Geo chem is try of the Igdekoy-Doganlar Na-Ca bo rate de posit, Emet Prov ince (west ern Anatolia, Tur key)
smail KOÇAK1, *
1 De part ment of En gi neer ing Sci ence, BandÏrma Onyedi Eylül Uni ver sity, BandÏrma-BalÏkesir, 10200, Tur key
Koçak, ., 2020. Geo chem is try of the Igdekoy-Doganlar Na-Ca bo rate de posit, Emet Prov ince (west ern Anatolia, Tur key).
Geo log i cal Quar terly, 64 (3): 807–817, doi: 10.7306/gq.1555
Bo rates at the Igdekoy-Doganlar lo cal ity were de pos ited in a Mio cene lac us trine en vi ron ment dur ing pe ri ods of Paleogene to Early Qua ter nary vol ca nic ac tiv ity. The min eral paragenesis con sists of probertite – NaCaB5O7(OH)4 × 3H2O, ul ex ite – NaCa[B5O6(OH)6] × 5H2O, hydroboracite – CaMg[B3O4(OH)3]2 × 3H2O, cole man ite – Ca[B3O4(OH)3] × H2O, ha lite, anhydrite, glau ber ite, smectite and illite. The ma jor el e ment, Ca, is higher in the Igdekoy-Doganlar de pos its com pared to the av er ages for an de site and the Earth’s crust. Within the trace el e ments, no ta ble en rich ment is iden ti fied in Li, Se, As, Sb, Sr and Cs. Lith ium and Se oc cur in suf fi cient con cen tra tions to be con sid ered as eco nom i cally valu able by-prod ucts. B and Sr anom a lies can be used as an im por tant marker in the ex plo ra tion for bo ron de pos its. The Y/Ho ra tio of the Igdekoy-Doganlar bo rates is close to chondritic val ues. The neg a tive Ce anom aly in bo rates from the Igdekoy-Doganlar de posit sug gests that de po si tion oc curred un der ox i da tive con di tions. The Eu and Ce anom a lies re flect a hy dro ther mal con tri bu tion of REE. Geo chem i cal and geo log i cal data sug gest that the Igdekoy-Doganlar bo rate de pos its were formed in high-pH playa lakes that were dis charged from vol ca - nic and ter res trial en vi ron ments un der evap o ra tive con di tions due to the ef fect of arid-semi arid cli mate.
Key words: REE, trace el e ment, bo rate, min er al ogy, ul ex ite, probertite.
INTRODUCTION
Nearly 72% of bo rate re serves in the world are lo cated in the west part of Tur key. In ad di tion to well-known de pos its, there is a new de posit near Igdekoy-Doganlar vil lages in the Emet re gion (Fig. 1). The de posit is lo cated 3 km north of the town of HisarcÏk. In pre vi ous stud ies, the for ma tion of bo rate de pos its in the Emet re gion was dis cussed in terms of gen eral ge ol ogy and min er al og i cal find ings (Gawlik, 1956; Ozpeker, 1969; Inan, 1975; Yalcin, 1984; Yalcin et al., 1985; Gundogdu and Yalcin, 1985; Yalcin and Gundogdu, 1987; Floyd et al., 1998; HelvacÏ and Orti, 1998, 2004; Colak et al., 2003; Gemici et al., 2004; Sayin, 2007; Ozkul, 2008; Gar cia-Veigas et al., 2010, 2011; Unlu et al., 2011; HelvacÏ, 2015a, b; Ozkul et al., 2015, 2017; Coo per et al., 2016; Orti et al., 2016). In these stud - ies, it was sug gested that the bo rate de pos its were de pos ited in Mio cene lac us trine en vi ron ments in as so ci a tion with vol ca nic ac tiv ity span ning from Paleogene to Qua ter nary times. Com po - si tions of ma jor, trace and rare earth el e ment (REE) of bo rates were also in ves ti gated (Ilhan, 2006; Kocak and Koc, 2009, 2012, 2016, 2018; Koc et al., 2017; Kocak, 2017).
Geo chem i cal data showed the fol low ing el e ment en rich - ments: Ca, As, Li, Sb, Cs, Se and Sr in the Kestelek de posit (Koc et al., 2017); Ca, Se, Sr, As, Li, Mo and Sb in the Bigadiç
de posit (Kocak and Koc, 2012); Ca, Na, Mg, Sr, Li, Se, As and Cs in the KÏrka de posit (Kocak and Koc, 2016); Ca, Sr, Li, Se, As, Cs, Sb and Pb in the Emet (HisarcÏk and Espey) de posit (Kocak and Koc, 2018); and Sb, Li, Se, Cs, As and Sr in the ªeyhler (Emet) de posit (Kocak, 2017). There has been no study of the re la tion ship be tween el e ment con tents and the for - ma tion en vi ron ment of bo rates in the Igdekoy-Doganlar de - posit. In this study, the abun dances of ma jor, trace and rare earth el e ments and their geo chem i cal fea tures were used to de fine the de po si tion con di tions of the bo rate min er als. The re - sults are com pared with other de pos its. Al though pres ent day tech nol ogy and eco nom ics are not suf fi cient to ac quire by-prod - ucts of the ore el e ments, this may be the pos si ble in the fu ture.
