Geo chem i cal and tec tonic char ac ter is tics of man ga nese min er al iza tion in the Yozgat re gion, Tur key
Nursel ÖKSÜZ1, smail KOÇAK2, * and UÈur TEMIZ1
1 Bozok Uni ver sity, De part ment of Geo log i cal En gi neer ing, Yozgat, Tur key
2 BandÏrma Onyedi Eylül Uni ver sity, De part ment of En gi neer ing Sci ence, Fac ulty of En gi neer ing and Nat u ral Sci ences, BalÏkesir, Tur key
Öksüz, N., Koçak, ., Temiz, U., 2021. Geo chem i cal and tec tonic char ac ter is tics of man ga nese min er al iza tion in the Yozgat re gion, Tur key. Geo log i cal Quar terly, 65: 31, doi: 10.7306/gq.1599
As so ci ate Ed i tor: Stanis³aw Mikulski
North of the Cen tral Ana to lian Crys tal line Com plex and bor dered by the zmir–An kara–Erzincan Su ture Zone, min er al iza tion oc curs within ophiolites known as Ana to lian Ophiolite Com plex. The min er al iza tion is pres ent within banded, lam i nated and len tic u lar radiolarites which are in tensely frac tured and folded. It is dis trib uted around Derbent, Baltasarilar, Cihanpasa, Buyukmahal, Eymir and Kadisehri where pyrolusite, psilomelane, manganite and braun ite com prise the main paragenesis and jacobsite, mag ne tite, li mo nite and goethite are mi nor phases. The neg a tive Eu anom aly sug gests that the hy dro ther mal source was dis tant from the min er al iza tion area or was mixed with sea wa ter. All sam ples from the Cihanpasa and Buyukmahal ar eas have a neg a tive Ce anom aly and re sem ble low-tem per a ture hy dro ther mal min eral de pos its. Sam ples from other lo ca tions (Derbent, Baltasarilar, Cihanpasa, Eymir, Buyukmahal, Tarhana) are char ac ter ized by both neg a tive and pos i tive Ce anom a lies. From this it can be in ferred that both hy dro ther mal and hydrogenetic pro cesses were ac tive in min er al iza tion. High Ba con tents and a LREE-en riched pat tern to gether with neg a tive Ce anom a lies and trace el e ment dis tri - bu tions in di cate that the min er al iza tion in the area was de rived from a pri mary hy dro ther mal source. In ad di tion, diagenetic and epigenetic pro cesses may also have played an im por tant role in the man ga nese min er al iza tion.
Key words: man ga nese, geo chem is try, hydrogenetic, hy dro ther mal, Yozgat (Tur key).
INTRODUCTION
Man ga nese ox ide de pos its are found within sev eral tec tonic set tings. Based on their min er al og i cal char ac ter is tics and tec - tonic set tings these de pos its are clas si fied into hydrogenetic, hy dro ther mal and diagenetic types (Roy, 1992; Hein et al., 1997). Some pa ram e ters such as ter res trial in put and mi cro bial pro cesses are im por tant geo chem i cal fea tures re gard ing the gen e sis of man ga nese min er al iza tion (Maynard, 2010; Polgári et al., 2012a, b, 2016). Through supergene pro cesses man ga - nese ox ides can be de pos ited both in ma rine and ter res trial en - vi ron ments (Maynard, 2010).
Man ga nese de pos its in Tur key are di vided into four groups based on their or i gin, age and struc tural char ac ter is tics (Öztürk, 1993). The first group is man ga nese de pos its of hydrogenetic and hy dro ther mal type within radiolarian cherts. These are rep - re sented by high Mn-Si and low Al-Fe com po si tions.
Palaeotethys units are ex posed in the ophiolites of Karakaya,
zmir–An kara–Erzincan and South east ern Anatolia Su ture Belts (Fig. 1). De pos its of the sec ond group are as so ci ated with black shales within lower Cre ta ceous car bon ates in the west ern Taurides. The Fe con tent of these diagenetic de pos its is greater than that of those as so ci ated with black shales while their Si con tent is lower. The third group com prises hy dro ther - mal de pos its within vol cano-sed i men tary units of the Black Sea and as so ci ated con ti nen tal arc. The fourth group are formed within Oligocene de pos its of the Thrace ba sin. These de pos its with low Mn-Si con tents are of high ton nage (Öztürk, 1993).
The man ga nese min er al iza tion in the study area is ex posed through out the Artova ophiolitic belt NE–NW of the Yozgat dis - trict at the base of the north ern branch of the Neotethys along the zmir–An kara–Erzincan (IAE) Su ture Zone (Figs. 1A and 2).
