 Eg-3 Eg-4 Eg-7 Eg-12 Eg-13 Eg-15 Eg-16 Eg-17 Eg-18 Eg-5 Eg-8 Eg-9 Eg-10 Major elements (wt %)

SiO2 0.016 66.6 44.0 82.1 24.9 73.8 71.6 58.8 93.1 58.3 92.6 86.5 58.0 51.1 69.9 62.3 68.1 86.9 70.5 80.9 52.1 Al2O3 0.026 15.2 1.9 1.0 2.1 0.5 13.2 3.3 1.7 6.1 1.7 1.0 3.6 3.9 10.8 6.2 15.4 5.5 8.5 5.8 10.1 Fe2O3 0.001 3.0 7.3 10.6 72.6 18.9 5.2 9.8 2.5 10.9 3.1 5.0 14.3 4.0 8.7 6.5 13.9 1.6 11.8 4.3 11.1 MgO 0.060 1.2 0.2 0.1 1.0 0.0 0.9 0.1 - 0.1 - - 0.1 0.1 0.2 0.1 0.7 0.1 0.1 0.1 0.1 CaO 0.001 2.9 0.1 0.0 1.6 0.1 4.3 0.1 - 0.1 0.1 - 0.1 0.1 0.5 0.2 2.3 0.1 0.1 0.1 0.2 Na2O 0.120 3.6 0.5 0.3 0.2 - 1.6 0.2 0.2 0.8 0.1 - 0.3 0.7 0.4 0.7 3.3 0.6 0.6 0.1 0.9 K2O 0.001 5.3 - - 0.6 - 1.8 - 0.1 1.5 0.2 0.1 0.3 0.8 2.7 1.6 4.8 2.8 4.0 2.9 3.8 TiO2 0.001 0.4 - - 0.1 - 0.2 - - 0.1 - - - 0.1 0.2 0.1 0.4 0.1 0.3 0.1 0.2 P2O5 0.012 0.20 - - 0.06 0.01 0.04 - - 0.02 0.04 - 0.03 0.03 0.12 0.06 0.14 0.04 0.06 0.03 0.10 MnO 0.001 0.05 0.30 1.32 0.04 0.46 0.10 0.25 0.01 0.11 - 0.01 0.05 0.12 0.09 0.06 0.08 0.02 0.22 0.01 0.01 SO2 0.002 0.04 13.67 0.24 - 1.06 3.65 9.43 10.82 18.89 - 13.48 9.50 13.95 4.86 26.50 8.06 0.77 0.45 2.52 6.39 LOI - 1.4 7.1 3.3 - 3.7 4.5 6.1 2.0 - 1.8 - 6.4 6.5 4.7 4.1 2.3 2.1 3.1 2.5 6.7 Trace elements (ppm) As 10 21 1417 36 1815 47 72 - 111 307 103 153 237 1625 111 71 739 55 63 80 373 Ba 24 1050 - 30 70 20 950 30 80 520 370 260 180 110 460 440 180 1040 1040 660 1010 Co 9 20 74 22 81 39 30 80 33 41 38 41 45 60 53 53 78 29 24 29 37 Cu 1 15 30,100 530 30,250 330 540 17,000 2440 8200 1900 6350 56,150 32,000 1880 1680 15,700 550 330 1000 57,800 Ga 6 15 - 10 - 7 15 - 12 83 - - 29 - 14 13 66 - 7 - - Nb 6 14 - - - - 8 ------39 - - 54 - 7 - - Ni 6 8 60 17 115 36 24 40 - 26 - 7 26 377,602 16 10 146,869 - 21 8 18 Pb 5 50 281,900 1400 375,500 3400 1560 - 260 52,700 870 9200 31,700 - 1660 1650 180 1800 3040 8130 65,030 Rb 3 168 - - - 10 78 - 3 - 3 - - - 34 40 14 68 100 77 106 S 20 221 68,450 1200 - 5320 18,260 47,180 54,150 94,540 67,450 47,540 69,850 24,350 132,640 40,360 3860 2260 12,600 32,000 Sr 3 196 22 10 56 10 59 - 14 - - 10 26 28 24 33 - 45 50 46 83 Y 3 24 306 19 384 32 20 108 3 74 4 16 48 377 9 11 174 8 21 19 98 Zn 9 42 188,030 6220 60,200 6150 8640 61,550 3180 128,500 290 1930 86,570 234,400 8500 6330 256,850 860 1950 2060 57,260 Zr 6 149 277 15 376 17 89 113 15 109 17 28 62 353 37 43 188 50 78 56 149 Density - 2.7 3.0 2.8 4.1 3.0 2.8 3.0 2.8 3.0 2.7 2.9 3.0 3.4 2.9 3.0 3.1 2.7 2.8 2.8 3.0 CIA - 49.4 65.6 61.0 37.5 74.2 52.2 85.9 80.8 67.6 90.5 81.9 81.0 67.6 74.1 68.4 52.2 58.2 63.2 63.7 65.6 Minerals 2016, 6, 13 15 of 23