This study pro vides new geo chem i cal data from the Igdekoy- Doganlar Na-Ca bo rate de posit. The data were used to re con struct the depositional con di tions that con trol for ma tion of the Na-Ca and Ca rich bo rates.
GEOLOGIC SETTING
The Ana to lian Plate is lo cated in the col li sion zone be tween the Eur asia and the Afro-Ara bian plates. The west ern Ana to lian bo rate de pos its were formed in par al lel with the Aegean vol ca - nic arc formed by the Af ri can plate sink ing along the Hel lenic trench, which was de vel oped in subduction en vi ron ments (HelvacÏ, 2015a). The ge ol ogy of the bo rate de posit and the sur round ing Emet Ba sin within the re gion was com piled from Ozkul (2008). In the Emet ba sin, pre-Mio cene rocks (HelvacÏ and Firman, 1977; Yalcin, 1984) con sist of schist (SarÏcasu For - ma tion), mar ble (ArÏkaya For ma tion), BudaÈan lime stone and
* E-mail: ikocak@bandirma.edu.tr
Received: March 13, 2020; ac cepted: July 2, 2020; first published online: August 31, 2020
EÈrigöz granitoid (Akdeniz and Konak, 1979). These units are over lain by Neo gene con glom er ate-sand stone (TaêbaêÏ For - ma tion), Koprucek fel sic base ment volcanics, basal sed i ments [lime stone (Karbasan For ma tion), Yeniceköy lime stones, con - glom er ate, sand stone (Beykoy For ma tion), Ergunler lime - stones, Igdekoy For ma tion], cover sed i ments [Emet cover lime - stones, sand stone (Merkezsihlar For ma tion)] and Derekoy mafic up per volcanics, re spec tively. The Neo gene units are cov ered by Qua ter nary trav er tine, old river ter races and al lu - vium (Fig. 2).
The Igdekoy For ma tion that hosts the bo rate lev els is dom i - nated by green, mod er ately con sol i dated siltstone and clay - stone and lesser amounts of thin lime stone-marl and tuff interlayers. The for ma tion is ex posed in a nar row area east of Igdekoy and Hamamköy, NW of HisarcÏk and around the Merkezsihlar and the Killik sites. The thick ness of the for ma tion is be tween 30 and 450 m (Akdeniz and Konak, 1979; Yalcin, 1984; Yalcin et al., 1985; Dundar et al., 1986; Ozkul, 2008). The marl, claystone and thin-bed ded lime stone lev els of the Igdekoy For ma tion con form ably over lie the Ergunler lime stones. To - wards the top, the se quence changes to green ish claystone and siltstone interbedded with small amounts of tuff lay ers which in clude the bo rate lay ers. The cole man ite nod ules are ra - dial and may at tain a ra dius of 5–60 cm. The clay min er al ogy in
this layer is illite and mont mo ril lo nite (HelvacÏ and Firman, 1977;
Gundogdu and Yalcin, 1985; Yalcin and Gundogdu, 1985, 1987; Dundar et al., 1986). Clays mostly sur round the cole man - ite nod ules as a film. In some lev els ar senic-rich claystone con - tains orpiment and realgar crys tals up 5–10 cm across, to gether with na tive sul phur. In the up per sec tion of the se quence, marl lay ers dom i nate. The marls show a col our dif fer ence from dirty white at the base to grey to the top. They have an eathy ap pear - ance and in clude peat and cole man ite nod ules. The marl and clay lay ers are rich in or ganic-ma te rial (as ev i dence by the pres - ence of peat; Ozkul, 2008).
MATERIALS AND METHODS
In this study, min er al og i cal and geo chem i cal anal y ses were car ried out on 17 bo rate sam ples col lected from bore hole BME 2003/1 which was drilled in 2003 by Etimine Emet Bor Ex ploi ta - tion Man age ment. The lo ca tions of the col lected sam ples are shown in the bore hole log (Fig. 3) drawn from the raw data.