Sev eral stud ies have been con ducted re gard ing the gen eral ge ol ogy, stra tig ra phy and tec ton ics of the re gion as well as the min er al ogy, geo chem is try and or i gin of the man ga nese mineralizations (Akçe and KadÏoÈlu, 2005; ªaºmaz et al., 2005;
KadÏoÈlu et al., 2006; Öksüz, 2011a, b; Öksüz and Okuyucu, 2014). The min er al iza tion in the study area is as so ci ated with the radiolarian cherts in cluded in the Up per Cre ta ceous ophiolite units. This study: (1) de ter mines the dif fer ences and sim i lar i ties be tween the types of min er al iza tion by com par ing
* Cor re spond ing au thor, e-mail: ikocak@bandirma.edu.tr Re ceived: No vem ber 25, 2020; ac cepted: May 3, 2021; first pub lished on line: June 24, 2021
Fig. 1A – map show ing ma jor tec tonic el e ments of Tur key, striped lines rep re sent su ture zones (mod i fied from Okay and Tüysüz, 1999); B – sim pli fied geo log i cal of the Cankiri Ba sin and sur round ing area (mod i fied from by Tüysüz and DellaloÈlu, 1992) Metamorphic massifs: IKM – Ilgaz–Kargi Massif, TK – Tokat Massif, GM – Galatya Massif, KM – Kirsehir Massif; NAF – North Anatolia
Fault, KEF – Kirikkale–Erba Fault
their min er al og i cal, orig i nal and geo chem i cal com po si tions; and (2) de vel ops a tec tonic model for the min er al iza tion.
GEOLOGICAL SETTING
Geo log i cally, Tur key is di vided into three tec tonic units: the Pontides, the Anatolide-Tauride and the Ara bian Plat form (Ketin, 1966; Okay, 2008; Fig. 1). These units, which were sur - rounded by oceans dur ing the late Me so zoic, are now sep a - rated by tec tonic lines or zones where oceans were subducted (Okay, 2008). The Pontides are lo cated north of the north ern branch of the Neotethys. Com plete clo sure of this ocean formed the zmir–An kara–Erzincan (IAE) Su ture. The IAE sep - a rates the Pontides in the north from the Anatolides–Taurides in the south. The north ern and south ern parts of the Kirsehir block are de mar cated by the IAE Su ture and In ner Tauride Su - ture, re spec tively. This block com prises the Kirsehir, Nigde and AkdaÈ mas sifs and sev eral bas ins. The Kirsehir block is also known as the Cen tral Ana to lian Crys tal line Com plex (CACC).
The Anatolide–Tauride con ti nent that com prises the CACC was a “foot wall” through out the Late Cre ta ceous and large ophiolite masses and ophiolitic melange at its base gave rise to the em - place ment of tec tonic slices (Fig. 1A). The geo log i cal units in the study area are com posed of al ter na tions of ophiolitic melange and ophiolitic block, and slice-bear ing vol ca nic and sed i men tary de pos its which are over lain by a re gres sive clastic se quence, termed the “Kalecik Unit” (Tüysüz and DellaloÈlu, 1992; Fig. 1B). This unit, at the east ern, west ern and north ern parts of the ÇankÏrÏ Ba sin, is rec og nized as a tec tonic slice be - tween the over ly ing Karakaya and Sakarya units and the un der - ly ing Iskilip Unit. The part of the Kalecik Unit in the study area and ophiolitic rocks ex posed along the IAE Su ture was named the Artova Ophiolitic Com plex (AOC) by (Ozcan et al., 1980).
The ophiolitic melange is a kind of tec tonic com plex con sist ing of rocks of the north ern branch of the Neotethys (ªengör and YÏlmaz, 1981) that was north erly subducted dur ing the Late Cre ta ceous, and var i ous rock units from the con ti nen tal mar gin (Temiz et al., 2010).
