Cassiterite (Tin) Mineralization Related with Erciyes Volcanic Activities and The Mode of Formation of The Hematite-Cassiterite-Yazganite-Tridymite Paragenesis and Its Implication for Bronze Alloys. Evren Yazgan 1.Abstract; Hematite - Cassiterite - Yazganite - Tridymite paragenesis have been first determined with in The Erciyes volcanics on the northeastern slope of Senir Sırtı , in housing excavation near Kıranardı village.These Minerals are in the form of fracture wall coating in the upper Pliocene porphyric pyroxene andesite.These volcanic rocks cover extensive areas in Senir Sırtı. Besides this Kıranardı mineral paragenesis, another ore deposit has been discovered along the Gümüş Dere river in the southeast of Alidağ about 5 km to the south of Zincidere district. Hematite and cassiterite mineral association has also been recognized aligned parallel to the pyroclastics’ bedding planes in the Lower Pleistocene of theBaşak Pınar pyroclastics. An antique mining adit of several ten meters of length , following the mineralized levels has been discovered with in these pyroclasts.The fact that the Kıranardı mineralization in the Erciyes volcanic complex occurs as coating material on near-surface, extension facture walls, reflects the importance of gaseous emanations at pneumatolytic stage and high temperature conditions. According to the fluid inclusions studies , the mineral paragenesis observed in tin deposits give a common formation temperature between 460 – 580°C.The emission of gases and vapors ascending to the surface along the tensional fractures related to cooling of the volcanic environment during the pneumatolitic phases.Iron ,tin,arsenic and silicon elements ,forming high temperature oxide minerals such as hematite , cassiterite, yazganite and tridymite(high temperature polymorph of quartz ) have been transported by means of halogene group elements such as chlorine, fluorine, bromine and iodine.These oxide minerals indicate that the oxygene fugacity reachead relatively high value in conditions of this paragenesis.This mineral association , although it includes an abundance of high tempereture minerals, possesses many of the characteristics of near surface deposition .The Kıranardı tin and arsenic mineralization, thus constitutes an excellent example of the high-temperature mineralization of the near surface volcanic environment where relatively high thermal gradient dominated. 2.Introduction; Hematite - cassiterite - yazganite - tridymite mineral paragenesis have been first determined within the Senir Sırtı , on the northeastern slopes of Erciyes volcanic mountain , namely in the Koçdağ porphyric pyroxene andesite(Fig.2,Fig.3). Discovery of the arsenic bearing tin mineralization and exploited antique mines within the Senir Sırtı and Zincidere has a primordial importance for the archaeometallurgy of Anatolia.Furter, Kültepe archaeological site, is only 26 km to these arsenic, tin mine.Some of the metallic objects (artifacts) excavated from the Early Bronze Age at Kültepe contain arsenic,tin and copper elements in their compositions. Arsenic –bearing antique tin mine at Senir Sırtı is the second discovered tin mining area , after the Kestel tin mine which is one of the earliest known mining region of the Bolkardağ mining district (Yener,1986;Yener and Özbal, 1986; Yener et al.,1989).Wijkerlooth (1944) and Göymen – Aslaner (1968) pointed out arsenic and antimony bearing mineral association of Ergani-Maden which is the oldest copper mining area known since historical ages in Anatolia. Fig.1 Simplified geological map of Cappadocian Volcanic Province (Toprak et al.,1994). Fig.2 Geological map of Kıranardı and Zincidere showing cassiterite – yazganite-hematite minerals deposit area (Türkecan et al.,1998). The historical settlement of Çayönü which is one of the oldest inhabited area, is the nearest archaeological site to Ergani-Maden copper mine , only 8 km to Ergani district. The use of cold-worked native copper begins during the ninth to seventh millenium BC in form of beads made by native copper at Çayönü village.This is just after the Würm glaciation ended. Copper, arsenic and antimony bearing archaeological raw material have been discovered at Norşuntepe(Seeliger et al. 1985) to the northwest of the Maden mine and 26 km to the east-southeast of Elazığ province. This may reflect a more local source that ore deposit has been transported to metal working village without any ore processing. Maden copper mine which contains tennatite (Cu,Fe)12 As4 S13 and tetraedrite (Cu,Fe)12 Sb4 S13 bearing ore deposit was the probable source of the raw material discovered at Norşuntepe. Peripheral archaeological sites to Ergani-Maden mine which contains As-Sb-Ni-Cr bearing copper minerals , were the principal villages where As-Cu ,As-Sb-Cu even Ni,Cr bearing alloys have been produced ;so metalic ores or raw materials have not been transported from a very long distance. 