BULLETIN of the MINERAL RESEARCH and EXPLORATION Bulletin of the Foreign Edition 2015 151 ISSN : 0026 - 4563 CONTENTS

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Bull. Min. Res. Exp. (2015) 151: 269-283

BULLETIN OF THE MINERAL RESEARCH AND EXPLORATION Bulletin of the Foreign Edition 2015 151 ISSN : 0026 - 4563 CONTENTS

The late Quaternary Tectono-Stratigraphic evolution of the Lake Van, Turkey ...... Naci GÖRÜR, M. Nam›k ÇA⁄ATAY, Cengiz ZABCI, Mehmet SAKINÇ, ...... Remzi AKKÖK, Hande ﬁ‹LE and Sefer ÖRÇEN 1

Late Cenozoic Extensional Tectonics In Western Anatolia: Exhumation Of The Menderes Core Complex And Formation Of Related Basins ...... Gürol SEYITO⁄LU and Veysel IﬁIK 49

Late Pleistocene Glaciations and Paleoclimate of Turkey ...... M. Akif SARIKAYA and Attila ÇINER 109

Late Permian Unconformity Around Ankara and New Age Data on The Basement Rocks, Ankara, Turkey ...... Mustafa SEV‹N, Mustafa DÖNMEZ, Gökhan ATICI, A. Hande ESATO⁄LU VEKL‹, ...... Ender SARIFAKIO⁄LU, Serap ARIKAN and Havva SOYCAN 131 Mineral Research and Exploration Differentiation Processes In Late Cretaceous Ultrapotassic Volcanics Around Amasya ...... Fatma GÜLMEZ and ﬁ. Can GENÇ 151

Geological Features Of Neogene Basins Hosting Borate Deposits: An Overview Of Deposits and Future Forecast, Turkey ...... Cahit HELVACI 171

Vertical And Horizontal Analysis Of Crustal Structure In Eastern Anatolia Region ...... Oya PAMUKÇU, Tolga GÖNENÇ, Ayça YURDAKUL ÇIRMIK, ﬁevket DEM‹RBAﬁ and Seyit TOSUN 210

Archaeological and Geological Concepts on the Topic of Ancient Mining ...... Prentiss DE JESUS and Gonca DARDEN‹Z 233

Evaluation Of Asbestos Exposure In Dumanli Village (Çanakkale-Turkey) From A Medical Geology Viewpoint: An Inter-Disciplinary Study ...... Erdinç Y‹⁄‹TBAfi, Arzu M‹R‹C‹, U¤ur GÖNLÜGÜR, ...... Coflkun BAKAR, Onur TUNÇ, F›rat fiENGÜN and Özgür IfiIKO⁄LU 249

Geological Heritage And Framework List Of The Geosites In Turkey ...... Nizamettin KAZANCI, Fuat ﬁARO⁄LU and Yaﬂar SULUDERE 261

Review of The Occurrence of Two New Minerals in The Emet Borate Deposit, Turkey: Emetite, Ca7Na3K(SO4)9 and Fontarnauite Na2Sr(SO5)[B5O8(OH)](H2O)2 http://bulletin.mta.gov.tr ...... Cahit HELVACI 271 Acknowledgement ...... 287

Notes to the authors...... 289

REVIEW OF THE OCCURRENCE OF TWO NEW MINERALS IN THE EMET BORATE DEPOSIT, TURKEY: EMETITE, Ca7Na3K(SO4)9, and FONTARNAUITE, Na2Sr(SO4)[B5O8(OH)](H2O)2

Cahit HELVACIa* a Dokuz Eylül Üniversitesi, Jeoloji Mühendisli¤i Bölümü T›naztepe Yerleﬂkesi, 35160 Buca/‹zmir TURKEY

ABSTRACT Keywords: The Emet borate deposit is situated in the middle of the known borate deposits of western Neogene borate basins, Anatolia. Emet is the world biggest colemanite-probertite deposit which is located in the Emet borate deposit, upper section of the volcano-sedimentary sequence of the Emet basin. Emet borate deposit Mineralogy, Emetite, is unique and has unusual mineral associations. The principal minerals in the Emet borate Fontarnauite, West deposit are colemanite with minor probertite, ulexite and hydroboracite. In addition, rare Anatolia. species such as meyerhofferite, veatchite-A, tunellite, terrugite and cahnite occur sporadically. This is the only deposit known to contain any of the minerals veatchite-A, tunellite, teruggite and cahnite. Arsenic minerals (realgar and orpiment) are very abundant and spatially related to the borates, indicating a common genetic origin. The mineralogical record of Do¤anlar boreholes is characterized by the alternation of Na-Ca borate (probertite) and Na-Ca sulphate (glauberite) units including a central halite beds. Colemanite is restricted to the base and top of the sequence in these boreholes and in the whole basin. In this part of the section the major mineral associations probertite-glauberite and halite, with several rare minerals and two new minerals (emetite and fontarnauite) were also discovered in these borehole logs. The Emet borate deposit was formed in two separate parts, possibly part of an interconnected lacustrine playa lake, in areas of volcanic activity, fed partly by thermal springs and partly by surface streams. The early colemanite, meyerhofferite, ulexite and teruggite nodules were formed directly from brines penecontemporaneously within the unconsolidated sediments below the sediment/water interface, and continued to grow as the sediments were compacted. Diagenetic alterations include the partial replacement of colemanite by veatchite-A, cahnite, hydroboracite and calcite. The new mineral, emetite, always appears as a diagenetic phase consisting of aggregates of tiny crystals that replace glauberite at the top of glauberite units. Fontarnauite is most commonly associated with probertite, glauberite and celestine in isolated colorless to light brown prismatic crystals or as clusters of crystals in core samples of these boreholes.