GEOLOGY OF THE STUDY AREA
Units in the study area are cat e go rized into four groups: (1) Permo-Tri as sic car bon ate units, (2) ophiolitic melange (3) intrusives cut ting these units and (4) sed i men tary and vol ca nic rocks of Ce no zoic bas ins, known as the Cen tral Ana to lian bas - ins, which over lie all these units (Fig. 2). The north ern sec tion of the area com prises Permo-Tri as sic car bon ate units. They have a block-like struc ture in part and are as so ci ated with vol ca nic rocks. The ophiolitic melange is found in the cen tral part of the study area. The em place ment of these ophiolitic rocks is re - ported to be re lated to an ensimatic arc (YalÏnÏz et al., 1996) and they are sug gested to be the rem nants of the north ern Neotethys Ocean (ªengör and YÏlmaz, 1981). Ophiolitic rocks are rec og nized as ei ther frag mented ophiolite bod ies or ophiolitic melange frag ments of var i ous sizes that were formed in front of ophiolite nappe. The CACC is in truded by sev eral granitoid and syenitoid plutons. Plutons at south of the study area cut the ophiolitic and meta mor phic units. 40Ar-39Ar bi o tite and hornblende, ti tan ite and zir con ages of these rocks are re - ported to be 95–70 Ma (Whit ney et al., 2003; Köksal et al., 2004; BoztuÈ et al., 2007). These units are over lain by sed i - men tary and vol ca nic units de pos ited in Eocene–Mio cene and Plio cene times. The cover units are com posed of ter res trial clastic rocks, car bon ates, ba salt and an de site.
MANGANESE MINERALIZATION
Six dif fer ent in stances of man ga nese min er al iza tion were in ves ti gated in the area de scribed, namely those of: Derbent, Baltasarilar, Cihanpasa, Buyukmahal, Eymir and Tarhana (Fig. 2). These min er al iza tion ex am ples ex pe ri enced in tense tectonism and all of them are interlayered with lam i nated and/or len tic u lar radiolarites (Fig. 3A–C). Both radiolarites and min er - al iza tion are frac tured and folded (Fig. 3A, B). In all these in - stances, syngenetic type pyrolusite is the main ore min eral.
How ever, in some of them diagenetic and epigenetic pyrolusite and other ox ide min er al iza tion are also ob served (dis cussed Fig. 2. Geo log i cal map of the study area (mod i fied by Ozcan et al., 1980)
be low). Quartz is the most abun dant gangue min eral. In ore mi - cros copy stud ies, the pres ence of radiolarian tests and fine-grained pyrolusite is at trib uted to rapid de po si tion from flu - ids (Fig. 4A; Zarasvandi et al., 2016). In ad di tion, pyrolusite veins of var i ous sizes with radiolarite lay ers and frac ture-fill ing struc tures are ev i dence of late-stage min er al iza tion (Zarasvandi et al., 2016).
DERBENT MINERALIZATION
The Derbent man ga nese min er al iza tion oc curs in the west - ern part of the AOC 35 km NW of the Yozgat dis trict (Fig. 2).
The re gion shows ev i dence of tectonism, the min er al iza tion and the radiolarite units con tain ing it show ing a frac tured and folded struc ture. The strike of the Derbent man ga nese veins ex tends dis con tin u ously N–W over 2 km, and dips 10–20°NE and SW.
The thick ness of the man ga nese vein zone var ies from 10 to 70 cm and the man ga nese ore is dark red and red dish with a frac tured and folded struc ture. Man ga nese and iron ox ides are the main ox ides. In the min er al iza tion, three dif fer ent min er al - iza tion stages-syngenetic, diagenetic and epigenetic were re - corded. In the syngenetic stage, typ i cally small euhedral crys - tals are ob served and only pyrolusite (I) was rec og nized (Fig. 4A). The diagenetic stage is rep re sented by re-mo bi li za - tion of ore min er als and is char ac ter ized by diagenetic manganite and goethite (Fig. 4B, C). The epigenetic stage is rep re sented by post- depositional supergene en rich ment and is char ac ter ized by frac ture-fill ing pyrolusite (II) (Fig. 4D). Tat Derbent man ga nese min er al iza tion has been sug gested to be of hy dro ther mal ex ha la tive type (Öksüz, 2011b).
BALTASARILAR MINERALIZATION
The Baltasarilar man ga nese min er al iza tion is lo cated 25 km NW of Yozgat dis trict (Fig. 2). The min er al iza tion is com posed chiefly of man ga nese ox ides and lesser amounts of iron ox ide and it oc curs within radiolarites as bands and laminae of thick - ness not ex ceed ing 10 cm. The strike of the Baltasarilar man ga - nese veins ex tends dis con tin u ously N–W over 5 m, and dips 20°SW. The man ga nese ore is dark red and red dish and frac - tured and folded struc ture. Like in the Derbent re gion, the min - er al iza tion is syngenetic, diagenetic and epigenetic. Based on this, two dif fer ent pyrolusite types are ob served. The pyrolusite may be fine-grained, partly euhedral syngenetic (I) or post- depositional, frac ture-fill ing epigenetic (II) (Fig. 4D). Goethite is diagenetically formed by the al ter ation of pyrolusite (Fig. 4E).