3.Geological Setting; The Central Anatolian Volcanic Province (CAVP) whit a 300km of length which extends as a belt in NE-SW direction, covers a large area between the Ecemiş Fault Corridor on the east , the Tuz Gölü Fault on the west and Kızılırmak Fault on the north. (Toprak et al.,1994). On the northeast part of the CAVP, the Erciyes volcanic roks of Pliocene-Pleistocene-Holocene ages,which were developed in a pull –apart basin, formed in response to the intra-plate extensional tectonics (Koçyiğit & Erol,2001;Dirik,2001) (Fig1). The Erciyes volcanic complex is the larges and one of the youngest stratovolcanoes of the CAVP , which consist of lava flows of basalt , basaltic andesite,trachyandesite , trachyte , dacite and rhyolite with ignimbrites and pyroclastics (Türkecan et al.;1998;Türkecan et al.,2004). Geochemical analyses indentify the rocks as calc-alkali series (Fig4).The geotectonic settings,geological context and the observed geochemical characters of the Erciyes volcanic activity may account for A-type intra plate granitic melt . The Erciyes volcanic mountain which is the most impressive within the CAVP , with its magnificent morphology and distinct geological characteristic , located to the south of Kayseri, has a summit of 3917 m and a width of about 40km . According to Baş et al. (1986) , the Erciyes volcanic complex which started to evolve in late Miocene and continued until Quaternary. The andesitic and dacitic lavas have given respetively 0.3 ± 0.1 and 0.9 ± 0.2 milion years (my) by radiometric dating (Innocenti et al. ,1975). As stated by Ercan et al.,(1994), the initial volcanic activity of the Erciyes first set off about 2,5 my ago with the Koçdağ volcanics, but the central crater has occurred 1.0 my ago according to K/Ar age determinations.The radiometric dating results given by diffrent authors presented by Türkcan et al. (2004) vary form 13.70 ± 0.3 to 1.73 ± 0.07 my for CAVP of the Neogene volcanism and from 1.15 ± 0.08 my to 0.06 ± 0.02 my even up to 0.003 my for the very recent volcanism of the Hasandağ (Kuzucuoğlu et al.,1998). Kuzucuoğlu et al.,(1998a)confirm the sub-recent activity of the Hasandağ volcano from a sample issued from near Dikmen village on the northwestern slopes.The youngest radiometric age on sample from Erciyes volcanics is 80 kyrs (kiloyears). Historic evidence suggests however that Mount Argée (Erciyes) located few kilometres from ancient Cesarée ( today Kayseri) was active 2000 years ago. In his Geography , Strabon (2000) also states that the flames and fires occur on the lowest parts of the volcano slopes.The volcanic CO2 emanation is still active and used for industrial needs. Fig.3 Photo showing Hisarcık , Kıranardı and Senir Sırtı. Fig.4 Geochemical characters of the Erciyes volcanics. 4.Hisarcık Mineral Paragenesis; The mineralogical and petrographic determination of the Hisarcık ore deposit attributed a mineral paragenesis bearing cassiterite (SnO2), and yazganite (Na Fe³+2(Mg,Mn)[AsO4]3.H2O] associated with hematite ( Fe2O3),tridymite (SiO2),and secondary hydrotermal minerals such as orpiment (As2S3) and realgar (AsS) (Yazgan et al. ,2002;Yazgan ,2005; Sarp &Cerny,2005). 4.1 Cassiterite is the principal mineral of tin ore and occurs in prismatic crystals of adamantin luster and also in massive form , either compact with concentric fibrous structure or in rolled or pebbly fragments.(Fig. 5) 4.2 Yazganite is a new arsenic oxide mineral discovered in the porphyric pyroxene andesitic rocks collected by The author on the northeastern slopes or Erciyes mountains near Kıranardı.The mineral name honors Dr.Evren Yazgan (1943-) a geologist in Turkey, who defined the samples containing cassiterite and yazganite minerals (Yazgan et al.,2002),when working in this volcanic region in collaboration with General Directorate of Mineral Research and Exploration of Turkey(MTA). The mineral and its name have been approved by the Commission on New minerals and Mineral Names of the International Mineralogical Association (Sarp & Cerny, 2005). 4.3 Hematite is the first mineral crystallized by covering the surface on the cavity walls as coating materials. Cassiterite minerals are observed in thin sections under the polarization microscope in the form of elongated exsolution lamellas(Fig.6) and also tin elements has been detected by microprob analyses within lattice texture of hematite minerals. In this way , iron and tin occur as cogeneic elements , either cassiterite contained within hematite crystals in the form of elongated exsolution lamellas, or without any additional crystal phase in hematite crystal but tin substitution in place of iron in lattice texture . 4.4 Tridymite is a high-temperature polymorph of quartz , and ussually occurs as tabular white or colorless (transparent) crystals(Fig.7) in acidic and intermediate volcanic rocks such as rhyolite,dacite,trachyte and andesite . This mineral occurs in late stage fumarolic activities of the hot gases (Deer et al.,1967) in siliceous volcanic rocks cavities and also may be found disseminated through such rocks. The quartz – tridymite inversion is placed at 870°C and stable between 870°and 1470°(Bates & Jakson , 1980) 4.5 Orpiment and Realgar are frequently associated as a deposit found in volcanic fumaroles , low temperature hydrotermal veins and hot springs , formed both by sublimation and as a by-product or the decay of some others arsenic minerals . 