4.2.1. Geochemistry of Least-Altered Rocks Minerals 2016, 6, x 1 of 4 The least-altered monzogranitic and quartz monzonitic E˘grigözgranitoids have SiO2 contents ranging4.2.1. from Geochemistry 64.9 to 68.8 of wtLeast-Altered % with an Rocks average differentiation index (D.I. = Qz + Ab + Or) of 81.2%. They have relatively high K contents with K2O/Na2O ratios ranging from 1.3 to 1.7. On the AFM The least-altered monzogranitic and quartz monzonitic Eğrigöz granitoids have SiO2 contents (Alkalis-FeOt-MgO) ternary diagram (Figure 11a) as defined by Irvine and Baragar [27], and the data ranging from 64.9 to 68.8 wt % with an average differentiation index (D.I. = Qz + Ab + Or) of 81.2%. points fall in the calc-alkaline field, being relatively rich in total alkali contents, coinciding with the They have relatively high K contents with K2O/Na2O ratios ranging from 1.3 to 1.7. On the AFM extensional(Alkalis-FeO trendt-MgO) of Petro ternaryet al. diagram[28]. The (Figure alumina 11a) as saturation defined by index Irvine (ASIand Baragar = A/CNK [27], =and molar the data Al2 O3/ (CaOpoints + Na2 fallO + in K the2O)) calc-alkaline of the studied field, samples being relatively of the granitoid rich in total rocks alkali is contents, mostly less coinciding than 1.0. with Therefore, the theseextensional samples are trend classified of Petro as et metaluminousal. [28]. The alumina in the saturation A/CNK indexversus (ASIA/NK = A/CNK diagram = molar [29 Al]2 (FigureO3/(CaO 11b). In the+ ternaryNa2O + K Na2O))2O-CaO-K of the studied2O diagram samples of [30 the], thegranitoid E˘grigözgranitoids rocks is mostly less are than plotted 1.0. Therefore, in the granite these and quartzsamples monzonite are classified field (Figure as metaluminous 11c). This in is the consistent A/CNK versus with theA/NK petrographical diagram [29] (Figure classification 11b). In ofthe these ternary Na2O-CaO-K2O diagram [30], the Eğrigöz granitoids are plotted in the granite and quartz based on modal analysis. According to the Mol. Al2O3/(CaO + Na2O + K2O)-Rb/Sr diagram [31], monzonite field (Figure 11c). This is consistent with the petrographical classification of these based these rocks are plotted within the I-type field (Figure 11d). Harris et al. [32] used the Rb/Zr versus SiO2 on modal analysis. According to the Mol. Al2O3/(CaO + Na2O + K2O)-Rb/Sr diagram [31], these rocks diagram to differentiate between two types of granites that are related to Group II and Group III. Group are plotted within the I-type field (Figure 11d). Harris et al. [32] used the Rb/Zr versus SiO2 diagram II granitesto differentiate are peraluminous between two syn-orogenic types of granites and similar that are to therelated S-type to Group granites II and of Chappell Group III. and Group White II [31] derivedgranites from are two peraluminous sources: hydrated syn-orogenic bases and of continentalsimilar to the thrust S-type sheetsgranites or of the Chappell sedimentary and White wedge [31] [32]. On thederived other from hand, two Group sources: III hydrated granites bases are post-collision of continental thrust calc-alkaline, sheets or derivedthe sedimentary from a wedge mantle [32]. source thathasundergoneextensivecrustalcontaminationsimilartovolcanic-arcgranite.TheE˘grigözgranitoidsareOn the other hand, Group III granites are post-collision calc-alkaline, derived from a mantle source classifiedthathasundergoneextensivecrustalcontamin as volcanic-arc granite (VAG) and Groupationsimilartovolcanic-arcgranite.TheE III granites (Figure 12a). Pearceğrigözgranitoidset al. [33] proposed a tectonicare classified classification as volcanic-arc of granitoids granite depending(VAG) and Group on Rb, III Nb, granites and Y(Figure abundances 12a). Pearce in theet al. Rb [33]versus (Y + Nbproposed) diagram. a tectonic All data classification plotted in of the granitoids VAG field depending are I-type on dueRb, Nb, to their and lowY abundances contents ofin Rb,the NbRb and versus (Y + Nb) diagram. All data plotted in the VAG field are I-type due to their low contents of Rb, Y (Figure 12b). Because the ratios of the large ion lithophile (LIL) relative to high field strength (HFS) Nb and Y (Figure 12b). Because the ratios of the large ion lithophile (LIL) relative to high field are increasingstrength (HFS) with increasingare increasing fractionation with increasing [34], thefractionation E˘grigözgranitoids [34], the Eğ arerigöz highly granitoids fractionated are highly with an averagefractionated LIL/HFS with ratio an of average 6.6. LIL/HFS ratio of 6.6.