CIHANPASA MINERALIZATION
The Cihanpasa man ga nese min er al iza tion is lo cated 30 km N of Yozgat dis trict (Fig. 2). The min er al iza tion is solely com - posed of syngenetic pyrolusite. As in the other min er al iza tion in - stances, it is in tensely folded and frac tured. The strike of the Cihanpaºa man ga nese veins ex tends dis con tin u ously N–W over 3 m, and dips 10°SW. The thick ness of the man ga nese vein zone var ies from 3 to 8 cm and the man ga nese ore is dark red and red dish and frac tured and folded.
BUYUKMAHAL MINERALIZATION
The Buyukmahal area is sit u ated 35 km NE of the Yozgat dis trict (Fig. 2). The min er al iza tion is com posed of syngenetic pyrolusite and diagenetic mag ne tite. Al though vol ca nic units are ex posed in the re gion, the min er al iza tion oc curs within the radiolarites as bands and lenses. As in the other min er al iza tion in stances, it is in tensely folded and frac tured. The strike of the man ga nese veins ex tends dis con tin u ously N–W and NE over 20 m, and dips 55–25°NE and NW. The thick ness of the man - ga nese vein zone var ies from 50 to 60 cm and the man ga nese ore is dark red and red dish and frac tured and folded.
EYMIR MINERALIZATION
The Eymir min er al iza tion, 80 km NE of the Yozgat dis trict, is the larg est man ga nese oc cur rence in the re gion (Fig. 2). The min er al iza tion has been ex ploited by var i ous com pa nies, al - though not cur rently. It oc curs as thin and thick bands and lenses. The min er al iza tion, formed in syngenetic, diagenetic and epigenetic stages, con tains iron and man ga nese ox ide min er als. The re gion has ex pe ri enced in tense tectonism, with Fig. 3. Lam i nated, banded and len tic u lar ore bod ies
in the study area
A – Buyukmahal min er al iza tion; B – Derbent min er al iza tion;
C – Eymir mineralization; mn – man ga nese, rd– radiolarite
Fig. 4A – ore mi cros copy view of fos sil radiolaria and fine-grained euhedral pyrolusite (pr I) // nicol; B – manganite (mn) // nicol; C – goethite (gt) and pyrolusite (pr I) // nicol; D – fine-grained pyrolusite (pr I), frac ture-fill ing pyrolusite (pr II) and gangue (g) // nicol; E – goethite (gt) as a prod uct trans for ma tion from pyrolusite and fine-grained pyrolusite (pr I) // nicol; F – euhedral pyrolusite (pr I) and diagenetic goethite (gt), mag ne tite (mg) // nicol; G – frac ture-fill ing psilomelane (ps II), euhedral pyrolusite (pr I) and diagenetic jacobsite // nicol; H – psilomelane (ps I), diagenetic braun ite (br) and gangue (g) // nicol
fold ing and frac tur ing. Ore min er als are as so ci ated with ex - tremely folded and frac tured radiolarites. The strike of the Eymir man ga nese veins ex tends dis con tin u ously N–W over 3 km, and dips 20–25°SW and SE. The thick ness of the man ga nese vein zone var ies from 1 to 10 m and the man ga nese ore is dark red and red dish and frac tured and folded (Fig. 3C). Euhedral pyrolusite is thought to have been formed syngenetically (Fig. 4F, G). Psilomelane is ob served as both syngenetic [psilomelan(I)] (Fig. 4H) and epigenetic types [psilomelan(II)]
(Fig. 4G). In ad di tion, diagenetic mag ne tite, goethite, jacobsite and braun ite are also rec og nized (Fig. 4F–H).
TARHANA MINERALIZATION
In the Tarhana re gion, 120 km east of the Yozgat dis trict, syngenetic man ga nese ox ide min er al iza tion oc curs (Fig. 2).
Ore paragenesis is solely com posed of pyrolusite and quartz is the main gangue min eral. The strike of the Tarhana man ga - nese veins ex tends dis con tin u ously N–W over 10 m, and dips 10–20°NE and SW. The thick ness of the man ga nese vein zone var ies from 10 to 15 cm and the man ga nese ore is dark red and red dish and frac tured and folded.