4.6 Cassiterite , Yazganite , Hematite and Tridymite as oxide minerals have been developed, in the higher oxygen fugacity and high temparature mineralization conditions according to the fluid inclusions studies on the cavity walls as coating materials in the late stage fumarolic activities within the prophyric pyroxene andesites(Fig.8) Fig.5 Cassiterite and yazganite minerals under the binocular microscope. Fig.6 Cassiterite exsolution lamellas inbetween hematite minerals. Fig.7 Yazganite and tridymite minerals under the binocular microscope. Fig.8 Cassiterite (Cass),hematite(Hem) and yazganite (Yaz) minerals development on the extension fracture wall surface, Plg (plagioclase),under polarization microscope. 5.Zincidere Ore Dposit ; Occurs in pyroclastics of the lower Pleistocene age of the Başak Pınar volcanic tuff. Cassiterite and hematite mineralization is contained inside pyroclastic layered rocks (Fig.10) . A remarkable antique mining gallery follows gently the slope down the mineralization levels. Some mill stone pieces , with a canal carved into local volcanic rocks carrying down water to the mill belonging probably to a more recent time and a mortar hollowed out on the upper face of the country volcanic rocks were discovered. At Zincidere , where cassiterite and hematite mineralization have been observed, the hydrothermal hematitic veins penetrated inbetween layered pyroclastics cutting primary depositional layers (Fig.11) These hematitic hydrothermal veins cutting the layered pyroclastics are insued probably below 400° C in a later volcanic activity phase . Zincidere ore deposit and mineral paragenesis are not sufficiently studied as this zone is the military shooting range and we need an offical permit form the military authorities. So this ore deposit would be our future geoarchaeological target. 6.Fluid Inclusion Studies; 6.1 Fluid Inclusion Technique;Fluid inclusions are microscopic droplets of liquid , gas and crystal trapped within minerals . They are generally less than 0.1 mm in size and occur in a wide varity of earth enviroments. They are mostly know for their occurrence in hydrotermal vein minerals. However , fluid inclusions could also be found in minerals occurred in fumarolic stage mineralization.Their analysis can provide valuable information about the conditions during the formation of the enclosing minerals. The determination of temperatures of phase changes within fluid inclusions during heating and cooling of samples is called microtermometry . This tecnique is invaluable for discovering the temperature at which minerals form , the thermal history a rock has experienced and the compositions of the fluids that traversed a rock in its history. Two important assumptions have to be accepted ; an inclusion represents a chemically closed system and the volume of an inclusion remains constant from the time of entrappement. It means that it has not been destroyed by tectonism or metamorphism as result of the system not being opened. 6.2 Microthermometric Analysis of Cassiterite and Yazganite from Hisarcık;The Microthermometric laboratory analyses have been conducted by Gülay Sezener on the diphased (liquid + gas) and triphased (liquid + gas + crystal) fluid inclusions within cassiterite and yazganite minerals. According to both fluid inclusion studies, the common homogenization temperatures for the inclusions within these minerals are between 460 – 580°C (Fig 9). This is the temperature interval which cassiterite and yazganite minerals have been crystallized. 400°C is a critical temperature for the hydrothermal solutions above which all the aqueous solutions transform at gasseous phase . Metalic and ametallic elements such as Sn , As , Fe, Mg, Mn , Na and Si forming cassiterite , yazganite , hematite and tridymite minerals , have been transported by means of halogen group elements , such as Br, Cl, F and I in the fumerolian gaseous phases up to oxygen rich atmospheric conditions where all these elements occur in form of oxide minerals in the near surface on the open extensional fracture walls as coating materials . Fig.9 Experimental measure numbers of triphased fluid inclusions homogenization temperatures (˚C). 7. Hisarcık Tin and Arsenic Ore Deposit , Development and Meaning of Bronze Alloys Production in Anatolian Archaeometallurgy; The widespread Würm glaciation on the Alps – Himalaya Mountain Chain had also spred on the Taurus Mountain and East Anatolian high plateau. The end of this glacial period was about 9.000 BC. probably much earlier in southernmost Mesopotamia. The climatic and enviromental conditions became similar to those of the present day, with the disappearance of the Würm glacier . 