For min er al og i cal stud ies, an op ti cal, Con fo cal Raman spec trom e ter and X-ray diffractometry (XRD) meth ods were used. XRD de ter mi na tions were con ducted at the Turk ish Pe -
808 smail Koçak
Fig. 1. Lo ca tion map for study area in west ern Anatolia
tro leum Cor po ra tion (TPAO) lab o ra to ries with a Rigaku D brand Max 2200 Ul tima/Pc de vice with a Cu-tube un der con di tions of 40 kV, 20 mA, 1.54059 A° (CuKa1) wave length and 2°/min scan ning speed. The Raman mea sure ments were car ried out with an Olym pus BX41 model Con fo cal Raman spec trom e ter at the Ge ol ogy De part ment in An kara Uni ver sity. A Horiba Jobin Yvon sys tem equipped with a 633 nm la ser set was used for the Raman mea sure ments. An elec tri cal cooled charg ing cou pling de vice (CCD) de tec tor was used to ob tain spec tra, and the la - ser spot was set on bo rate sur faces with 10x or 50x long-fo - cused ob jec tives, en abling a work ing dis tance of 65 and 13 mm, with a lat eral res o lu tion of 5 and 2 mm re spec tively. The po lar iza tion of the in ci dent la ser beam was cho sen anal o gous with the pref er en tial do main ori en ta tion of sam ples (y) and
spec tra were ob tained in a strict back scat ter ing ge om e try. The phonon mode in ten sity val ues for bo rate were ob tained us ing the Lab spec 4.02 (Horiba Jobin Yvon) kit, based on Gaussi an- Lorentzian mixed func tions af ter sub tract ing a base line and ap - ply ing the ini tial mode ap prox i ma tions ac cord ing to the bo rate and min eral Raman anal y ses by Kadioglu et al. (2009) and Gullu and Kadioglu (2017).
Be fore chem i cal anal y sis, sam ples were cleaned with pres sur ized air and then dis tilled washed to re move im pu ri ties.
The geo chem i cal anal y ses were con ducted as the LF202 pack age at Bu reau Veri tas Min eral Lab o ra tory (LF202 pack - age). REE anal y sis was per formed us ing In duc tively Cou pled Plasma -Mass Spec trom e try (ICP-MS) and ma jor and trace el - e ments were de ter mined by In duc tively Cou pled Plasma - Fig. 2. Ge ol ogy map of study area and sur round ings (sim pli fied af ter Ozkul, 2008)
-Emis sion Spec tro s copy (ICP-ES) method. B2O3 anal y sis was com pleted with Thermo Sci en tific ARL Perorm’x wave dispersive X-ray Flu o res cence (WD-XRF) spec trom e ter at the Sci ence and Tech nol ogy Ap pli ca tion and Re search Cen ter of Bozok Uni ver sity.
RESULTS AND DISCUSSION
MINERALOGY
From the op ti cal, con fo cal Raman spec tros copy and X-ray diffractometry (XRD) stud ies, cole man ite, ul ex ite, hydrobora - cite and probertite were iden ti fied, to gether with ha lite, anhy - drite, glau ber ite, smectite and illite.
MICROSCOPY INVESTIGATIONS
Mi cros copy stud ies re vealed the pres ence of cole man ite, hydroboracite, ul ex ite and probertite. Ulexites show ra dial growth formed as sep a rate crys tals (Fig. 4A). In thin-sec tion ul - ex ite is ra dial, yel low ish-white un der plane po lar ized light. It shows sec ond or der in ter fer ence col our un der cross polars (Fig. 4B). Probertite is rec og nized as small crys tals (Fig. 5A) and is char ac ter ized by a dirty white-grey col our un der plane po lar ized light and blu ish green, grey, blue, or ange and pur plish blue un der cross polars (Fig. 5B).
CONFOCAL RAMAN SPECTROMETER ANALYSES
The Con fo cal Raman spec tros copy method al lows de ter mi - na tion of the min er al ogy of a sam ple based on the re sults of
810 smail Koçak
Fig. 3. Log of BME 2003/1 drill ing and bo rate sam ple depths
point anal y sis. Min er als iden ti fied un der thin-sec tion were also ver i fied from Raman spec tra. In Fig ure 5C, the blue line in con - fo cal Raman spec tros copy is the ref er ence line for probertite and the red line is the peak value for sam ple. The pres ence of cole man ite, hydroboracite, and ul ex ite min er als was iden ti fied by the con fo cal Raman spec tros copy.
X-RAY DIFFRACTOMETRY (XRD) ANALYSES
The XRD was used to de fine clay types and min er als which could not be rec og nized by mi cros copy and con fo cal Raman spec tros copy stud ies. XRD study of the Igdekoy-Doganlar bo - rates re vealed the pres ence of cole man ite, ul ex ite (Fig. 4C), hydroboracite and probertite min er als. Ha lite and anhydrite ac - com pany the bo rate min er als. Smectite and illite are the ma jor clay types.