1. Introduction formation of thick volcano-sedimentary successions and associated mineral deposits. In this respect, The Geological evolution of western Anatolia tectonic evolution of the Neogene basins is a during Neogene time is characterized by basin fundamental theme in studying the Neogene volcanic formation and contemporaneous widespread volcanic evolution as well as the related mineral deposits of activity. The Neogene volcanic activity in western the region (Travis and Cocks, 1984; Fytikas et al., Anatolia was developed contemporaneously with 1984; Ercan et al., 1985, 1996; Ersoy and Helvac›, development of NE trending basins, giving rise to 2007; Ersoy et al., 2011, 2012, 2014; Palmer and

* Corresponding author: Cahit Helvac›, [email protected] 269 Two New Minerals In The Emet Borate Deposit

Helvac›, 1997; Floyd et al., 1998; Helvac›, 1995; 1986, 1989; Helvac› and Firman, 1976; Helvac›, 2005). 2005). The pre-Miocene basement of the basins is represented by the Menderes Massif, which The borate deposits of Turkey occur in western composed of Mesozoic and Paleogene rock units and Anatolia, south of the Marmara Sea within an area volcanics. The main borate districts of Turkey are roughly 300 km east-west by 150 km north-south. Bigadiç, Kestelek, Sultançay›r, Emet and K›rka The main borate districts are Bigadiç, Sultançay›r›, (Helvac›, 1989, 2005; Kistler and Helvac›, 1994; Kestelek, Emet, and K›rka (Figure l), and Turkish Helvac› et al., 1993; Helvac› and Alonso, 2000). The production supplies most of the commercially traded important borate minerals from a worldwide ulexite and colemanite from mines in the Bigadiç, commercial standpoint are borax, ulexite and Kestelek and Emet Districts, plus borax from the colemanite. Colemanite, a very common calcium deposit at K›rka. borate, is the predominant mineral in all borate The western Anatolia borate district contains the districts except for K›rka. A large number of other largest borate reserves in the world (Lyday, 1982; borate minerals are found in the deposits, including Kistler and Smith, 1983; Helvac›, 1989; Kistler and pandermite, inyoite, meyerhofferite, tincalconite, Helvac›, 1994; Helvac› and Alonso, 2000). All the kernite, hydroboracite, inderite, inderborite, western Anatolia borate deposits were formed during kurnakovite, cahnite, terrugite, veatchite-A and the Miocene time in closed lacustrine basins with tunnelite (‹nan et al., 1973; Helvac›, 1977, 1978, abnormally high salinity and alkalinity (Helvac›, 1983; Helvac› and Orti, 1998, 2004; Orti et al., 1998).

Figure 1- Location of Do¤anlar boreholes and geological map of the Emet borate district showing the location of open pit mines and boreholes in western Turkey (after Helvac›, 1986). 270 Bull. Min. Res. Exp. (2015) 151: 269-283