7.1Native Copper Period; The nomadic tribes, that migrated along the Euphrates and Tigris rivers for the seasonal cereal reaping and wild animals hunting (Hunting and Gathering stage) , were already attracted certainly by native and brillant metal nuggets of copper , gold and silver . These nomadic tribes equipped with antecedent (previous) knownledges of the native metals , started to use them as an object of interest , from the first appearance of the sedentary (settled) life. Only few metals , such as copper , gold , silver and electrum are found in nature in the form of a pure elemnt. So use of native copper begins as early as around 9.000 BC since the begining of the Anatolian Neolithic Age. Pursuing the use of the native metals, human communities discovered the smelting of the metalic ores , by which alloys production period started to develop.The discovery of smelting method enabled antique metal workers to create different metal object which were better and harder than their native copper. At first , bronze was produced of copper and arsenic to form arsenical bronze, since the begining of the Chalcolithic Period around 6.000 – 5.500 years BC. Fig.10 Cassiterite and hematite mineralization in layered pyroclastic levels at Zincidere antique tin mine Fig.11 Hydrothermal hematite veins cutting pyroclastic rock at Zincidere antique tin mine. 7.2 Arsenical Copper (Arsenical Bronze) Period; If the artifacts analyses from different archaeological sites indicate the presence of Cu, As, Sb, Ni and Co elements , this makes clear that the provenance of the raw metarial used in production of the alloys were derived from a unique and same ore deposit;if especially the analysed objects come from the archaeolgical sites in close periphery of a copper mine . These trace elements , such as As, Sb, Cr, Ni and Co indicate ore deposit origin as a footprints. 7.2.1 Ergani – Maden , Arsenical Antique Copper Mine; The ore bearing hydrothermal veins at Ergani Maden , traverse the ultrabasic rocks at deeper levels , which are very rich in Ni, Co, and Cr elements. For this reason, Ergani – Maden Cu, As, And Sb bearing ore deposit , has been also enriched in Ni, Co, and Cr bearing minerals. That is why ; the mineral association of Maden present a wide range of various elements. Ergani – Maden polymetallic ore deposit, which is the well known antique copper mining quarry , has been used without any doubt at the nearby archaeological sites; such as Çayönü (Ergani – Diyarbakır) , Norşuntepe (Elazığ), Arslantepe Höyüğü and Değirmentepe (Malatya). Arsenic bearing copper minerals; tennantite (Cu,Fe)12 As4 S13, antimony bearing copper mineral tetrahedrite (Cu, Fe)12Sb4 S13) , nickel-bearing pentlandite (Fe,Ni)9 S8, linneite (Co, Ni Cu, Fe)3 S4 and chalcopyrite (Cu2Fe2S4)minerals have been determined by Wijkerslooth(1944) and Güner Göymen –Aslaner(1969) at Ergani – Maden which is the most well known antique copper deposit mine situated close to all these Chalcolitic Sites . In a copper mine, first secondary sulphide minerals, such as covellite (CuS), chalcocite(Cu2S) occur by means of late magmatic hydrothermal activities. Then , these copper sulphide compounds are transformed by reducing agents, such as H2, C, CO2 to an elemental copper under anaerobic condition (watter logged soil or cementation zone).Chemical expression of this transformation is given bellow: CuS + H2 → Cu +H2S Cu2S + H2 →2 Cu +H2S As one could see from these chemical equations, a reducing agent causes the decomposition of a metal compound to an elemental metal. 1. Covellite (CuS) + water(H2O) → Tenorite (CuO) +Hydrogen Sulphide (H2S) 2. Cholcocite(Cu2S) + H2O → Cuprite(Cu2O)+ (H2S) 3. 4CuS + 4H2O → 4Cu + 4H2 SO4 4. Cu2S + 4H20 → 8Cu + 4H2 SO4 First copper sulphide is decomposed to produce copper oxide and hydrogen sulphide.Under aerobic conditions (oxidization zone), H2S can be further oxidized to sulphates H2S+2O2 → H2SO4 (Sulphuric acid).Sulphuric acid produced by oxidization of H2S is transformed by means of ionization process to hydrogen and sulfate: H2SO4 → 2H+SO4 Sulphuric acid can react also with iron to produce hydrogen and iron sulfate by ionization process: H2SO4 + Fe → FeSO4 + H2 . Finally , hydrogen produced by this chemical reaction could be used as reducing agent to create further native copper metal , as explained before. In the presence of limestone (CaCo3) in an oxidization zone or of CO2 gas even in atmospheric conditions, copper carbonate minerals , such as azurite [Cu3(CO3)2(OH)2] deep-blue to violet-blue colors and malachite [Cu2CO3(OH)2] bright green color , occur as encrustation coating native copper metal.In every unworked copper mine, one would meet with native copper which occurs at the superficial levels of the mine outcrops.When the native copper rich surface level could be first used , then ore production workers would reach down to deeper levels which contain sulfidic ores. So,the surface deposits would be used first and with some work, deeper sulphidic ores would be discovered and worked . So on , smelting of this arsenic bearing sulfide copper ore deposit involved the production of “arsenical copper alloy”. Begining in the late fifth and first half of the fourth millenium BC.,peoples of the Near East , specially inbetween the Tigris and Euphrates valleys in the Upper Mesopotamia worked with arsenic bronze, particularly all around Ergani Maden copper mine region. 