GEOCHEMISTRY OF THE IGDEKOY-DOGANLAR DEPOSIT
MAJOR ELEMENTS
The ma jor el e ment con cen tra tions with the av er age val ues, and av er age con cen tra tions in the Earth’s crust – ECA (val ues af ter Krauskopf, 1979), andesites – AA (val ues af ter Schroll, 1975) and fresh wa ters – FWA (val ues af ter Sahinci, 1991;
Abollino et al., 2004) are shown in Ap pen dix 1*. The ranges of ma jor el e ment ox ides of the bo rate sam ples are: 0.06–5.06 wt.% for SiO2, <0.04–0.88 wt.% for Fe2O3tot, 0.03–3.53 wt.% for MgO, 12.95–27.49 wt.% for CaO, 0.02–19.70 wt.% for Na2O, and 28.46–46.26 wt.% for B2O3. Based on these val ues, the av - er age con cen tra tions of ma jor el e ment ox ides are cal cu lated:
2.38 wt.% for SiO2, 0.22 wt.% for Fe2O3tot, 1.22 wt.% for MgO, Fig. 4A – ra dial ul ex ite, B – ul ex ite un der crossed polars, C – XRD pat terns for ul ex ite
* Supplementary data associated with this article can be found, in the online version, at doi: 10.7306/gq.1555
19.39 wt.% for CaO, 5.82 wt.% for Na2O, and 41.05 wt.% for B2O3 (Ap pen dix 1). The av er ages val ues of CaO, Na2O and B2O3 con cen tra tions in Igdekoy-Doganlar bo rates are in - creased 3.38, 1.80 and 41047-fold with re spect to ECA and 2.98, 1.44 and 27364-fold with re spect to AA. All other ma jor el - e ment ox ides show pro por tional de ple tions com pared to both ECA and AA (Ta ble 1).
TRACE ELEMENT
The con cen tra tions and av er age con cen tra tion of trace el e - ments in the Igdekoy-Doganlar bo rates and their av er age con - cen tra tions in the ECA, AA and FWA are shown in Ap pen dix 2.
All trace el e ments in Igdekoy-Doganlar bo rates are en riched with re spect to FWA (Ap pen dix 2). Ac cord ing to the re sults of anal y sis, Ni, Co, Cu, Pb, Mo, S, As, Se, Sb, Te, Ag, Rb, Ba, Sr, Cs, Li, Nb, Zr, Y, Th, and U were de ter mined in bo rate sam ples.
Re gard ing ECA and AA, con tent of Se, As, Sr, Sb, Cs and Li in the Igdekoy- Doganlar bo rates are found to be higher than other el e ments. The con cen tra tions of these el e ments-vary in the range: 0.3–21.4 ppm for Se, 6.6–8250 ppm for As, 459–13154 ppm for Sr, <0.02–3.57 ppm for Sb, 2.2–101 ppm for Cs, and 3.7–296 ppm for Li. Ac cord ing to these re sults, the av er age value of Se, As, Sr, Sb, Cs and Li is cal cu lated as 12.9, 1523, 3607, 0.7, 44.8, and 91.3 ppm, re spec tively. With re spect to ECA and AA, re spec tively, the con cen tra tions are in creased by:
As (845–801 fold), Se (258–258 fold), Cs (14.92–19.46 fold), Sr (9.62–4.51 fold), Sb (3.63–3.63 fold), and Li (4.56–4.56 fold) el - e ments are vari ably in creased (Ap pen dix 2). S con tent is in - creased 14.39–21.58 fold.
Pre vi ous stud ies in west ern Anatolia re vealed sim i lar re - sults. Re ported el e ment en rich ments are As, Sb, Se, Mo, Li and Sr (Kocak and Koc, 2012); for the Bigadiç de posit; Li, Se, Mo, Sr, Sb, Cs and As (Koc et al., 2017); for the Kestelek de posit;
Cs, Se, Sr, As and Li (Kocak and Koc, 2016); for the KÏrka de -
812 smail Koçak
Fig. 5A – gran u lar crys tal line probertite, B – probertite un der crossed polars, C – Raman spec trum for probertite
posit; Sb, Se, Li, Pb, As, Sr and Cs (Kocak and Koc, 2018) for the Espey-HisarcÏk (Emet); and As, Cs, Li, Se, Sb and Sr (Kocak, 2017) for Þeyhler (Emet) bo rate de posit. These data show that Se, Sr, Li and As en rich ments are com mon for KÏrka, Bigadiç, Emet (Espey-HisarcÏk), Kestelek, ªeyhler (Emet) and the stud ied Igdekoy-Doganlar de pos its.