The boron in the deposits is assumed to have been interbedded with tuffaceous beds (Helvac› and derived by leaching of the surrounding rocks by Alonso, 2000). geothermal activity associated with local volcanism (Floyd et al., 1998). The borates then formed when The Emet borate deposits are situated in the the hydrothermal and spring waters evaporated after middle of the known borate deposits of western flowing into shallow playa lakes (Helvac›, 1995). Anatolia (Helvac› 1977, 1984, 1986, 2005). The Emet Boron-rich fluids are presumed to have also district includes Palaeozoic metamorphic rocks circulated along faults into these basins (Helvac›, intruded by granite, and overlying Tertiary sediments 1986, 2005). associated with volcanic rocks (Holzer 1954; Gawlik 1956; Akkuﬂ 1962). The principal minerals in the The borate deposits of Turkey were formed in the Emet borate deposits are colemanite with minor lacustrine sediments of Neogene age during periods ulexite and hydroboracite. The deposits are mined by of volcanic activity. Although the sediments open-pit mining methods in the southern basin deposited in the borate lakes show some differences, (Hisarcik and Derekoy deposits) and underground they are generally represented by tuffaceous rocks, and recently open-pit mining methods in the northern claystones, limestones and Ca, Na, Mg, Sr-borates. basin (Espey and Killik deposits). Investigations have Sandstone and conglomerates occur near the base of been carried out on various sections of the basin and each basin (Gawlik, 1956; Özpeker, 1969; ‹nan et al., samples have been collected from the open-pit, 1973; Helvac› and Firman, 1976; Helvac›, 1977). underground workings and the drill cores. Sediments in the borate lakes often show clear evidence of volcanic cyclicity. Borate minerals were Earlier published papers by Helvac› and Firman deposited in a separate or possibly interconnected (1976) and Helvac› (1984, 1986) indicated that the lake basins under arid or semi-arid climatic deepest part of the N-S trending Emet basin is around conditions. Pyroclastic and volcanic rocks of the Do¤anlar-‹¤deköy locality, where there were only rhyolitic, dacitic, trachytic, andesitic and basaltic weathered outcrops on both side of the Emet composition are intercalated with these lacustrine (Kocaçay) River. In this locality whole sequence was sediments. The existence of volcanic rocks in every covered with recent Quaternary and alluvial borate district suggests that volcanic activity may sediments, and deep drillings were suggested to the have been necessary for the formation of borates. Eti Maden Company. Concequently, in the years of Much of the sediments in the borate basin seems to 1986 and 2003 deep drilling project took place in the have been derived from volcanic terrain. Generally, Do¤anlar-‹¤deköy locality. A number of deep the borates are enveloped between tuff and clay-rich boreholes intersected the thickest part of the borate horizons. The lithologies of the borate deposits show zone in this area, with deepest one at about 700 some differences from one to another, and they are meters below the surface (Figures 1, 2 and 3). generally interbedded with conglomerate, sandstone, tuff, claystone, marl, and limestones, and are usually This paper is a preliminary report on the enveloped by, or grade into, limestones or claystones petrographic and geochemical characteristics of a (‹nan et al., 1973; Helvac›, 1977, 1986, 2005; Sunder, new sulphate and a borate-sulphate minerals 1980; Helvac› et al., 2012); and sediments often associated with lacustrine probertite-glauberite layers exhibit both lateral and vertical facies changes. in these Do¤anlar boreholes. These minerals are Volcanic rocks in the vicinity of the playa lakes in present in two boreholes recently drilled in the Emet which the borate deposits were formed are extensive borate district (Miocene; western Anatolia, Turkey). (Floyd et al., 1998). Intense calc-alkaline volcanic These boreholes were drilled with continuous rock activity took place simultaneously with the borate sampling by the Eti Maden Company (Turkish sedimentation. The volcanic rocks are generally Government) during 2003 for exploratory purposes in represented by a calc-alkaline series of flows ranging the vicinity of Do¤anlar village, located seven from acidic to basic and by associated pyroclastic kilometres to the south-west of Emet. The two rock (Ersoy et al., 2011, 2012). boreholes were drilled on the Quaternary alluvium of the Kocaçay River with a distance of 1.8 km between All of these sediments were generated during them. Figure 1 shows the borehole sites on a periods of high volcanic and hydrothermal activity. simplified geological map. The main colemanite open Although the mineral association of each district pit mines (Espey and Hisarc›k) in the area are also shows particular differences, the borates, in indicated (Figures 1 and 3). The evaporitic succession association with minor sulphates, are always in these boreholes is mainly formed of a glauberite- 271 Two New Minerals In The Emet Borate Deposit

the name “emetite” for the new sulphate mineral after the town of Emet. It is also noted that the fine crystal size of this new mineral hinders the appropriate chemical and crystallographic characterization required to propose it as a new mineral to the International Mineralogical Association (Garcia- Veigas et al., 2010a). This mineral still needs to be worked on in order to get all the data to be approved by IMM.

Fontarnauite is a new mineral found in core samples of the Do¤anlar boreholes no: 2 and no: 188 drilled in the vicinity of the Do¤anlar village, located seven kilometres to the southwest of the Emet town (western Anatolia, Turkey) (Figure. 1 and 4). Fontarnauite is a double salt (borate-sulphate) of sodium and strontium with minor contents of potassium and calcium. The proposed name is for deceased Dr. Ramon Fontarnau (1944-2007), Director of the Material Characterization Section of the Scientific-Technical Survey at the University of Barcelona for his effort to promote the development of scientific facilities focused on mineral characterization (Garcia-Veigas et al., 2010b; Cooper et al., in press).