ANALYTICAL PROCEDURES
Fifty 500 g ore sam ples were col lected from the Derbent, Baltasarilar, Cihanpasa, Buyukmahal, Eymir and Tarhana man ga nese min er al iza tion oc cur rences, with sys tem atic sam - pling from top to bot tom of the ore. Sam ples were taken at 30 cm in ter vals. Pow ders of 12 sam ples (<200 mesh) were ana lysed at ACME Lab o ra to ries (CANADA). Ma jor ox ide and trace el e ment con tents were de ter mined by ICP-ES and REEs were ana lysed by ICP-MS. 30 g sam ples were pow dered to 100 µm for geo chem i cal anal y sis. 0.5 g sam ples were pro - cessed in HCl-HNO3-H2O so lu tion at ~95°C for 1 hour and then the amount of each sam ple was in creased to 10 ml for the fi nal fil ter ing. An a lyt i cal re sults are given in Ap pen di ces 1 to 3*. In ad di tion, in or der to de ter mine the paragenesis and tex tural char ac ter is tics of the min er al iza tion, 40 pol ished sec tions were stud ied by ore mi cros copy. XRD anal y sis of twenty sam ples was done at TPAO (Turk ish Pe tro leum Cor po ra tion) lab o ra to - ries. A Rigaku DMAX IIIC model X-ray diffractometer with a Cu tar get (2–70° 2q) was used in the anal y ses. Ore min er als were also stud ied with a Thermo Sci en tific DXR Raman Mi cro scope at the Geo log i cal En gi neer ing De part ment of An kara Uni ver - sity. The Raman spec tra ob tained were eval u ated with the Crys tal Sleuth pro gram to de ter mine the min eral paragenesis.
Chem i cal com po si tions of some ore min er als (manganite, psilomelane, pyrolusite, braun ite) were de ter mined by microprobe anal y sis (EPMA) con ducted at Montan Uni ver sity in Leoben (Aus tria).
RESULTS
GEOCHEMISTRY
The main, trace and REE con tents of 50 ore sam ples col - lected from the min er al iza tion oc cur rences stud ied in the AOC are given in Ap pen di ces 1, 2 and 3. Ma jor ox ide and some trace el e ment data on man ga nese min er al iza tion of dif fer ent or i gins are shown in Ta ble 1. REE con tents of sam ples from sim i lar
and dif fer ent types of man ga nese min er al iza tion are given in Ta ble 2.
MAJOR AND TRACE ELEMENTS GEOCHEMISTRY
Ma jor and trace el e ment con cen tra tions and their as so ci a - tions are com monly used to ana lyse man ga nese and ferro - manga nese de pos its (Öksüz, 2011b; Polgári et al., 2012b;
Zarasvandi et al., 2013). Mn con tents of ore sam ples from the AOC are 5.62–62.86 wt.% (n = 50 sam ples; av er age 46.76 wt.%) and Fe con cen tra tions are 0.03–31.11 wt.% (av er - age 2.83 wt.%; Ap pen dix 1).
SiO2 con tents of the sam ples stud ied are 1.76–55.92 wt.%
(av er age 17.24 wt.%; Ap pen dix 1). Al though Co/Zn ra tios of all sam ples are >0.15, the ra tios of the Baltasarilar and Cihanpasa sam ples in par tic u lar are <2.5. Co/Zn ra tios in other re gions are very close to 2.5 or higher (Ap pen dix 1) in di cat ing that a hydrogenetic pro cess was in volved in the for ma tion of the man - ga nese ox ide min er al iza tion in the AOC. If Co/Ni <1, the de - posit has a sed i men tary or i gin (Fernandez and Moro, 1998) while Co/Ni >1 in di cates a ma rine en vi ron ment (Delian, 1994).
Like wise, Co/Ni is <1 for the Baltasarilar and Cihanpasa sam - ples and it is <1 for other min er al iza tion in stances. These data im ply that min er al iza tion in the area is of an ex ha la tive sed i men - tary type. Co is a no ta ble bioessential el e ment (Moffett and Ho, 1996; Polgári et al., 2012b). This fea ture of co balt can be con - sid ered as ev i dence for sub se quent se lec tive en rich ment of bioessential el e ments in AOC Mn ox ides and their for ma tion via mi cro bial pro cesses (Zarasvandi et al., 2016).
As, Ba, Cu, Li, Mo, Pb, Sb, Sr, V and Zn con tents are en - riched in hy dro ther mal flu ids (Nichol son, 1992a). Con cen tra - tions of As, Ba, Cu, Pb, Sr, V and Zn tend to be en riched in all min er al iza tion ex am ples in the area stud ied (Ap pen dix 2). In hy - dro ther mal sys tems, Zn con cen tra tion is ex pected to be frac - tion ated in prox i mal sul phide de pos its (Hein et al., 2008). Zn con cen tra tions of the mneralization stud ied in the AOC are 35–407 ppm (av er age 113.6 ppm) which may be at trib uted to leach ing from sul phide min er al iza tion at depth (Ap pen dix 2;
ªaºmaz et al., 2014). High Ni and Cr con tents could be ex - plained by leach ing from ultra mafic rocks or con tri bu tions from ultra mafic clastic ma te rial (Hein et al., 2008). Ni may also oc cur in sul phide zones and there fore high Ni con cen tra tions may in - di cate mul ti ple sources. If high Ni con cen tra tions are not cor re - lated with high Cr con tents, ultra mafic ma te rial may not be the source (Hein et al., 2008). How ever, when con cen tra tions of these el e ments are high and if Ni con tent is rel a tively lower than Cr, leach ing from ultra mafic rocks might be plau si ble (ªaºmaz et al., 2014). Ni con cen tra tions in the sam ples are 38.0–950.9 ppm (av er age 204.8 ppm) and Cr con cen tra tions are 13.68–2737.0 ppm (av er age 155.59 ppm; Ap pen dix 1).