Gundogdu and Yalcin (1985) have ex am ined the re la tion - ship be tween the dis tri bu tion of bo rate for ma tion and trace el e - ments and they men tion that the use of Sr in bo rate ex plo ra tion is more im por tant than Li and Ba. Fur ther more, geo chem i cal stud ies of Emet soils by Ozkul et al. (2017) re vealed Na, K, Sr, As, Sb, Cs, Li and Be anom a lies. As in di cated by this study, B, Sr, Sb, Cs, Li, Se and As that es pe cially en hanced in the bo rate de posit can be uti lized as in di ca tor el e ments for ex plo ra tion of bo rate de pos its.
As known in many ore de pos its, other el e ments may be ex - tracted as by-prod ucts in ad di tion to the main ore (e.g., Se in Cu de pos its). Flo ta tion con cen trates of most cop per ores con tain 100–400 ppm Se which is an im por tant source for Se pro duc - tion (Habashi, 1997). The same is also valid for Li. Li is pro - duced from salt de pos its, lakes and sea. Li con cen tra tions are 320 ppm in Salar de Uyuni (Bolivia), 52 ppm in Great Salt Lake (Utah), 65 ppm in Searles Lake (Cal i for nia), 160 ppm in Clay ton Val ley (Ne vada) and 10 ppm in Dead Sea (Is rael–Jor dan) (Munk et al., 2016). In ad di tion, there are stud ies about ob tain - ing Li from sea wa ter in which Li con cen tra tion is 0.17 ppm (Habashi, 1997). There fore, when eval u at ing bo ron de pos its ex trac tion of Se (0.34–21.4 ppm) and Li (3.7–295 ppm) el e - ments could also be con sid ered.
Ac cord ing to Webb and Kamber (2000) low con cen tra tions of Th, Sc, and Hf and ab sence of a strong cor re la tion be tween Y/Ho and Zr (0.3 for this study) shows a low ter res trial con tri bu - tion. In the pres ent study, con cen tra tions Sc and Hf are be low de tec tion limit and Th has a low con cen tra tion.
Li and Cs are con cen trated mainly in the wa ter of rhyolitic or andesitic en vi ron ments or of sed i men tary ar eas of com pa ra ble rock com po si tions (Ellis, 1979). Li can be as so ci ated with hy - dro ther mal phases of vol ca nic ac tiv ity. Ab sorp tion of lith ium
ions by clay min er als caused high con cen tra tions in sed i men - tary for ma tions. Hy dro ther mal al ter ations and leach ing mo bi lize lith ium. Cs is found es pe cially in Li-bear ing micas and K-bear - ing min er als (Burkut, 1977). Cs, one of the larg est al kali cat ions, is larger than that of ma jor el e ments, but it can re place K. Dur - ing the course of mag matic crys tal li za tion, Cs is in vol a tile phase and since it is more vol a tile than Rb and K, Cs is mostly found in K-rich vol ca nic rocks (Koc et al., 2017). The main source of Se, a chalcophile el e ment, is vol ca nic ac tiv ity. Se is gen er ally found in hy dro ther mal for ma tions es pe cially epi ther - mal Sb, Ag, Au and Hg, sul phur de pos its and vol ca nic rocks (Elkin and Mar grave, 1968; Halilova, 2004). In ad di tion, Se is en riched in low tem per a ture ther mal bi car bon ate wa ters in vol - ca nic ar eas (Malisa, 2001). Vol ca nic in put and hy dro ther mal so lu tions are the main cause of As en rich ment (Goldschmidt, 1954). Ar senic en ters the sed i men tary cy cle by al ter ation of mag matic rocks, vol ca nic gas ses, and hot wa ters (Krauskopf, 1979). It is known that stron tium is found in acidic rocks and volcanics rather than ba sic rocks and en riched in supergenic en vi ron ments and hy dro ther mal sys tems (Kocak and Koc, 2012). Sb is a chalcophile el e ment and as so ci ated with low tem per a ture hy dro ther mal flu ids, to gether with Au, Ag, As, Sb, Pb, Zn, Cd, Hg, Tl, Ga (Hannington et al., 1991; Lorand et al., 2018) It is known that Sb is closely re lated to vol ca nic ac tiv ity (Petrascheck and Pohl, 1982). Fol low ing the so lid i fi ca tion of mag mas, Sr can be en riched in vol a tile-rich so lu tions (e.g., Cl, F, and B) and post-mag matic for ma tions (Burkut, 1977). Ad di - tion ally, many stud ies show that Sr is car ried into bo rate de pos - its via bo ron-rich hy dro ther mal so lu tions (Ata man and Baysal, 1978; Yalcin, 1984; Gundogdu and Yalcin, 1985).