This paper presents the short story of the two new minerals, emetite and fontarnauite (borate and borate- sulphate minerals), recently discovered in the Emet borate deposits, and attempts to define both the Figure 2- Generalized stratigraphic section of the Emet relationships between mineral associations, and the basin (without scale). MM: Paleozoic Menderes Metamorphic basement; EG: E¤rigöz Granitoid; nature of their occurrences. The full papers of these IAZ: carbonates and ophiolitic rocks of Izmir- minerals were treated elsewhere. Ankara Zone; Taﬂbaﬂ› formation: conglomerates; K›z›lbük formation: clastic unit containing coal; 2. Geological Setting of Emet Basin Akdag, Kestel, Köprücek and Dereköy: volcanic Emet basin (Akdeniz and Konak, 1979; Helvac›, units; Hisarc›k formation: carbonates with clastic, and tuff deposits, containing borates; 1984, 1986; Figure 3), is located between the E¤rigöz Emet formation: upper limestone unit (modified granitoid intruded into the Menderes Massif after Helvac›, 1984). metamorphic rocks to the west, and the Afyon zone metamorphic rocks to the east (Figures 1, 2 and 3). The Neogene sequence rests unconformably on Paleozoic metamorphic rocks that consist of marble, probertite alternation. In this part of the section the mica-schist, calc schist and chlorite schist. major mineral associations probertite-glauberite and halite, with several rare minerals and two new The borate deposits of Turkey were formed in minerals (emetite and fontarnauite) were also lacustrine environments during periods of volcanic discovered in these boreholes. They were already activity. The borates of the Emet area are part of the published elsewhere (Garcia-Vegias et al., 2010a, Tertiary lacustrine sediments which rest 2010b, 2011; Cooper et al., in press). unconformablv on Palaeozoic metamorphic rocks, consisting of marble, micaschist, calc-schist and Emetite was found in core samples from the chlorite-schist (Figure 3). The sediments of the Emet boreholes Kütahya-Emet no: 2 (UTM: 35S 691346 / district consist of predominantly lacustrine sequence. 4350558) and no: 188 (UTM: 35S 691800 / 4348815) The stratigraphy of Emet basin comprises two (called “Do¤anlar boreholes”) (Figure 4). We suggest Neogene volcanosedimentary units separated by a 272 Bull. Min. Res. Exp. (2015) 151: 269-283

Figure 3- Geological map of the Emet borate district (modified after Helvac›, 1984) showing the location of the colemanite open pit mines and the studied boreholes. 273 Two New Minerals In The Emet Borate Deposit

regional unconformity (Figures 2 and 3). These units the southwest of the basin, and are composed of syn- can be correlated with similar rocks from other basins sedimentary mafic lava flows. These volumetrically on the basis of their age, lithology and deformational small volcanic rocks conformably overlie the features, and they are named as the Hac›bekir and K›z›lbük Formation. The age of the Kestel volcanics ‹nay groups. In the Emet basin, the ‹nay Group hosts is stratigraphically accepted to be early Miocene. the world’s biggest colemanite and probertite borate deposits (Gawlik, 1956; Helvac›, 1984, 1986; Helvac› The ‹nay Group in Emet basin is made up of the and Orti, 1998; Helvac› and Alonso, 2000; Garcia et Hisarc›k and Emet formations that interfinger with al., 2011). the Köprücek volcanics and th Dereköy basalt (Figure 3). The Hisarc›k formation (Akdeniz and Konak, The Hac›bekir Group consists of the Taflbafl› and 1979) crops out in a large area in the Emet basin and K›z›lbük formations and the Akda¤ and Kestel is composed of conglomerates, pebblestones and volcanics (Figures 2 and 3). The Taflbafl› formation sandstone intercalations. The age of the Hisarc›k crops out to the western and southwestern parts of the formation is accepted to be middle Miocene on the Emet basin, and is made up of reddish-brown colored basis of volcanic intercalations in the ‹nay Group. conglomerates with grayish sandstone intercalations Towards the center of the basin, the Hisarc›k deposited in alluvial fan facies. The Taflbafl› formation passes laterally into the Emet formation formation is locally interfingered with rhyolitic that is composed of sandstone – claystone – mudstone pyroclastic rocks of the Akda¤ volcanics, and is - limestone alternations of fluvio-lacustrine origin. conformably overlain by the K›z›lbük formation. The fine-grained parts of the unit, especially the mudstone – claystone levels contain large borate The age of the unit is early Miocene on the basis deposits which are mined for colemanite and of radiometric age data from the volcanic rock probertite (Helvac› and Alonso, 2000; Helvac› and intercalations. The K›z›lbük formation crops out in a Ersoy, 2006; Helvac› et al., 2006; Ersoy et al., 2012). large area to the western and southwestern parts of the Emet basin, and is composed of coal-bearing In the Emet basin, the Köprücek volcanics yellowish sandstone–siltstone–mudstone alternations (16.8±0.2 Ma K–Ar age; Helvac› and Alonso, 2000) and laminated limestone of fluvio-lacustrine origin. crop out to the northern part of the Emet basin. The The K›z›lbük formation is interfingered with unit is composed of andesitic to rhyolitic lava flows, pyroclastic rocks of the Akda¤ volcanics, which are dykes and associated pyroclastics which interfinger composed of rhyolitic lava flows, domes, pyroclastics with the Hisarc›k formation. The thickness of the and epiclastics. The Akda¤ volcanics have yielded pyroclastic intercalations in the Hisarc›k formation 20.3±0.6 (Seyito¤lu et al., 1997) and 19.0±0.2 Ma increases towards the north of the basin, which (Helvac› and Alonso, 2000) K–Ar ages (Table 1). The suggests that the Köprücek volcanics originated from Kestel volcanics emplaced in a NE–SW-direction to this area. The Köprücek volcanics are overlain by the

Figure 4- Cross section along the Do¤anlar locality and Hisarc›k opencast mine showing the deep boreholes numbers 2 and 188. 274 Bull. Min. Res. Exp. (2015) 151: 269-283

Table 1- Borates, sulphates and sulphides recognised in the Emet basin and their chemical formulas.