7.2.2 Archaeological Sites Nearby Ergani-Maden ;Ergani Maden ore deposit,containing Cu, As, Sb, Ni, Co and Cr elements , which were directly reflected into the alloys compositions in the archaelogical sites excavations, is one of the well known antique copper production mine. Societies using the arsenical bronze , since the Chalcolithic Age, all based around (nearby)Ergani-Maden arsenic bearing copper mine. 7.2.2.1 Çayönü Settlement; Begining of the copper production and first mining activity probably dates to the historical settlement of Çayönü vllage (7.250 – 6.750 BC), 20 km to the south of maden copper mine . This village is situated on the Boğazçay, a small tributary of the Dicle river, only 7km to the southwest of Ergani. Inhabitants of the village have learnt to work on the cold – hammering and annealing the copper first , then on the arsenical copper alloys.The copper used at Çayönü was very pure(98,80%)and its provenance was likely the Ergani-Maden copper mine about 20 km away. 7.2.2.2 Nevali Çori Settlement; This Neolithic archaeological site is situated to the northeast of Hilvan on the Kantara çayı a branch of the Euphrates.The inhabitants of Nevali Çori have learnt to work first on the hammered, then heated copper (7.500BC). C14 isotopes dating provided 8.400 – 8.100 BC as the first settlement age.The Sanctuary or cult building excavated at Nevali Çori have a similarity with those found at Çayönü, Hallan Çemi and Göbekli Tepe archaeological sites of the Neolithic Period. 7.2.2.3 Norşun Tepe Setlement; Norşun Tepe , actually inundated by the lake of the Keban Dam , is situated on the Euphrates river , 26 km to the southeast of Elazığ and approximately 35 km to the nord of Maden copper mine outcrops. The presence of both arsenic and antimony in high concentration suggests a weathered tennantite and tetrahedrite type ore minerals .Such ores would normally weather to malachite,azurite and copper,arsenic and antimony oxide minerals. Zwiker’s 1980 present analyses of such weathered ore excavated at Norşun Tepe in a Chalcolithic context. It seems that at about 3500 BC, in Norşun Tepe an oxidized copper ore was smelted and at later time , 2800 BC, the workshops of Norşun Tepe were among the early users of smelted sulphide ore to obtain metalic copper and arsenical bronze(Zwicker,1980).During the Middle Bronze Age (2200 – 1600 BC) arsenic and tin bronzes remained the more common alloys throughout Southwestern Asia (Lechtman,1996). The tin bronze replaced the arsenic bronze only in the Late Bronze Age. According to Late Chalcolitic slags chemical analyses from Norşun Tepe,Yalçın et al., (1992) arrived to the conclusion that metal workers used copper oxide minerals which contain the chromium (0.3 – 1.5 Cr2 O3 percent) and nickel (1.4 per thousand ); that is an excelent provenance indicator with the result that Ergani-Maden antique copper mine is unique ore deposit in the region , possessing ultramalic rocks affinity bearing Cr , Ni and Co elements. 7.2.2.4 Tulintepe, Korucutepe and Makaraz Tepe Settlements;Tulintepe , 21 km to the East of Elazığ where an ore smelting furnace of 1.5 meter of diameter have been excavated and the age of the first settlement in this area is dated as 5.000 BC. Korucutepe,30 km to the East of Elazığ where objects excavated gave Early and Late Chalcolithic Ages dated by C14 isotopes (5.350 – 3.800 BC.) Makaraz Tepe, 31 km to the East of Elazığ is inhabited since Early Chalcolithic Age. It appears that the copper was smelted according to copper ore and copper bearing slags findings. The analyses of slags and copper ore fragments indicate that malachite and azurite type ore were smelted at Tulintepe and Makaraz Tepe (Tepecik). The high Ni and As contents in some of the samles suggest that the copper used was from The Ergani-Maden ore deposits. 7.2.2.5 Arslantepe and Değirmentepe Settlement; Arslantepe Settlement, 7km to the northeast of Malatya is inhabited since the Middle Chalcolithic Age along the Euphorates river in The Upper Mesopotamia. Arslantepe metal workers used polymetallic ores bearing As, Sb, Ag, Ni, Co elements (Palmieri et al.,1993;Lehner & Yener 2014). Arslantepe excavation yielded fragments of copper minerals from the Chalcolithic and Early Bronze Age levels . These minerals were found associated to crucible fragments , stone pestles indicating probably a metal workshop.The Analysis of these minerals provided a relatively high Ni,As and Sb content, approving that these raw materials have been supplied from Ni,As and Sb bearing Ergani-Maden copper deposit. Finished artifacts from Arslantepe reflect also Ni,As and Sb encrichment in different alloys composition (Hauptmann et al.,2002).The arsenical alloys from Arslantepe indicate an arsenic percentage of 3-4 percent , but in the weapon alloys, this percentage rises up to 7 percent which makes it more resistant and harden these arsenical alloys.Chalcopyrite’s (Cu Fe S2) melting point is 950°C; but mixed with arsenic – antimony bearing minerals, melting point decreases down to 800°C.Consequently, this is another advantage to product arsenical bronze.Değirmentepe site ,23 km to nordeast of Malatya is located on the Upper Euphrates river first evidence of extractive metallurgy was observed at the end of the fifth and begining of the fourth millenium BC (Esin & Harmankaya.,1988). The copper slags were discovered at Değirmentepe site and studies of these slags demonstrated that ore deposit was heated up to 1200°C.Many metallurgical activities from ore processing , smelting, possibly melting and casting were metal workers activities and that raw metarials could have been transported directly from the source areas and consumed at the Değirmentepe site (Lehnert & Yener 2014). 