Tholeiitic

Calc-Alkaline

c d

FigureFigure 11. (a )11. AFM (a) diagramAFM diagram for the for studied the studied granitic granitic rocks, afterrocks, [27 after], the [27], compositional the compositional and extensional and

trendextensional after [28]; trend (b) Molar after [28]. A/NK (b) Molarversus A/NKA/CNK versus [29 A/CNK]; (c) Na [29].2O-CaO-K (c) Na2O-CaO-K2O diagram2O diagram for the for studiedthe studied granitoid rocks after [30]. (d) Molecular Al2O3/(CaO + Na2O + K2O) versus Rb/Sr diagram granitoid rocks after [30]; (d) Molecular Al2O3/(CaO + Na2O + K2O) versus Rb/Sr diagram showing the classiﬁcationshowing the ofclassification the rocks intoof the the rocks ﬁelds into of the I-type fields andof I-type S-type and granitoids S-type granitoids [31]. [31].

Minerals 2016, 6, 13 16 of 23 Minerals 2016, 6, x 2 of 4

1000 syn-COLG a WPG b

100

10 ORG

VAG

1 10 100 1000 Y+Nb

2 FigureFigure 12. (a 12.) Zr( aversus) Zr versus SiOSiO diagram2 diagram for for the the studied studied E E˘grigözgranitoidsğrigöz granitoids that that indicating indicating the the Group Group III (post-collisional)III (post-collisional) affinity afﬁnity [32]. [(32b];) Rb (b) Rbversusversus (Y(Y + + Nb) Nb) discriminationdiscrimination diagram diagram [33]; [33]; syn-COLG: syn-COLG: syn-collisionsyn-collision granites; granites; VAG: VAG: volcanic-arc volcanic-arc granites; granites; WPG: WPG: within-plate granites; granites; ORG: ORG: ocean-ridge ocean-ridge basalt. basalt.