Borates Ca Colemanite CaB3O4(OH)3 H2O

Meyerhofferite Ca(B3O3(OH)5).H20

Ca-Na Probertite NaCaB5O7(OH)4 3(H2O)

Ulexite NaCaB5O6(OH)6 5(H2O)

K Fontarnauite (Na,K)2(Sr,Ca)SO4[B4O6(OH)2] 3H2O

Kaliborite KMg2H(B6O8(OH)5)2 4(H2O)

Mg-Na Aristarainite NaMgB12O16(OH)8 4(H2O)

Rivadavite Na6Mg(B6O7(OH)6)4.10H2O

Hydroboracite CaMg(B3O4(OH)3)2 3(H2O)

Sr Tunellite SrB6O9(OH2) 3H2O

Veatchite-A Sr2(B11O16(OH)5).H2O

As Cahnite Ca2B(AsO4)(OH)4

Teruggite Ca4MgAs2B12O22(OH)12.12H2O

Sulphates Ca Anhydrite CaSO4

Gypsum CaSO4 2H2O

Ca-Na Glauberite Na2Ca(SO4)2

Na Thenardite Na2(SO4)

K Emetite Ca7Na3K(SO4)9

Sr Celestine SrSO4

Kalistrontite K2Sr(SO4)2 Sulphides As Arsenopyrite FeAsS

Orpiment As2S3

Realgar As4S4 limestones of the Emet formation. The pyroclastic mineralization, as well as having a close spatial and intercalations yield 16.8±0.2 Ma K–Ar age (Helvac› temporal relationship with the borates and it is and Alonso, 2000; table 1). In the southern part of the therefore considered a likely source. Possible basin, the Hisarc›k formation is also conformably mechanisms by which volcanism might supply B, S, overlain by basaltic lava flows of the Dereköy basalt. Sr, As and Li to the basin sediments include the Along the basal contact of the Dereköy basalt several leaching of volcanic rocks by hydrothermal waters, pepperitic textures are developed, indicating a syn- the direct deposition of ash into the lake sediments, or sedimentary emplacement of the lavas. The Dereköy the degassing of magmas (Helvac›, 2015, in this basalt has been dated as 15.4±0.2 and 14.9±0.3 Ma volume). (K–Ar ages; Seyito¤lu et al., 1997; Helvac› and Alonso, 2000). 3. Mineralogy of Emet Deposit

The volcanic activity in the Emet basin is thought Mineralogical studies have shown that the borate to be the source of the borate deposition. Thermal deposits in the Emet district are far more complex springs associated with local volcanic activity are than previously thougt in addition to the minerals thought to be the possible source of the borates previously recorded (Özpeker 1969). The Emet basin (Helvac›, 1977; Helvac›, 1984; Helvac› and Alonso, is one of the Neogene basins in western Turkey 2000). The older acidic lavas contain higher B levels containing significant amounts of rare borate than the more recent intermediate alkaline lavas. The minerals. The borates are interlayered with tuff, clay Early Miocene acidic volcanism at Emet basin has and marl with limestone occurring above and below high levels of elements associated with the borate lenses. Sedimentary and early diagenetic 275 Two New Minerals In The Emet Borate Deposit