7.3 Arsenik ,Tin and Copper Period; From the arsenical bronze (As Cu), to tin bronze (Sn Cu) period ,there is a transitional ternary usage period of As ,Sn and Cu elements in Early Bronze Age ,which is most likely in close relation with Hisarcık yazganite(As) and cassiterite(Sn) minerals association .The metal objects excavated from the Early Bronze Age at Kültepe, indicate the presence of As, Sn and Cu in ternary alloys derived probably from the smelting of Hisarcık polymetallic ore deposit . It is more likely that the addition of cassiterite and yazganite in direct fusion with copper would have been the method used by antic smelters in Kültepe. Discovery of the Hisarcık and Zincidere cassiterite and yazganite bearing ore deposit and exploitation galleries dating Early Bronze Age (Yener et al.,2014 in press) 26 km from Kültepe has a primordial importance to clarify this As , Sn and Cu bearing ternary alloy period. Yener et al.(2014 in press) suggest that , the destination of the Hisarcık ore was the Early Bronze Age regional center, Kanesh. Palmieri et al.,(1999) note already significant relationship between the types of alloys and ore deposits nearby archaeological sites where the metallic artifacts were excavated.Hisarcık and Zincidere As and Sn bearing ore deposits were certainly principal ore production mines in the Early Bronze Age and more likely were the source of tin and arsenic for Kültepe – Kanesh metal workers. 8.Tin Mineralizatin Associated to the Volcanic and Subvolcanic Rocks; Hisarcık tin mineralization in the Erciyes volcanic complex occurs as coating material on near-surface extension fracture walls. Similar shallow levels of emplacement was also observed in the porphyry tin mineralization at the Llallagua district in Bolivia (Sillitoe et al.,1975) and at the Toyoha Mine , in Japan (Ohta,1989) 8.1 Llallagua Tin Deposit; Llallagua district forms a part of the highly mineralized belt of Central Bolivia, which includes Potosi, Oruro, Colquechaca, Huanuni and many other districts. This region is Characterized by a silver - tin mineralization in genetic association with small quartz – prophyry stocks and volcanic vents formed within the near – surface developement . The mineralized veins cut plant – bearing beds of Late Miocene and Pliocene age. The ore is largely confined to the fractures, the filling is commonly frozen to the vein walls , and drusy cavities are abundant. Llallagua is regarded as a high-temperature deposit of the near-surface volcanic enviroment (Turneaure,1935). The Formation of a prophyry tin deposit in Bolivia is believed to be one of the last events at a volcanic center (Sillitoe et al.,1975).Llallagua tin mineralization possesses many of the characteristics of near – surface deposition although it includes an abundance of high-temparature minerals, as it is observed at Hisarcık cassiterite , yazganit, hematite and tridymite mineralization. 8.2 Polymetallic Tin and Indium Mineralization at The Toyoha Mine Hokkaido, Japan ; Yajima & Ohta (1979) indicated a remarkable mineral assemblage characterized by high grade zinc-lead ore containing notable amounts of silver , tin and indium . Occurrence and chemistry of indium containing minerals and accompanied tin minerals from the Toyoha Mine were reported by Ohta (1989). The deposit is the most productive supplier of silver , lead and zinc in Japan , and of indium in the world. A tin bearing chalcopyrite and a chalcopyrite –stannite solid solution occurrence was pointed out by Yajima et al.,(1991). Toyoha is the largest Ag-Pb-Zn vein-type deposit in Japan , and is situated about 40 km on road to the southwest of the center of Sapporo City. This deposit is hosted by Tertiary clastic and pyroclastic rocks, basalt , andesite and rhyolite from the Pliocene to Pleistocene Ages (Ohta.1991). Cassiterite is commonly observed in sphalerite and in fine grained aggregates of quartz and contains considerable amount of iron and tungsten. The distribution and mode of occurrence suggest that the cobalt-nickel mineralization is related to the tin-indium mineralization in both time and space.The Toyoha type deposits may be related to Est-Pacific subduction zone tectonism,occuring only in regions dominated by very shallow angles of subduction . It is possible that heat from deep portions of the subduction zone produced partial melt at the base of the thickened continental crust. Then ,the magma rose slowly assimilating continental material and becoming enriched in Sn and In. Fig.12 Chemical composition of yazganite mineral (Sarp and Černý,2005) Fig.13 Electron microscope analysis of yazganite mineral. 