4.2.2. Alteration4.2.2. Alteration Geochemistry Geochemistry The hydrothermally altered rocks in E˘grigözgranitoids include pervasive silicification, sulfidation, The hydrothermally altered rocks in Eğrigöz granitoids include pervasive silicification, sericitization, and selective carbonatization and albitization which are distributed in three main sulfidation,alteration sericitization, zones, based onand the selective geological andcarbonatization petrographic studies. and albitization The major and which trace elements are distributed of the in three mainaltered alteration rocks are shown zones, in base Tabled2. on The the relative geological degree ofand alteration petrographic is determined studies. by calculation The major of theand trace elementschemical of the index altered of alteration rocks are (CIA shown = molar in Table proportion 2. The [Al 2relativeO3/(Al2 Odegree3 + CaO* of +alteration Na2O + K 2isO)] determinedˆ 100)) by calculationof Nesbitt of the and chemical Young [35 index]. CIA of ratios alteration show that (CIA the = altered molar rocks proportion (an average [Al of2O 58.1,3/(Al 75.0,2O3 + and CaO* 62.7 + Na2O for zones 1, 2, and 3, respectively) were affected by a significant change in chemical composition with + K2O)] × 100)) of Nesbitt and Young [35]. CIA ratios show that the altered rocks (an average of 58.1, 75.0, andreference 62.7 for to the zones least-altered 1, 2, and rocks 3, (anrespectively) average of 49.4). were Generally, affected these by a hydrothermally significant change altered in rocks chemical have higher iron content along with variable enrichments in SiO . They contain a large proportion of composition with reference to the least-altered rocks (an2 average of 49.4). Generally, these sulfide minerals (e.g., pyrite, chalcopyrite, sphalerite, galena and covellite) that display enrichments hydrothermallyof Cu, Cu-Pb, altered and Cu-Pb-Zn rocks have in zones higher 1, 2,iron and content 3, respectively. along with The wt variable % loss onenrichments ignition (LOI) in SiO2. They containincreases a significantly large proportion in samples of displayingsulfide minerals an intense (e.g., alteration. pyrite, An chalcopyrite, increase of K2O sphalerite, in zone 3 reflects galena and covellite)sericitization/muscovite that display enrichments with chlorite of Cu, and Cu-Pb, kaolinite, and while Cu-Pb-Zn zone 1 samplesin zones show 1, 2, local and enrichment 3, respectively. The wtof % CaO loss along on ignition with MgO (LOI) and Fe increases2O3 relative significantly to the least-altered in samples rocks, displaying which reflects an the intense occurrence alteration. of carbonate alteration (calcite, ankerite and dolomite). The relationship between Na O and K O An increase of K2O in zone 3 reflects sericitization/muscovite with chlorite and kaolinite,2 while2 zone with the Ishikawa alteration index (Ishikawa AI = [100(K2O + MgO)/(K2O + MgO + CaO + Na2O)]) 1 samples show local enrichment of CaO along with MgO and Fe2O3 relative to the least-altered of Ishikawa et al. [36] for the altered rocks shows that the data are plotted close to calcite/albite rocks, forwhich zone reflects 1, chlorite/sericite the occurrence as well of ascarbonate dolomite/ankerite alteration for (calcite, zone 2, ankerite and chlorite/sericite and dolomite). for The relationshipzone 3 (Figurebetween 13a,b). Na2O and K2O with the Ishikawa alteration index (Ishikawa AI = [100(K2O + MgO)/(K2O + MgO + CaO + Na2O)]) of Ishikawa et al. [36] for the altered rocks shows that the data are plottedMass-Balance close to Analyses calcite/albite for zone 1, chlorite/sericite as well as dolomite/ankerite for zone 2, and chlorite/sericiteThe mineralogical for zone and 3 bulk(Figure chemical 13a,b). changes reveal differences in the geochemical composition of the hydrothermally altered and unaltered rocks. Hydrothermal alteration associated with the Mass-Balancebrittle-ductile Analyses shear zones suggests the presence of a chemical ion exchange between the wall rocks and hydrothermal fluids, and its zonation reflects changes in the fluid composition with time and the Theinteraction mineralogical of this fluid and with thebulk host chemical rocks [37]. Thechanges hydrothermal reveal alterationdifferences processes in arethe typically geochemical compositionassociated of the with hydrothermally the gain and loss ofaltered components and unaltered of the entire rocks. rock mass Hydr [18othermal]. alteration associated with the brittle-ductile shear zones suggests the presence of a chemical ion exchange between the wall rocks and hydrothermal fluids, and its zonation reflects changes in the fluid composition with time and the interaction of this fluid with the host rocks [37]. The hydrothermal alteration processes are typically associated with the gain and loss of components of the entire rock mass [18]. Gresens [15] suggested that the composition-volume comparison of the altered and unaltered rocks is a useful way to determine changes in elemental compositions due to gains/losses or dilution. Grant [16,17] improved the equation of Gresens and suggested that the immobile elements should be plotted along an isocon line that has no mass transfer during the alteration processes. The recent version of software for determining and plotting mass balance/volume change during the alteration processes is the GEOISO-Windows™ program [21]. The mass balance/volume change by the absolute mobility of elements is determined by using Gresens' [15] equations and drawing the isocon diagrams of Grant [16]. This method requires selecting immobile elements to define a best-fit

Minerals 2016, 6, 13 17 of 23

Gresens [15] suggested that the composition-volume comparison of the altered and unaltered rocks is a useful way to determine changes in elemental compositions due to gains/losses or dilution. Grant [16,17] improved the equation of Gresens and suggested that the immobile elements should be plotted along an isocon line that has no mass transfer during the alteration processes. The recent version of software for determining and plotting mass balance/volume change during the alteration processes is the GEOISO-Windows™ program [21]. The mass balance/volume change by the absolute mobilityMinerals 2016 of, elements6, x is determined by using Gresens’ [15] equations and drawing the isocon diagrams3 of 4 of Grant [16]. This method requires selecting immobile elements to define a best-fit isocon line, whichisocon enablesline, which determination enables determination of mass gains/losses of mass gains/losses of the mobile of the elementsmobile elements in the alteredin the altered rocks. Therocks. high The field high strength field strength (HFS) elements, (HFS) elements, particularly particularly Al, Ti, and Al, Zr,Ti, wereand assumedZr, were toassumed be immobile to be elementsimmobileor elements their mobility or their was mobility not significant was not significant during the during alteration the alteration processes. processes. In addition, In addition, in many studies,in many aluminum studies, isaluminum considered is immobile considered under immobile low- to moderate-temperature under low- to moderate-temperature hydrothermal and greenschist-gradehydrothermal and metamorphic greenschist-grade conditions metamorp [38]. Whenhic conditions plotting TiO[38].2 Whenversus Alplotting2O3 in TiO least-altered2 versus Al and2O3 alteredin least-altered rocks, a singleand altered trend ofrocks, alteration a single isformed trend of from alteration the least-altered is formed precursor from the to least-altered the altered samplesprecursor (Figure to the 13alteredc). samples (Figure 13c).