processes controlled the crystal growth both 4. Occurrence of Emetite (a new sulphate subaqueously and interstitially. The principal borate mineral): Ca7Na3K(SO4)9 in the Emet Borate minerals are colemanite and probertite (Table 1; Deposit figures 5 and 6), with minor ulexite, hydroboracite and meyerhofferite. The Emet borate deposits contain Emetite, a new sulphate mineral, Ca7Na3K(SO4)9, many of the rare borate minerals such as veatchite-A, has been identified in two boreholes drilled in the tunellite, teruggite, and cahnite (Helvac› and Firman, Emet borate district. The evaporitic succession in 1976; Helvac›, 1977, 1984, 1986; Helvac› and Orti, these boreholes is mainly formed of a glauberite- 1998; Garcia-Veigas et al., 2011). Montmorillonite, probertite alternation. The chemical characterization illite and chlorite are clay minerals that have been of the mineral phases in the Do¤anlar boreholes has identified, and zeolites are abundant along the tuff led to the identification of a new K-bearing sulphate horizons (Helvac› et al.,1993; Çolak et al., 2000). mineral, Ca7Na3K(SO4)9 named here as “emetite”. The new mineral always appears as a diagenetic The petrologic study of core samples from two phase consisting of aggregates of tiny crystals that exploratory wells in the Do¤anlar sector, reveals a replace glauberite at the top of glauberite units. The complex mineral association in which probertite, replacement was caused by the interaction of glauberite and halite constitute the major primary glauberite with K-rich in terstitial brines, which are phases precipitated in a saline lake within a volcano- more concentrated than those from which glauberite sedimentary context (Garcia-Veigas et al., 2011). had precipitated (Garcia-Veigas et al., 2010a). Other sulphates (anhydrite, gypsum, thenardite, celestite and kalistrontite), borates (colemanite, This paper is to report on the petrographic and ulexite, hydroboracite, tunellite, kaliborite and geochemical characteristics of a new sulphate mineral aristarainite) and sulphides (emetite, arsenopyrite, associated with lacustrine glauberite layers. The realgar and orpiment) are attributed to early evaporitic succession in these boreholes is mainly diagenesis. The Do¤anlar deposit is the most formed of a glauberite-probertite alternation. Emetite important deposit of probertite known up to now was found in core samples from the boreholes (Garcia-Veigas et al., 2011). Emetite paper is already Kütahya-Emet no: 2 (UTM: 35S 691346/4350558) published in an international journal (Garcia-Veigas and no: 188 (UTM: 35S 691800/4348815) (Do¤anlar et al., 2010a). A new sulphate-borate mineral boreholes). This mineral is present in two boreholes (fontarnauite) has been found in the deposit (Garcia- recently drilled in the Emet borate district (Miocene; Veigas et al., 2010b) (Table 2) and the paper western Anatolia, Turkey). The name “emetite”, after concerning this mineral is in press in the Canadian the town of Emet, is suggested for the new sulphate Mineralogist (Cooper et al., in press). mineral (Garcia-Viagas et al., 2010a).

The mineralogical record of Do¤anlar boreholes The new sulphate, Ca7Na3K(SO4)9, always is characterized by the alternation of Na-Ca borate appears as a diagenetic mineral replacing millimetre- (probertite) and Na-Ca sulphate (glauberite) units sized crystals of glauberite. It consists of aggregates including a central halite beds. Colemanite is of tiny, elongated and anhedral crystals, frequently restricted to the base and top of the sequence. curved, which exhibit second order interference Kalistrontite is abundant in the sequence indicating a colours. They are arranged in fascicular and radial significant concentration of Sr in brines. Fontarnauite fabrics and resemble intergrowth textures (Figures 7 appears as an early diagenetic phase, replacing both and 8) (Garcia-Veigas et al., 2010a). The aggregates probertite and glauberite, as a consequence of an form round or irregularly-shaped masses, of less than anomalous chemical composition achieved by the 1 mm in length, that replace the glauberite crystals residual brines duringevaporation in a saline lake from their margins, in contact with the matrix, environment with volcaniclastic contribution. Other towards the centre (Figure 7). Commonly, these minor minerals found in the boreholes include: masses, as well as the host glauberite crystals, are borates (aristarainite, colemanite, hydroboracite, replaced by equant, euhedral crystals of anhydrite kaliborite tunellite and ulexite), sulphates (anhydrite, from tens of mm up to 3 mm across (Figure 8). In celestine, gypsum, kalistrontite and thenardite), and borehole no: 188, emetite also occurs at the top of a sulphides (emetite, arsenopyrite, orpiment and glauberite unit, at a depth of 312 m, where the host realgar) (Helvac›, 1984; Garcia-Veigas et al., 2011) glauberite crystals are replaced by secondary gypsum (Figures 5 and 6; table 1). (Figure 6). The new mineral and the anhydrite 276 Bull. Min. Res. Exp. (2015) 151: 269-283

Figure 5- Lithological log correlation of the Do¤anlar boreholes based on mineral associations. C-1: Basal Colemanite Unit, P-2: Lower Probertite Unit, P-2/g1: Lower-Anhydrite Subunit, P- 2/g2: Intermediate Glauberite-Kalistrontite Subunit, P-2/g3: Upper Glauberite- Fontarnauite Subunit, H-3: Halite Unit, G-4: First Glauberite Unit, P-5: Intermediate Probertite Unit, G-6: Second Glauberite Unit, P-7: Upper Probertite Unit, C-8: Upper Colemanite Unit (Garcia-Veigas et al., 2011).

Figure 6- Schematic distribution of the evaporitic minerals with depth (borehole Do¤anlar no. 2). Units as in figure 5 (Garcia-Veigas et al., 2011). 277 Two New Minerals In The Emet Borate Deposit

Table 2- Documents of new mineral Fontarnauite published in Mineralogical Magazine October 2014.