9.Conclusion; During the microscopic and XRD studies of the Kıranardı mineralization of Senir sırtı, we accounted for a new mineral (Yazgan et al.,2002). Then , Sarp and Cerny (2005) completed all the mineralogical and crystallographic works in the Department of Mineralogy of the Natural History Museum of Geneva, Switzerland under reference no:478178 (Fig.12,Fig.13).The mineral and name have been approved by the Commission on New Minerals and Mineral Name of The International Mineralogical Association. Arsenic-bearing yazganite and tin bearing cassiterite minerals association was first discovered and used to produce As-Sn-Cu bronze alloys in Anatolia. Arsenic and tin association has a great importance for the “Anatolian Archaeometallurgy” ;because first bronze alloys produced at the Early Bronze Age , contain arsenic together with tin and copper .The various bronze made artifacts and casting moulds have been excavated at Kültepe arhaeological site ,26 km north-northeastern of the Senir Sırtı at Hisarcık village , 20 km to the northeast of Kayseri on the Sivas route . The first chemical analyses confirm that arsenic and tin bearing ore deposit was exploited from the Senir Sırtı , antique pit mine and from The Zincidere adits , and used for making various As-Sn-Cu bearing bronze artifacts at Kanesh.Polymetalic ore deposit, near modern Hisarcık in Central Anatolia reflects relatively pronounced concentration of tin bearing findings, that may have been utilized for the production of early As, Sn, Cu bearing alloys . The humain communities used the polymetallic ores with varying mineraogical and chemical composition , even in different parts of the same ore bodies. The heterogeneity of an ore deposit in tenor (percentage) and in space of antique polymetallic ore deposits,such as Ergani-Maden and Hisarcık-Senir Sırtı , were reflected directly within the metallic compound of the bronze artifacts excavated in nearby archaeological sites . Metal workers acquired indeed the necessary experience for various technologies of making bronze.But, they learnt from choosing the best by trial and error method to produce Cu-As alloys first , ternary alloys Cu-Sn-As after . Finally, they could make real Cu-Sn alloys when they could get almost pure tin metal (Kaptan 1983) from Assyrian Trade Colonies. Analyses of some metallic artifact findings from Kültepe Kanesh demonstrated that the metals used have a various compound from the almost pure copper , to arsenical copper , arsenical tin copper and almost pure and real tin copper . In our assumtion , there is not a special formula to combine the different metal pourcentages or consciously chosen metallic combinations excluding copper , until “Assyrian Trade Colonies Period”. Kaptan (1983) already pointed out that possiblity of restricted small size tin deposits could be exploited in The Early Bronze Age during 3000-2000 BC in Anatolia , before the Assyrian Trade Colonies imported perfect tin (Anakum damqum vatrum)or good tin (Anakum damqum). Kaptan (1992) give also a brief description of ancient underground tin mining in Anatolia. The Early Bronze Age tin production, such as at Kestel (Yener & Özbal,1987; Yener et al.,2014) and Hisarcık-Senir Sırtı (Yazgan,2005;Pehlivan et al.,2005) have been documented much before the Assyrian Trade Colonies were involved in the import to Anatolia. 10.Acknowledgements; The auther gratefully acknowlege Ali Kemal Işıker General Director of Mineral Research and Exploration for the material support on the field works, Prof.Aslıhan Yener and Prof.Fikri Kulakoğlu for valuable comments and suggestions.Sincere thanks are also due to Gülay Sezener for fluid inclusions studies and Dr.Halil Sarp for two years troublesome works to establish all the mineralogical and crystallographic data file of yazganite mineral and to submit to IMA. Finally , I would like to express my sincere thanks to Atilla Çağlayan for important suggestion on data processing and critical reading with his personal computer and Umut Tümöz for typewritting and working up the the text.I am grateful to A.M.C Şengör for critical reading of the manuscript. Bibliograhy Baş,H.,Güner,Y & Emre,Ö. 1986 Erciyes Dağı Volkanitlerinin Özellikleri,Sivas Üniv.Müh.-Mim.Fak.Dergisi 1,29-44. Bates,R.L.&Jakson,J.A. 1980 Glossary of Geology , Amer. Geol. Inst. Falls Church, Virginia. Deer,W.A.,Howie,R.A & Zussman,M.A. 1967 Rock Forming Minerals, V.5 Non-Silicates. Dirik,K. 2001 Neotectonic Evolution of the Northwestward Arched Segment of the Central Anatolian Fault Zone,Central Anatolia,Turkey,Geodinamica Acta,14, 147-158. Ercan ,T.,Tokel,S.,Matsuda,J.I.,Ui,T.,Notsu,K.&Fujitani,T. 1994 Erciyes Dağı (Orta Anadolu) Pliyo-Kuvaterner Volkanizmasına İlişkin Yeni Jeokimyasal,İzotopik Radyometrik Veriler ve Jeotermal Enerji Açısından Önemi , 6.Enerji Kongresi,Türkiye , 208-222. Esin,U.& Harmankaya , S. 1988 Değirmentepe(Malatya)Kurtarma Kazısı, Kazı Sonuçları Toplantısı,9(1),79-125. Göymen – Aslaner,G. 1969 Doğu Anadolu’da bulunan Ergani-Maden bakır yatağının ve bilhassa yantaşlarının maden mikroskopik incelenmesi. MTA Bül. 72, 176-188. Hauptmann,A.,Schmitt-Strecker,S.,Begemann,F. & Palmieri,A . M. 2002 Chemical composition and lead istotopy of metal objects from the “Royal” tomb and other related finds at Arslantepe,Eastern Anatolia.Paléorient, 28(2), 43-69. Innocenti,F., Mazzuoli,R.,Pasquare,G., Redicati de Brozolo, F. & Villari,L. 1975 The Neogene calc-alkaline volcanism of Central Anatolia: geochronological data of Kayseri-Niğde area Geol.Mag. , 112,349-360. Kaptan,E. 1983 Türkiye Madencilik Tarihi İçinde Kalayın Önemi ve Kökeni , MTA Bull.95/96,164-172. Kaptan ,E. 1992 Tin and acient underground tin mining in Anatolia. Geol. Eng. Bull., 40,15-19. Koçyiğit,A. & Erol,O. 2001 A Tectonic Escape Structure: Erciyes Pull-Apart Basin, Kayseri Central Anatolia, Turkey, Geodinamica Acta, 14,133-145 Kuzucuoğlu,C. & Roberts, N. 1998 Evolution of the enviroment in Anatolia from 20,000 to 6,000 BP. Paléorient, 23/2,7-24. Kuzucuğlu,C.,Pastre,J-F.,Black,S., Ercan ,T. Fontugne , M., Guillou,H., Hatte,C., Karabıyıkoğlu,M., Orth,P. & Türkecan,A. 1998a Identification and Dating of Tephra layers from Quaternary Sedimentary Sequences of Inner Anatolia,Turkey, J.Volcanol. Geotherm. Res. 85, 153-172. Lechtman,H. 1996 Arsenic Bronze:Dirty Copper or Chosen Alloy? A View from the Americas,Journal of Field Archaeology, 23, 477-514. Lehner,J.W.