12 12 Albite a Zone-1 b Sericite Zone-2 Zone-3

8 8 O wt% O wt% 2 2 K Na 4 4 Plagioclase

Epidote Ankerite Calcite Ch l o r i te Sericite 0 Albite 0 Chl o r ite 20 40 60 80 100 Ca l c ite 20 40 60 80 100 Do lo mi te AI Dol o mi te AI Ankerite

Figure 13. Relationship between alteration index (AI) and (a) Na2O and (b) K2O for the altered rocks [39]. Figure 13. Relationship between alteration index (AI) and (a) Na2O and (b)K2O for the altered (c) TiO2-Al2O3 binary plot of the least-altered and altered rocks (alteration trend is the best fit line rocks [39]; (c) TiO2-Al2O3 binary plot of the least-altered and altered rocks (alteration trend is the best ﬁtbetween line between the different the different samples). samples).

The immobile elements in the three alteration zones were determined by drawing The immobile elements in the three alteration zones were determined by drawing discrimination discrimination diagrams between the main immobile elements (Al2O3, TiO2, and Zr) that are plotted diagrams between the main immobile elements (Al2O3, TiO2, and Zr) that are plotted around a slope of around a slope of 1 (Figure 14). Al2O3 and TiO2 are in zones 1 and 2 with an R (coefficient of 1 (Figure 14). Al2O3 and TiO2 are in zones 1 and 2 with an R (coefﬁcient of determination value) of 0.79 determination value) of 0.79 and 0.92, respectively, whereas Al2O3 and Zr are the immobile elements and 0.92, respectively, whereas Al O and Zr are the immobile elements in zone 3 with an R of 0.71. in zone 3 with an R of 0.71. 2 3 Based on the mass and volume changes (gains and losses), each of the alteration zones has different additions and depletions of major/trace elements (Tables 3 and 4). According to mass balance calculations and isocon diagrams, samples from zone 1 have enrichment in SiO2, Fe2O3, MgO, CaO, Na2O, MnO, SO2 and LOI with high S and Cu (Figures 15a and 16a,b). The mass change (MC) and volume change (VC) of this zone are calculated as 307.2 and 247.7, respectively. Samples from zone 2 exhibit enrichment of SiO2, Fe2O3, MnO, K2O, SO2, and LOI with S, Cu, and Pb (Figures 15b and 16c,d), which led to estimated values of 183.6% MC and 156.0% VC. This zone has a lower amount of S and that refers to a local leaching and this leads to enrichment in Cu and Pb. Finally, common additions of SiO2, Fe2O3, K2O, SO2, and LOI with significant S, Cu, Zn, and Pb enrichments characterize the major chemical changes in the altered rocks in zone 3 (Figures 15c and 16e,f) with 103.3% MC and 94.6% VC.

Minerals 2016, 6, 13 18 of 23

Based on the mass and volume changes (gains and losses), each of the alteration zones has different additions and depletions of major/trace elements (Tables3 and4). According to mass balance calculations and isocon diagrams, samples from zone 1 have enrichment in SiO2, Fe2O3, MgO, CaO, Na2O, MnO, SO2 and LOI with high S and Cu (Figures 15a and 16a,b). The mass change (MC) and volume change (VC) of this zone are calculated as 307.2 and 247.7, respectively. Samples from zone 2 exhibit enrichment of SiO2, Fe2O3, MnO, K2O, SO2, and LOI with S, Cu, and Pb (Figures 15b and 16c,d), which led to estimated values of 183.6% MC and 156.0% VC. This zone has a lower amount of S and that refers to a local leaching and this leads to enrichment in Cu and Pb. Finally, common additions of SiO2, Fe2O3,K2O, SO2, and LOI with signiﬁcant S, Cu, Zn, and Pb enrichments characterize the major chemical changes in the altered rocks in zone 3 (Figures 15c and 16e,f) with 103.3% MC and 94.6% VC.