RARE EARTH ELEMENTS
REE con cen tra tions were used to de fine some of physico - chemical con di tions of the Igdekoy-Doganlar de posit. For this pur pose, re sults of REE anal y sis (Ap pen dix 3) were nor mal ized rel a tive to Post Archean Aus tra lian Shale (PAAS) av er ages En rich ment and de ple tion co ef fi cients for Igdekoy-Doganlar bo rate sam ples
Co ef fi cient of en rich ment by Earth crust
Co ef fi cient of en rich ment by an de site
Co ef fi cient of de ple tion by Earth crust
Co ef fi cient of de ple tion by an de site
B2O3 46904 31269 – –
SiO2 – – 25.39 23.41
Al2O3 – – 50.59 55.28
Fe2O3tot – – 34.67 37.56
MgO – – 3.13 2.96
CaO 3.38 2.98 – –
Na2O 1.80 1.44 – –
K2O – – 8.70 9.53
TiO2 – – 32.43 51.89
P2O3 – – 12.60 18.33
Se 257.88 257.88 – –
Li 4.56 4.56 – –
As 845.88 801.36 – –
Cs 14.92 19.46 – –
Sr 9.62 4.51 – –
Sb 3.63 3.63 – –
S 14.39 21.58 – –
(Tay lor and Mclennan, 1985), and spi der di a grams were cre - ated (Fig. 6).
SREE data of Igdekoy-Doganlar sam ples are very low rang - ing from 1.4 to 23.7 ppm (Ap pen dix 3) which is at trib uted to low REE ac cu mu la tion un der high pH (>7.5) con di tions (Michard and Albarede, 1986). Also the REE con tent of min er al iz ing flu - ids de pends on the pH, wa ter/rock ra tio, tem per a ture, re dox po - ten tial, and the dis tance be tween the mag matic source and the de po si tion site (Palinkas et al., 2013).
There are Eu and Ce anom a lies in the stud ied sam ples (Fig. 6 and Ap pen dix 3). These anom a lies were cal cu lated from the equa tions of Eu/Eu* = [Eu /(Sm×Gd)]0.5 (Yang et al., 2014), Ce/Ce* = [Ce/(0.5La+0.5Pr)]N (Bau, 1991; Webb and Kamber, 2000) and Ceanom= log [3Ce / (2La+Nd)] N (Wright et al., 1987).
In the Igdekoy-Doganlar area, the av er age Ce/Ce* is 1.07 (0.73–1.78) and av er age Eu/Eu* value is 1.96 (0.87–3.77).
If Ceanom>–0.1 Ce is en riched, whereas Ceanom<–0.1 is in - dic a tive of neg a tive Ce anom aly (Wright et al., 1987). As shown in Fig ure 6 and Ap pen dix 3, neg a tive Ce anom aly is pres ent in 6 of the Igdekoy-Doganlar bo rate sam ples and pos i tive Ce anom - aly in 5 bo rate sam ples. In ad di tion, pos i tive Eu anom aly was found in 13 sam ples and neg a tive Eu anom aly in 4 sam ples, re - spec tively.
Ce and Eu anom a lies are re lated with changes in re dox con di tions (Loveland, 1989; Wood, 1990; Bau, 1991). A neg a - tive Ce anom aly, dem on strates high ox y gen fugacity in the en - vi ron ment. Early-stage flu ids are rep re sented by pos i tive Eu and Ce anom a lies and high SREE, whereas hy dro ther mal flu - ids of later stages are rep re sented by neg a tive Eu and Ce anom a lies and low REE (Jiang et al., 2004). For the Igdekoy - -Doganlar bo rates, Ceanom<–0.1 (Ap pen dix 3) in di cates a high ox y gen fugacity (fO2) of the en vi ron ment and pos i tive Eu anom - aly is rep re sen ta tive of a hy dro ther mal source (Constanto - poulos, 1988; Canet et al., 2005). Hence, it ap pears that low REE con tent, late-stage, hy dro ther mal flu ids en tered the depositional en vi ron ment. Both neg a tive and pos i tive Ce anom a lies may in di cate that the en vi ron ment un der went re dox pro cesses due to the ef fect of ox y gen ated and H2S-bear ing hy - dro ther mal so lu tions. These anom a lies show that the lake wa - ter in the depositional en vi ron ment had a con tri bu tion from hy -
dro ther mal flu ids. Kato (1999) and Habaak (2004) found LREE en rich ment (LREE/HREE is ~8), en rich ment in La and low to tal REE con tent in the iron de posit and sug gested that min er al iza - tion formed un der shal low ox i dized con di tions from me te oric and hy dro ther mal flu ids. A slightly neg a tive Ce anom aly is in ter - preted to in di cate the in flu ence of vol ca nic ma te rial (Fleet et al., 1976; Sasmaz et al., 2014).