These re sults show that the min er al iza tion in the study area is prob a bly as so ci ated with leach ing from ultra mafic rocks.
Ac cord ing to Hein et al. (2008), high Cu, Zn, Pb and Cd con - tents typ i cally re flect the ef fect of sulphides. Cu and Pb en rich - ment in the sam ples stud ied may in di cate leach ing from sul - phide at depth (27.13–1606.5 ppm, av er age 274.3 ppm and 0.1–147.8 ppm, av er age 18.9 ppm, re spec tively; Ap pen dix 2;
ªaºmaz et al., 2014). Low Mn con tents in ferro manga nese ores are in dic a tive of low-tem per a ture hy dro ther mal so lu tions (Hein et al., 2008; ªaºmaz et al., 2014). The Mn con cen tra tions of the sam ples are 3.7–198.2 ppm (av er age 38.8 ppm) im ply ing the in volve ment of low-tem per a ture hy dro ther mal flu ids (Ap pen - dix 2). Co con tents in hy dro ther mal de pos its is lower than those
* Supplementary data associated with this article can be found, in the online version, at doi: 10.7306/gq.1599
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)6( tnekulUnedaM )7( xel pmoCilriyaC )8(agamisaK )9(DBCMBET ni g irOyra tne m ides-ona clov yra tne m ides-la mreh tor dyh suo n egor dyhla mreh tor dyhla mreh tor dyhyra tne m ides /yra tne m ides citenegaid-ona clov yra tne m ides-ona clov yra tne m ides OiS2]%[ )-(96.3414.9*20.228.0486.3171.4220.3634.3143.655.0246.4424.3252.4109.53 lA2O3]%[ )-(37.035.21*72.084.094.285.456.059.233.088.089.233.408.025.0 eF2O3]%[ )-(69.233.02*03.292.227.370.4386.033.4157.053.081.6220.762.050.0 ]%[ OgM)-(06.095.0*85.150.099.151.102.027.2134.083.095.011.236.083.0 ]%[ OaC)-(82.134.6*79.025.050.442.942.028.684.265.141.480.565.292.0 aN2]%[ O)-(92.070.0*46.030.042.070.050.060.040.050.011.032.010.020.0 K2]%[ O)-(22.088.0*22.060.050.050.011.091.036.052.173.085.030.034.0 OiT2]%[ )-(23.048.0*40.030.001.071.030.001.010.020.041.091.020.010.0 P2O5]%[ )-(52.037.3*40.060.081.049.040.080.070.030.094.041.070.080.0 ]%[ OnM)-(88.5487.33*25.8425.9387.3607.8122.9234.0435.8628.0633.1138.4477.3703.35 ]mpp[ aB65.21200.514403676.190743.830100.72405.305104.922104.91726.678018.805510.3988.87261.88523.0272 ]mpp[ V68.76100.44137533.27186.03)-(14.99607.34101.6016.9313.7618.5146.6146.1318.402 ]mpp[ rC12.70100.6474298.8)-()-(05.0207.3100.0161.02254.12186.3136.4276.4366.075 ]mpp[ oC77.400.1140433.53153.3300.3165.6612.5205.946.7636.9511.6015.1260.4014.333 ]mpp[ iN93.9800.6350376.00316.8900.0172.53704.9600.326.4323.8535.0931.6624.279.001 ]mpp[ uC30.1300.2757300.62281.16100.6541.43409.45108.6215.0818.290.2569.6242.098.299 ]mpp[ nZo63.73100.4608522.32121.4600.0710.48207.6605.368.493.1213.8234.9217.668.27 ]mpp[ bP94.6100.947532)-(65.600.5639.33105.605.353.17.59.3315.039.99.51 ]mpp[ hT)-(00.21300.182.0)-(84.204.002.3342.05.02.37.36.02.0 ]mpp[ rS43.147)-()-(44.77856.76600.58101.904104.34200.5520.53032.83833.3034.4671.5118.8741 ]mpp[ bN07.6)-()-(05.172.0)-(02.507.001.111.01.02.45.21.03.0 ]mpp[ rZ)-()-()-(22.978.5)-(99.9800.409.621.618.91.994.859.85.2 iN/oC50.013.023.154.005.003.190.063.051.26.24.03.04.20.25.3 