Table 3. Element/oxide mass changes in relation to original whole rock mass ((Mﬁ-Moi)/Mo) and in relation to original element/oxide mass in original rock ((Mﬁ-Moi)/Moi) (data from GEOISO-A Windows™ program).

Zone 1 Zone 2 Zone 3 Sample ID (Mfi-Moi)/Mo (Mfi-Moi)/Moi (Mfi-Moi)/Mo (Mfi-Moi)/Moi (Mfi-Moi)/Mo (Mfi-Moi)/Moi

SiO2 174.8 2.6 131.6 2.0 81.0 1.2 Al2O3 0.0 0.0 0.0 0.0 0.0 0.0 Fe2O3 90.3 30.2 19.3 6.5 11.7 3.9 MgO 0.7 0.6 ´0.7 ´0.6 ´1.0 ´0.8 CaO 2.1 0.7 ´1.9 ´0.7 ´2.7 ´0.9 Na2O ´1.5 ´0.4 ´1.7 ´0.5 ´2.5 ´0.7 K2O ´3.2 ´0.6 ´1.8 ´0.3 1.6 0.3 TiO2 ´0.2 ´0.4 ´0.2 ´0.4 ´0.1 ´0.2 P2O5 ´0.1 ´0.4 ´0.1 ´0.3 ´0.1 ´0.4 MnO 1.7 34.8 0.2 3.5 0.1 1.4 SO2 18.9 473.4 36.3 908.7 5.1 127.6 LOI 13.8 10.0 8.2 5.9 5.9 4.3 As 2737.7 131.6 1068.6 51.4 269.6 13.0 Ba 27.2 0.0 ´310.4 -0.3 853.1 0.8 Co 180.4 9.0 128.0 6.4 40.6 2.0 Cu 50,265.7 3466.6 40,625.5 2801.8 30,310.9 2090.4 Ga 28.3 1.8 74.6 4.9 ´3.1 ´0.2 Nb 4.0 0.3 23.7 1.7 ´5.2 ´0.4 Ni 197.2 24.7 1487.8 18,597.1 18.4 2.3 Pb 5405.3 10,810.7 34,790.4 695.8 39,597.8 792.0 Rb ´45.3 ´0.3 ´122.1 ´0.7 11.0 0.1 S 94,685.2 429.4 1819.4 825.1 25,563.1 115.9 Sr ´67.6 ´0.3 ´131.7 ´0.7 ´81.6 ´0.4 Y 596.3 25.4 210.2 8.9 50.7 2.2 Zn 2192.3 5282.7 2234.7 5384.7 31,540.5 760.0 Zr 481.6 3.2 124.9 0.8 20.6 0.1

Table 4. Whole rock mass and volume change in different zones of alteration in the Tavs, anlı area.

Sample ID Zone 1 Zone 2 Zone 3 Whole rock mass change (MC) 307.2 183.6 103.3 Whole rock volume change (VC) 247.8 156.0 94.7 Minerals 2016, 6, 13 19 of 23 Minerals 2016, 6, x 5 of 4

Minerals 2016, 6, x Zone-1 5 of 4 0.2 400 400 R² = 0.792 0.18 350 350 0.16 300 300 0.14 Zone-1 0.2 250 400 250400 0.12 R² = -0.46

wt % wt R² = 0.792 0.1 0.18 200 350 200350 2 R² = -0.79 0.08 0.16 Zr (ppm) Zr (ppm) Zr TiO 150 300 150300 0.06 0.14 100 250 100250 0.04 0.12 R² = -0.46

wt % wt 0.1 50 200 20050 0.02 2 R² = -0.79 0.08 Zr (ppm) Zr (ppm) Zr 0 TiO 0 150 1500 0.06 02468101214 10002468101214 100 0 0.05 0.1 0.15 0.2 0.04 Al2O3 wt % Al2O3 wt % TiO2 wt % 0.02 50 50 0 0 0 02468101214 02468101214Zone-2 0 0.05 0.1 0.15 0.2 Al O wt % Al O wt % TiO wt % 0.4 2 3 400 2 3 400 2

0.35 350 350 R² = 0.921 Zone-2 0.3 300 300 0.4 400 400 0.25 250 250 0.35 350 350

wt % wt 0.2 R² = 0.921 200 R² = -0.09 200 R² = -0.25 2 0.3 300 300 Zr (ppm) Zr (ppm)

TiO 0.15 150 150 0.25 250 250 0.1 100 100 wt % wt 0.2 200 R² = -0.09 200 R² = -0.25 2 0.05 50 50 Zr (ppm) Zr (ppm)