As shown in Fig ure 6 and Ap pen dix 3, there are pos i tive Eu anom a lies in the Igdekoy-Doganlar area in 13 sam ples and neg a tive Eu anom a lies in 4 sam ples. It is dif fi cult to make an eval u a tion based on this anom aly be cause neg a tive Eu anom a - lies are rec og nized in var i ous en vi ron ments. Con sid er ing the re la tion ship of bo ron with a lac us trine en vi ron ment and vol ca nic ac tiv ity (by hy dro ther mal flu ids) in the Igdekoy-Doganlar de - posit, REE dis tri bu tion in hy dro ther mal flu ids and nat u ral should also be taken into con sid er ation. Mclennan (1989) sep a rated the ter res trial wa ters into low and high-pH types. Wa ters with a neg a tive Eu anom aly are de fined as high-pH hy dro ther mal wa - ters in the ter res trial en vi ron ment (Mclennan, 1989). Within the Igdekoy-Doganlar depositional en vi ron ment a neg a tive Eu anom aly may re cord dis charge from high-pH hy dro ther mal wa - ters. Al ter na tively, a neg a tive Eu anom aly is also sug gested as an in di ca tor of re duc ing en vi ron ments (Henderson, 1984;
Constanto poulos, 1988). Hy dro ther mal flu ids (Sverjensky, 1984; Bau, 1991) and leach ing pro cesses cause a re duc tion of Eu3+ to Eu2+ and ac cord ingly, a neg a tive Eu anom aly. A neg a - tive Eu anom aly may also be gen er ated by low-tem per a ture hy - dro ther mal wa ters (Hekinian et al., 1993). A pos i tive Eu anom - aly is re garded as an in di ca tor of a mag matic source (Nance and Tay lor, 1977; Bhatia, 1985; Sant’anna et al., 2006). It also shows the pres ence of CO2 (Graf, 1977; Gale et al., 1997) that can be re lated to CO2 pro duced by vol ca nic ex ha la tions.
Hence, the neg a tive Eu anom aly in the Igdekoy-Doganlar re - gion be comes a prob lem atic in in ter pret ing the bo rate oc cur - rences as form ing within ox y gen ated lake wa ters. In such an ox - y gen ated en vi ron ment, Eu2+ is eas ily ox i dized to Eu3+ and is in - cor po rated in bo rate for ma tion be cause its ionic ra dius is sim i lar to that of Na and Ca which re sults in pos i tive Eu anom aly (Constantopoulos, 1988; Canet et al., 2005). So, there must be an other ex pla na tion for the neg a tive Eu anom aly in the
814 smail Koçak
Fig. 6. REE dis tri bu tion for the Igdekoy-Doganlar de posit (nor mal ized with Tay lor and Mclennan, 1985)
anom aly in di cates dis so lu tion of Ca-plagioclase (Weill and Drake, 1973). If the Ca-plagioclase con tent of vol ca nic rocks in the study area was high and the al ter ation was suf fi cient, Eu would be in creased in the lac us trine en vi ron ment where the Igdekoy-Doganlar bo rates were de pos ited. The pres ence of neg a tive Eu anom aly may arise from low de grees of hy dro ther - mal al ter ation (Usui and Mita, 1995; Sasmaz et al., 2014).
Ho is ex pected to show a pos i tive anom aly in Ca-bo rate sam ples be cause its ionic ra dius is iden ti cal to that of Ca. In - deed, a slightly pos i tive Ho anom aly was rec og nized.
The av er age Y/Ho value of bo rates in the Igdekoy-Doganlar area is 30 (5 to 44). Mod ern sea wa ter has no ta bly high Y/Ho ra - tio (44) with re spect to chondrite (26–28) (Kamber and Webb, 2001). Most geo log i cal ma te ri als (in clud ing all vol ca nic rocks and clastic de pos its) have Y/Ho ra tio close to chondritic value (Nozaki et al., 1997). The av er age of Y/Ho of the Igdekoy- Doganlar bo rates is very sim i lar to the chondritic ra tio.
Low REE con tents (<6.4 ppm), LREE de ple tion in PAAS - -nor mal ized pat terns and pos i tive Eu anom aly prob a bly in di - cate a hy dro ther mal source (Sant’anna et al., 2006).