nZ/oC30.071.007.001.118.091.042.083.087.03.44.13.09.43.26.4 eF/nM )-(00.99161.298.6203.72189.8116.071.7920.2156.20935.21675.016.931.350193.2331 )1( morfnekat se s ylanA)6002( .la te eiX )3 dna 2( ;)7002( nooM dna hahS )4( ;)6002( .la te dlaregztliF )5( ;)0102( .la te ºukaraK )8( ;)4102( .la te zamºaª )7( ;)3991( krützÖ )6( ;)6102( .la te idnavsaraZ )9( ;.la te çoK )0002(si s ylana on si ereht )-( ;anahraT – T ;rimyE – E ;lahamkuyuB – MB ;asapnahiC – C ;ralirasatlaB – B ,tnebreD – D ;epyt tne m ele morfera se ulav – * ; 1el baT tiso ped ese na gnam fo sepyt su o irav fo stne tnoc tne m ele ecart dna ro jaM
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in hydrogenetic de pos its and there fore high Co con cen tra tions re flect deep ma rine en vi ron ments (Del Rio Salas et al., 2008).
Co con cen tra tions of the man ga nese min er al iza tion in the AOC are 27.2 to 1432.1 ppm (av er age 268.1 ppm) which are rel a - tively high, re flect ing a hydrogenetic con tri bu tion (Ap pen dix 2).
Ac cord ing to Hein et al. (2008), high Ba and low Fe, Co, Ni, Cu and Zn con tents of man ga nese ox ides may in di cate leach ing from or ganic-rich sed i ments or in suf fi cient bar ite dis so lu tion at depth. Due to sed i men ta tion and vol ca nic ac tiv ity ef fects, Ba con cen tra tions in hy dro ther mal flu ids are greater than in sea wa - ter (Monnin et al., 2001; Öksüz, 2011a). Ba con cen tra tions in the man ga nese min er al iza tion of the AOC are 91.0–37137.0 ppm (av er age 6807.7 ppm; Ap pen dix 2). Based on these high Ba con tents, min er al iza tion in the study area re - flects a hy dro ther mal or i gin. High ar senic con tents are in dic a - tive of sed i ment in put to the hy dro ther mal man ga nese for ma - tion (Nichol son, 1992a, b). Ar senic con cen tra tions in the sam - ples are 5.9–199.9 ppm (av er age 46.3 ppm; Ap pen dix 2). This en rich ment might in di cate the role of hy dro ther mal flu ids (ªaºmaz et al., 2014).
Trace el e ment con cen tra tions (As, Cu, Ni, Pb and Zn) in the AOC sam ples are lower than those of hydrogenetic de pos its but sig nif i cantly higher than those of hy dro ther mal de pos its (Ap - pen dix 2). Al and Ti con cen tra tions are also used for de scrip tion
of man ga nese min er al iza tion and Al is gen er ally as so ci ated with clay min er als in sed i ments (Crerar et al., 1982). Ti is im mo - bile in hy dro ther mal so lu tions and it de fines the rate of clastic in - put (Sugisaki, 1984). High Al con tents in man ga nese ox ide de - pos its are an im por tant in di ca tor of sed i men tary in put dur ing sed i men ta tion (Choi and Hariya, 1992). Al con cen tra tions in the AOC sam ples are 0.01–3.19 wt.% (av er age 0.61 wt.%) and Ti con cen tra tions are 0.01–0.17 wt.% (av er age 0.03 wt.%; Ap - pen dix 1). Rel a tively high Al con cen tra tions in the AOC ores may have been de rived from the radiolarite. Low Ti con tents might in di cate lim ited clastic in put dur ing de po si tion (ªaºmaz et al., 2014).