TiO 0.15 150 150 0 0 0 0.1 100 100 024681012141618 024681012141618 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.05 50 50 Al2O3 wt % Al2O3 wt % TiO2 wt % 0 0 0 024681012141618 024681012141618 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4

Al2O3 wt % Zone-3Al2O3 wt % TiO2 wt % 0.3 160 160

140 Zone-3 140 0.25 R² = 0.532 0.3 160 160 120 R² = 0.71 120 R² = 0.098 0.2 100 140 100140 0.25 R² = 0.532 120 120 wt % wt 0.15 80 R² = 0.71 80 R² = 0.098 2 0.2 100 100 Zr (ppm) Zr (ppm)

TiO 60 60 0.1 wt % wt 0.15 80 80 2 40 40 Zr (ppm) Zr (ppm) 0.05 TiO 60 60 0.1 20 20 40 40 0 0 0 0.05 024681012 02468101220 20 0 0.05 0.1 0.15 0.2 0.25 0.3 0 0 0 Al2O3 wt % Al2O3 wt % TiO2 wt % 024681012 024681012 0 0.05 0.1 0.15 0.2 0.25 0.3 Al2O3 wt % Al2O3 wt % TiO2 wt % FigureFigure 14. ImmobileImmobile element element discrimination discrimination diagrams diagrams of alteredof altered rocks rocks of the of Tavsanli the Tavsanli area from area zones from 1, Figure 14. Immobile element discrimination diagrams of altered rocks of the Tavsanli area from zones2, and 1, 3. 2, Higher and 3.R 2Higher(coefﬁcient R2 (coefficient of determination) of determination) value refers value to a best refers ﬁt indicatingto a best fit high indicating immobility high in zones 1, 2, and 3. Higher R2 (coefficient of determination) value refers to a best fit indicating high immobilitya zone [40]. in a zone [40]. immobility in a zone [40].

a b a b

FigureFigure 15. 15.Isocon Isocon diagram diagram comparing comparing the the mean mean compositioncomposition ofof least-alteredleast-altered samples samples and and altered altered Figuresamplessamples 15. from Isocon from (a) ( zone adiagram) zone 1, (1,b )(comparingb zone) zone 2, 2, and and the (c ()c zone)mean zone 3. 3.composition of least-altered samples and altered samples from (a) zone 1, (b) zone 2, and (c) zone 3.

Minerals 2016, 6, 13 20 of 23 Minerals 2016, 6, x 6 of 4

Figure 16. Profile-histograms showing the gain/loss of major oxides (wt %) and trace elements (ppm) Figure 16. Profile-histograms showing the gain/loss of major oxides (wt %) and trace elements (ppm) during alteration in the different zones of hydrothermal alteration of the Tavșanlı area based on during alteration in the different zones of hydrothermal alteration of the Tavs, anlı area based on mean mean data of the least-altered samples as a reference for calculations, (a) and (b) for zone 1, (c) and data of the least-altered samples as a reference for calculations, (a) and (b) for zone 1, (c) and (d) for (d) for zone 2, and (e) and (f) for zone 3. zone 2, and (e) and (f) for zone 3. 5. Conclusion 5. Conclusions In west Turkey, Mesozoic blueschist Tavsanli and greenschist Afyon terranes, which enclose In west Turkey, Mesozoic blueschist Tavsanli and greenschist Afyon terranes, which enclose the Balikesir-Kütahya (or Bursa-Kütahya) district, are dominated by early Miocene plutonic-hosted, the Balikesir-Kütahya (or Bursa-Kütahya) district, are dominated by early Miocene plutonic-hosted, volcanic-hosted, and low-sulfidation epithermal Au deposits. This district was controlled by NE- to volcanic-hosted, and low-sulfidation epithermal Au deposits. This district was controlled by NE- to ENE-trending graben systems, including early Miocene (20–18 Ma) syn-tectonic Eğrigöz granitoid ENE-trending graben systems, including early Miocene (20–18 Ma) syn-tectonic E˘grigözgranitoid intrusions [41]. The Cu, Pb-Zn, W or Mo skarn that are distributed throughout Turkey are closely intrusions [41]. The Cu, Pb-Zn, W or Mo skarn that are distributed throughout Turkey are closely associated with porphyry systems in this district [41]. This mineralization is confined to associated with porphyry systems in this district [41]. This mineralization is confined to NW-trending NW-trending faults that are commonly associated with pervasive hydrothermal alterations, faults that are commonly associated with pervasive hydrothermal alterations, brecciation, and quartz brecciation, and quartz stockwork veinlets. stockwork veinlets. Three main alteration zones with gradual boundaries border the mineralized quartz veins Three main alteration zones with gradual boundaries border the mineralized quartz veins and/or shear zone in the mine area; zone 1 (silicified/iron carbonatized alterations ± albite), zone 2 and/or shear zone in the mine area; zone 1 (silicified/iron carbonatized alterations ˘ albite), zone 2 (argillic-silicic alterations), and zone 3 (phyllic alterations). Zone 1 occurs in the center and has high (argillic-silicic alterations), and zone 3 (phyllic alterations). Zone 1 occurs in the center and has high amounts of chalcopyrite and pyrite. Zone 2 occurs along with zone 1 in the north, characterized by amounts of chalcopyrite and pyrite. Zone 2 occurs along with zone 1 in the north, characterized by high amounts of chalcopyrite, sphalerite and pyrite. Zone 3 is in southern contact with zone 1 with high amounts of chalcopyrite, sphalerite and pyrite. Zone 3 is in southern contact with zone 1 with high amounts of chalcopyrite, sphalerite and galena with pyrite. The ore minerals, i.e., chalcopyrite, sphalerite, galena, covellite, malachite, azurite and pyrite, are abundant at the contact between quartz veins and the altered rocks as well as in disseminations in the alteration zones. A three-fold