In gen eral, the Igdekoy-Doganlar bo rate sam ples are char - ac ter ized by LREE and me dium rare earth el e ment (MREE) en - rich ments. LREE en rich ments may in di cate a hy dro ther mal source. MREE en rich ment is also char ac ter is tic of high tem per - a ture acidic hy dro ther mal flu ids (Fee et al., 1992; Johannesson et al., 1996). REE com pounds orig i nat ing from mod er ately acidic rocks also show MREE en rich ment and pos i tive Eu anom aly (Johannesson et al., 1996).
The REE con tents and el e men tal anom a lies pro vided the fol low ing in for ma tion:
–low REE con tents and LREE de ple tion in di cate a hy dro ther - mal source;
–Ce val ues and neg a tive anom a lies show that the bo rates were de pos ited in an ox y gen ated en vi ron ment. How ever, the ab sence or weak neg a tive Ce anom a lies in some sam - ples show a partly ox y gen ated en vi ron ment (Kato and Isozaki, 2009), and H2S-bear ing hy dro ther mal flu ids are thought to had em a nated from some parts of the lake, which is sup ported by the pres ence of realgar, orpiment and na - tive sul phur min er als in bo rate de pos its at Igdekoy- Doganlar;
–sam ples with a pos i tive Eu anom aly in di cate a mag matic or - i gin and a CO2 con tri bu tion from vol ca nic ex ha la tions;
–the weak neg a tive Eu anom a lies in four sam ples is ex - plained by a high pH, low de grees of hy dro ther mal al ter - ation and low Eu con tri bu tions to the lake en vi ron ment.
In west ern Anatolia, a low REE con tent is a com mon fea ture in all de pos its. Neg a tive Eu anom a lies were found in KÏrka, HisarcÏk (Emet) and ªeyhler (Emet) bo rate de pos its and pos i -
ªeyhler (Emet) de pos its as well. Small Ce anom a lies are com - mon in all de pos its in west ern Anatolia (Kocak and Koc, 2016, 2018; Koc et al., 2017; Kocak, 2017). As seen in pre vi ous stud - ies, both pos i tive and neg a tive Eu anom a lies are ob served in all de pos its with a low Ce anom aly.
CONCLUSIONS
In the Igdekoy-Doganlar de posit, cole man ite, ul ex ite, hydro - boracite and probertite were found to be the ma jor bo rate min - er als. In ad di tion, ha lite, anhydrite, glau ber ite, smectite and illite were also found.
B, Li, Se, As, Sb, Sr and Cs are con cen trated in these de - pos its and can be used as in di ca tor el e ments for ex plo ra tion of bo rate de pos its. B and Sr are par tic u larly use ful for ex plo ra tion of bo rate de pos its.
Among the el e ments that are en riched in the Igdekoy - -Doganlar re gion, such as Sr, As, Cs, Se, Li and Sb, some of them, es pe cially Li and Se may be pro duced as by-prod ucts.
Low con cen tra tions of Sc, Hf, and low Th and a very weak cor re la tion be tween Zr and Y/Ho in di cate ex cep tion ally low ter - res trial con tri bu tions.
In the Igdekoy-Doganlar re gion, Ce and Eu show both neg - a tive and pos i tive anom a lies, but pos i tive Ce and Eu anom a lies are dom i nant. This data in di cates that the sed i men tary en vi ron - ment of the Igdekoy-Doganlar bo rate de posit was ox y gen ated and high-pH hy dro ther mal wa ters con trib uted to bo rate for ma - tion pro cesses. Due to a con ti nen tal crust con tri bu tion and low tem per a ture con di tions, the in ter ac tion be tween vol ca nic rocks and ground wa ter was lim ited which re sulted in a neg a tive Eu anom aly in some sam ples.
Geo log i cal data, ev i dence of hy dro ther mal con tri bu tions, the pres ence of min er als form ing in al ka line con di tions, and REE anom a lies all sug gest that the Emet Igdekoy-Doganlar bo - rate de pos its formed in high-pH playa lakes. The wa ter was sourced from vol ca nic and ter res trial en vi ron ments and con - cen trated un der evap o ra tive con di tions due to the ef fect of an arid to semi-arid cli mate.
Ac knowl edge ments. Thanks to Prof. ª. Koç at the An kara Uni ver sity for re view, rec om men da tions and con tri bu tion.
I would also like to thank all the em ploy ees of Eti Mine Works Gen eral Di rec tor ate. I would like to thank Prof. H. YalçÏn for his me tic u lous and valu able con tri bu tions as the re viewer of my manu script, and also to thank the jour nal ref er ees for their com - ments and sug ges tions.
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