&Yener,K.A. 2014 Organization and Specialization of Early Mining and Metal Technologies in Anatolia, in B.W Roberts and C.P Thornton, eds.,Global Archaeometallurgy: Methods and Syntheses, 529-557. New York:Springer Verlag. Palmieri,A.M,Sertok,K. & Evganij,C. 1993 From Arslantepe metalwork to arsenical copper technology in eastern Anatolia. In M.Frangipane, H.Hauptmann, M.Liverani, P.Matthiae & M. Mellink(Eds.) Università di Roma La Sapienza, 573-599. Palmieri, A.M., Fragipane, M., Hauptmann,A. & Hess,K. 1999 Early metallurgy at Arslantepe during the Late Chalcolithic and the Early Bronze Age IA-IB periods. In A. Hauptmann , E.Penicka,Th.Rehren & Ü.Yalçın (Eds.)The beginning of metallurgy, 141-148. Der Anschnittg, 9. Bochum: Deutsches Bergbau-Museum. Ohta,E. 1989 Occurrence and chemistry of indium – containing minerals from the Toyoha mine,Hokkaido,Japan.Bull.Geol.Surv.,Japan,Mining Geol.,39, 355-372. Otha,E. 1991 Polymetallic Mineralization at the Toyoha Mine, Hokkaido, Japan, Mining Geology,41(5),279-295. Sarp,H.& Černý,R. 2005 Na Fe+3 2(Mg,Mn)(AsO4)3 .H2O,a new mineral : its description and crystal structure , Eur. J.Mineral., 17, 367-373. Strabon 2000 Geographika,Arkeoloji Sanat Yayınları , Antik Kaynaklar Dizisi ,İstanbul, vol.XII-XIII-XIV (In Prof.Dr Adnan Pekman Trad.) Seeliger,T.C.,Pernicka,E.,Wagner,G.A.,Begemann,F.,Schmitt-Strecker,S.,Eibner,C.,Öztunalı,Ö.&Barnayi,I. 1985 Archäometallurgische Untersuch ungen in Nord-und Ostanatolien jahrbuch des Römisch –German isches Zentralmuseum, 32,597-659. Sillitoe,R.H., Halls,C. & Grant,J.N. 1975 Porphyry Tin Deposits in Bolivia, Econ. Geol., 70, 913-927. Turneaure,F.S. 1935 The tin deposits of Llallagua,Bolivia,Econ. Geol., 30,170-190. Türkecan ,A., Acarlar,M., Dönmez,M., Hepşen,N. & Bilgin,R. 1998 Kayseri (Bünyan – Develi – Tomarza) yöresinin jeolojisi ve volkanik kayaçların petrolojisi, MTA report No:10186. Türkecan ,A.,Kuzucuoğlu,C.,Mouralis,D.,Pastre,J-F., Atıcı,Y., Guillou,H. & Fontugne,M. 2004 Upper Pleistocene volcanism and Palaeogeography in Cappadocia,Turkey,MTA-CNRS-TÜBİTAK 2001-2003 Research Programme Tübitak Project No: 101Y109, MTA Report No: 10652. Wijkerslooth,P. 1944 Ergani madeni bakır zuhuratının primer mineralleri. MTA Bull.,Ankara , 31,66-71. Yajima,J & Ohta,E. 1979 Two-stage mineralization and formation process of the Toyoha deposits, Hokkaido,Japan, Mining Geol., 29, 291-306. Yajima,J., Ohta , E.& Kanazawa,Y. 1991 Toyohaite, Ag2 Fe Sn3 S8 , a new mineral, Mineral. J., 15(5) ,222-232. Yalçın,Ü.,Hauptmann H.,Hauptmann , A. & Pernica,E. 1992 Norşuntepe’de Geç Kalkolitik Çağı Bakır Madenciliği Üzerine Arkeolojik Araştırmalar,VIII.Arkeometri Sonuçları Toplantısı,T.C. Kültür Bakanlığı Anıtlar ve Müzeler Genel Müdürlüğü,Ankara, 25-29Mayıs. Yener,K.A. & Özbal,H. 1987 Tin in the Turkish Taurus Mountains: The Bolkardağ Mining District , Antiquity , 61, 64-71. Yener, K.A., Özbal,H., Kaptan,E., Pehlivan, N. & Goodway,M. 1989 Kestel: An Early Bronze Age Source of tin ore in the Taurus Mountains, Turkey. Science ,244, 200-203. Yener, K.A., Kulakoğlu,F.,Yazgan,E., Kontani,R., Hayakawa,Y.S., Lehner,J.W.,Dardeniz,G.,Öztürk,G., Johnson,A. & Hacar,A. 2014 The Discovery of New Tin Mines and Production Sites Near Kültepe Ancient Kanesh in Turkey: a Third Milennium BC Highland Production Model (in press). Yazgan ,E., Çağatay,A. & Yaşar, T. 2002 Mineralogical determination report No: 413, MTA – MAT Ankara,Turkey. Yazgan ,E. 2005 Cassiterite(tin) Mineralization Related with Erciyes Volcanic Activities and Mode of Formation of The Magnetite-Cassiterite-Yazganite-Tridymite Paragenesis, 58th Geological Congress of Turkey, Abstracts, 135-138. Captions Fig.1 Simplified geological map of Cappadocian Volcanic Province (Toprak et al.,1994). Fig.2 Geological map of Kıranardı and Zincidere cassiterite – yazganite hematite minerals deposit area (Türkecan et al.,1998). Fig.3 Photo showing Hisarcık , Kıranardı and Senir Sırtı. Fig.4 Geochemical characters of the Erciyes volcanics. Fig.5 Cassiterite and yazganite minerals under the binocular microscope. Fig.6 Cassiterite exsolution lamellas inbetween hematite minerals. Fig.7 Yazganite and tridymite minerals under the binocular microscope. Fig.8 Cassiterite (Cass),hematite(Hem) and yazganite (Yaz) minerals development on the extension fracture wall surface, Plg (plagioclase). Fig.9 Experimental measure numbers of triphased fluid inclusions homogenization temperatures (˚C). Fig.10 Cassiterite and hematite mineralization in layered pyroclastic levels at Zincidere antique tin mine. Fig.11 Hydrothermal hematite veins cutting pyroclastic rock at Zincidere antique tin mine. Fig.12 Chemical composition of yazganite mineral. Fig.13 Electron microscope analysis of yazganite mineral. ~ 18 ~