Minerals 2016, 6, 13 21 of 23 high amounts of chalcopyrite, sphalerite and galena with pyrite. The ore minerals, i.e., chalcopyrite, sphalerite, galena, covellite, malachite, azurite and pyrite, are abundant at the contact between quartz veins and the altered rocks as well as in disseminations in the alteration zones. A three-fold paragenetic sequence was likely responsible for the ore deposition, including the pre-ore, hydrothermal ore, and supergene stages. The E˘grigözmonzogranitic and quartz monzonitic rocks represent the least-altered rocks. These rocks are metaluminous and calc-alkaline rocks classified as I-type VAG granite. Representative samples from the different alteration zones have high CIA relative to the least-altered rocks. The high Fe contents are probably caused by sulphidation with chloritization along with silicification. Based on the values of the changes (gain and loss) of mass and volume, each alteration zone has different major/trace additions and depletions calculated by the GEOISO-Windows™ program assuming Al, Ti, and Zr are immobile elements or their mobility was not significant during the alteration processes. Samples from zone 1 have enrichment in SiO2, Fe2O3, MgO, CaO, Na2O, MnO, SO2, and LOI with high S and Cu. Zone 2 has rocks enriched in SiO2, Fe2O3, MnO, K2O, SO2, and LOI with S, Cu, and Pb. Zone 3 samples have enrichment of SiO2, Fe2O3,K2O, SO2, and LOI with significant amounts of S, Cu, Zn, and Pb. Based on these data, the zonal arrangement of zones 1, 2, and 3 gives the impression of non-systematic distribution of alterations around the ore vein in the center from silicic-carbonate alterations +/´ albitization to phyllic-argillic alterations with increased base metals (Cu-Pb-Zn) from Cu, Cu-Pb, to Cu-Pb-Zn in zones 1, 2, and 3, respectively. Therefore, the studied Cu-Pb-Zn mineralization is mainly linked with the quartz veins within the main silicic and carbonate alteration types along the NW fault system which post-dated the E˘grigözintrusion. Furthermore, the morphology of these quartz veins and superimposed alteration types imply a significant role of shearing in the mobilization of metals and ore deposition from the host intrusion.

Acknowledgments: This study was financially supported by the BAP Project (No. 37860) by Istanbul Technical University (ITU), Turkey. The authors are grateful to Paul A. Schroeder (University of Georgia, USA) and Fuat Yavuz (ITU, Turkey) for critical reading, providing language help, and improving an earlier version of this manuscript, as well as to Muhittin Karaman (ITU, Turkey). Additionally, the authors are much more grateful to the editor and the anonymous reviewers for their constructive comments, corrections and helpful suggestions which greatly improved the manuscript. Author Contributions: Mustafa Kumral did the field work together with Amr Abdelnasser, as well as the ore geology part. Amr Abdelnasser contributed the classification and geochemistry of hydrothermal alteration zones around the mineralized veins, with Mustafa Kumral. Murat Budakoglu completed the geochemical characteristics of the least-altered host rocks. All authors participated in the writing of the earlier and last versions of this manuscript. Conflicts of Interest: The authors declare no conflict of interest.

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