NEW MINERAL PROPOSALS APPROVED IN SEPTEMBER 2014 IMA No. 2009-096a Fontarnauite Kütahya-Emet 2 and 188 boreholes, near the village of Do¤anlar, Kütahya Province, Western Anatolia, Turkey Mark A. Cooper, Frank C. Hawthorne, Javier Garc›´a-Veigas, Xavier Alcobe´, Cahit Helvaci, Edward S. Grew* and Neil A. Ball *E-posta: [email protected] Chemical Properties of Fontarnauite

Formula: (Na,K)2(Sr,Ca) (SO4)[B5O8(OH)]·2H2O Crystallography of Fontarnauite Crystal System: Monoclinic: P21/c; structure determined (New structure type) Class (H-M): 2/m – Prismatic Space Group: P21/b Space Group Setting: P21/c Cell Parameters: a = 6.458(2) Å b = 22.299(7) Å c = 8.571(2) Å β = 103.05(1)° Ratio: a:b:c = 0.29 : 1 : 0.384 Unit Cell Volume: V 1,202.41 Å? (Birim Hücreden hesaplanm›flt›r) X-Ifl›nlar› Powder Diffraction Data: d-spacing Intensity 11.15 -100 3.395 -8 3.339 -20 3.199 -30 3.046 -10 3.025 -7 2.750 -10 2.400 -8 Type material is deposited in the collections of the Royal Ontario Museum, 100 Queens Park, Toronto, Ontario M5S 2C6, Canada, accession number M56745 How to cite: Cooper, M.A., Hawthorne, F.C., Garc›á-Veigas, J., Alcobe´, X., Helvaci, C., Grew, E.S. and Ball, N.A. (2014) Fontarnauite, IMA 2009-096a. CNMNC Newsletter No. 22, October 2014, page 1244; Mineralogical Magazine, 78, 1241-1248.

278 Bull. Min. Res. Exp. (2015) 151: 269-283

A A

B B

Figure 7- Glauberite crystal partially replaced by Figure 8- Round aggregate of the new sulphate mineral aggregates of the new sulphate mineral emetite emetite (arrows) replacing glauberite crystals (A: (arrows) (A: parallel nicols, B: crossed nicols) parallel nicols, B: crossed nicols) (Garcia-Veigas (Garcia-Veigas et al., 2010a). et al., 2010a). crystals have also been partly transformed to fontarnauite between 249 and 351.9 m (Garcia- secondary gypsum, although to a lesser extent in the Veigas et al., 2011). case of the anhydrite (Garcia-Veigas et al., 2010a). Fontarnauite is most commonly associated with probertite, glauberite and celestine (Figures 9, 10 and 5. Occurrence of fontarnauite (a new sulphate- 11). In addition, García-Veigas et al. (2010b) borate mineral): reported fontarnauite with (1) halite, (2) kaliborite Na2Sr(SO4)[B5O8(OH)](H2O)2 in the Emet replacing probertite, and (3) kalistrontite, which borate deposit replaced fontarnauite in pseudomorphs after glauberite. Other minerals occurring in the boreholes, Fontarnauite was recovered from the Kütahya- most abundantly colemanite, ulexite, dolomite, Emet 2 and 188 (Do¤anlar boreholes) boreholes arsenopyrite, realgar and orpiment, have not been drilled in the Emet basin near the village of Do¤anlar found with fontarnauite (Garcia-Veigas et al., 2011). (García-Veigas et al. 2010b, 2011; Helvac› 1986,

Helvac› and Orti 1998). The exploration holes were Fontarnauite, Na2Sr(SO4)[B5O8(OH)](H2O)2, drilled during 2003 in the area to the north of the was discovered in 2009 in cores recovered from the Hisarc›k open cut mine in Quaternary alluvium of the borate-bearing Miocene Emet basin (García-Veigas Kocaçay River (Figure 4). The distance between the et al. 2010b, 2011). The mineral and its name have two boreholes is about 1.8 km. Borehole 2 is 716 m been approved by the International Mineralogical in depth; fontarnauite was observed between 530 and Association Commission on New Minerals, 581.5 m depth; borehole 188 (516 m in depth) yielded Nomenclature (IMA no. 2009-64a). The holotype is 279 Two New Minerals In The Emet Borate Deposit

Figure 11- Photomicrograph of fontarnauite crystals with hexagonal outline formed from the {010} side pinacoid and the {011} prism (crossed polars) (after Cooper et al., in press).

deposited in the mineralogy collection of the Royal Ontario Museum, 100 Queen’s Park, Toronto, Ontario M5S 2C6, Canada, accession number M56745 (Cooper et al., in pres) (Table 2).

Fontarnauite is most commonly associated with probertite, glauberite and celestine in isolated Figure 9- Optical (upper) and BSE-SEM (lower) images of a cluster of fontarnauite crystals. (F: colorless to light brown prismatic crystals or as fontarnauite, P: probertite,T: tuff). (García- clusters of crystals less than 5 mm long (Figure 10). Veigas et al., 2010b). More often it displays pseudohexagonal sections less than 1 mm in diameter. Under microscope it shows a perfect cleavage parallel to (010) (Figure 11). It has a pearly, transparent to translucent lustre, a brittle tenacity and a white streak (Cooper et al., in press).

Fontarnauite is interpreted to be an early diagenetic phase, replacing both probertite (Figures 9, 10 and 11) and glauberite, as a consequence of the K- SO4-enriched composition in residual brines during the evaporation in a saline lake environment to which volcaniclastic material had been added (Helvac› and Alonso, 2000; Orti et al., 1998; Garcia-Veigas et al., 2010b; Cooper et al., in press).

6. Conclusions Figure 10- Prismatic fontarnauite crystals in thin section with crossed polars. Photomicrograph of The Emet borates were formed in playa lakes, fed prismatic fontarnauite crystals elongate along partly by thermal springs and partly by streams [100] (crossed polars) (García-Veigas et al., draining the catchment areas, and it may be assumed 2010b). that the initial brines at all times contained an abundance of calcium and boron with minor amounts of arsenic, sulphur, strontium, magnesium and sodium. Early precipitated minerals seem to have formed within the clastic sediments. Brines were evidently rich in Ca and B in both the northern and 280 Bull. Min. Res. Exp. (2015) 151: 269-283 southern parts of the basin throughout the sequence. References Both lateral and vertical changes from calcite-marls to colemanite bearing clays have been observed and a Akdeniz, N., Konak, N. 1979. Simav–Emet–Dursun- bey–Demirci yörelerinin jeolojisi [Geology of the gross zoning both laterally and vertically from calcite Simav–Emet–Dursunbey–Demirci areas]. Maden to colemanite and back to calcite seems to be general Tetkik ve Arama Genel Müdürlü¤ü Rapor No: in both areas. Ca borates, ulexite and teruggite 6547, Ankara (unpublished). crystallized within the sediments and did not Akkufl, M.F. 1962. Geology of the Kütahya-Gediz area. Jo- precipitate from open water. Co-precipitation of urnal of Mineral Research and Exploration Insti- ulexite and later diagenetic formation of tunellite tute of Turkey, 58: 21-30 occurs only rarely in the northern basin. Field and Cooper, M.A., Hawthorne, F.C., Garcia-Veigas, J., Alcobé, textural evidence clearly indicates the sequence Ca X., Helvac›, C., Grew, E. S., Ball, N. A. 2014. Fon- borate + Ca-Na borate + Sr borate. tarnauite, (Na,K)2 (Sr,Ca) (SO4) [B5O8 (OH)] (H O) , a new sulfate-borate from Do¤anlar In the southern area the sporadic occurrence of 2 2 (Emet), Kütahya Province, Western Anatolia, Tur- gypsum suggests that where sulphates are present the key. Candian Mineralogist (bask›da). sequence is calcite + gypsum + colemanite. Çolak, M., Helvac›, C., Maggeti, M. 2000. Saponite from Two new minerals, emetite and fontarnauite, have the Emet colemanite mines, Küthahya, Turkey. Clays and Clay Miner been discovered in the Do¤anlar boreholes located in ., 48: 409–423. the central part of the Emet borate basin. The Ercan, T., Sat›r, M., Kreuzer, H., Türkecan, A., Günay, E., chemical characterization of the mineral phases in the Çevikbafl, A., Atefl, M., Can, B. 1985. Bat› Anado- Do¤anlar boreholes has led to the identification of a lu Senozoyik volkanitlerine ait yeni kimyasal, izo- topik ve radyometrik verilerin yorumu (Interpreta- new K-bearing sulphate mineral, Ca Na K(SO ) , 7 3 4 9 tion of new chemical, isotopic and radiometric da- named as “emetite”. This mineral always appears ta on Cenozoic volcanics of western Anatolia). forming aggregates that partially replace the Bullettin of Geological Society of Turkey, 28, 121- glauberite crystals at the top of the glauberite units. 136. Fontarnauite is most commonly associated with Ercan, E., Sat›r, M., Sevin, D., Türkecan, A. 1996. Bat› probertite, glauberite and celestine. Fontarnauite is Anadolu’daki Tersiyer ve Kuvaterner yafll› volka- interpreted to be an early diagenetic phase, replacing nik kayaçlarda yeni yap›lan radyometrik yafl öl- both probertite and glauberite in the çümlerinin yorumu [Some new radiometric ages volcanostratigraphic sequence of the Emet basin. 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Schroeder NE–SW-trending Neogene volcano-sedimentary and ‹brahim Uysal for their constructive comments basins in western Anatolia: implications for associ- and suggestions, which have considerably improved ations of supradetachment and transtensional stri- the final version of the manuscript. ke-slip basin formation in extensional tectonic setting. J. Asian Earth Sci. 41, 159–183. Received: 03.04.2015 Ersoy, E. Y., Helvac›, C., Palmer, M. R. 2012. Petrogenesis Accepted: 18.06.2015 of the Neogene volcanic units in the NE–SW-tren- Published: December 2015 ding basins in western Anatolia, Turkey. Contrib Mineral Petrol (2012) 163:379–401. Ersoy E.Y., Çemen, ‹., Helvac›, C., Billor, Z. 2014. Tecto- no-stratigraphy of the Neogene basins inWestern Turkey: Implications for tectonic evolution of the Aegean Extended Region. Tectonophysics 635 (2014) 33–58. 281 Two New Minerals In The Emet Borate Deposit

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