Var i ous ma jor and trace el e ment di a grams have been used for dis crim i na tion of man ga nese de pos its of dif fer ent or i gins (Bonatti et al., 1972; Toth, 1980; Crerar et al., 1982; Adachi et al., 1986; Pe ters, 1988; Choi and Hariya, 1992; Nichol son, 1992a; Shah and Moon, 2007). These di a grams are use ful for dis tin guish ing hy dro ther mal (ter res trial or ma rine) ver sus hydrogenetic or i gins. The term hy dro ther mal has been used for sed i men tary-ex ha la tive man ga nese min er al iza tion or for pools in ter res trial en vi ron ments and man ga nese ox ides de pos ited di rectly from hot springs in geo ther mal sys tems (Nichol son, 1992a). The term hydrogenetic com monly re fers to ad sorp tion of ma te ri als dis solved in sea wa ter or de pos its that are de pos - Fig. 5A – Fe-(Ni+Co+Cu)´10Mn dis crim i na tion di a gram (Bonatti et al., 1972; Crerar et al., 1982; Hein et al., 1992);
B – Fe-Si´2Mn di a gram (Toth, 1980); C – Ni-Zn-Co di a gram (Choi and Hariya, 1992)
ited slowly (Bonatti et al., 1972; Crerar et al., 1982; Nichol son, 1992a). In the Fe-(Cu+Ni+Co)´10-Mn tri an gu lar di a gram, the ore sam ples stud ied are com pared to sam ples from other re - gions as so ci ated with ophiolites (Bonatti et al., 1972; Crerar et al., 1982; Hein et al., 1992; Shah and Moon, 2007; Karakuº et al., 2010; Zarasvandi et al., 2016; Fig. 5A). Based on this, all sam ples plot in the hy dro ther mal field. In ad di tion, some sam - ples show con tri bu tion from diagenetic or mi cro bial pro cesses.
In the Fe-Six2-Mn di a gram, all Cihanpasa sam ples are dis trib - uted in the hydrogenetic field, while oth ers plot in the vi cin ity of the hy dro ther mal field (Toth, 1980; Fig. 5B). In the Ni-Zn-Co di - a gram, ore sam ples are com pared with sam ples as so ci ated with ophiolites (Choi and Hariya, 1992; Fig. 5C). Based on this di a gram, ore sam ples from the Derbent, Eymir, Buyukmahal and Tarhana ar eas mostly plot in the hydrogenetic field and the Cihanpasa sam ples clus ter in the hy dro ther mal field while sam - ples from the Baltasarilar area are dis trib uted in both fields (Choi and Hariya, 1992; Fig. 5C).
Ma jor and trace el e ment con tents of var i ous man ga nese de pos its of hy dro ther mal and hydrogenetic or i gin in Tur key and world wide are given in Ta ble 1. Ma jor and trace el e ment con - cen tra tions of AOC man ga nese min er al iza tion are com pared with those of Guichi (China), Waziristan, Hazara (Pa ki stan), Baby Bare (NE Pa cific Ocean), and the Sorkhvand (Iran), Ulukent, Maden Com plex, Cayirli, Kasimaga (Tur key) de pos its (Koç et al., 2000; Fitz ger ald and Gillis, 2006; Xie et al., 2006;
Shah and Moon, 2007; Karakuº et al., 2010; ªaºmaz et al., 2014; Zarasvandi et al., 2016; Ta ble 1).
REE GEOCHEMISTRY
Re sults of REE anal y sis and some REE ra tios of the ore sam ples stud ied are given in Ap pen dix 3. In ad di tion, REE con - tents of var i ous man ga nese ox ide de pos its from Tur key and world wide are com pared with those of the sam ples stud ied (Ta - ble 2). More over, chondrite-nor mal ized pat terns of the sam ples are shown in Fig ure 6. El e ment vari a tion di a grams for deep ma - rine, MOR hy dro ther mal, EPR Fe-Mn sed i ments, Phanerozoic Fe-Mn umbers and hydrogenetic Mn crusts and an el e ment vari a tion di a gram con structed us ing av er age val ues of the sam - ples stud ied are shown in Fig ure 7.
Ex am i na tion of the REE geo chem is try of ore de pos its pro - vides an in sight into their or i gin (Bau and Möller, 1991). There - fore, REE con tents of man ga nese ox ide de pos its from var i ous re gions are com pared with those from the study area (Ta ble 2).
As shown in Ta ble 2 and Fig ure 7, REE con cen tra tions of hy - dro ther mal de pos its are lower than those of hydrogenetic de - pos its (Hein et al., 1990; Usui and Someya, 1997; Kato et al., 2011). To tal REE (SREE) con tents of hy dro ther mal oc cur - rences vary widely (Mills et al., 2001). SREE con tent of the AOC sam ples is 6.68–518.27 ppm (av er age 74.54 ppm). Al though these val ues are higher than for the Cihanpasa and Fig. 6. Chondrite-nor mal ized REE di a gram for the ore sam ples (nor mal iza tion val ues after Evensen, 1978)
Buyukmahal ar eas (305.13–518.27 ppm, av er age 385.66 ppm and 99.09–178.36 ppm, av er age 142.75 ppm, re spec tively), they are gen er ally higher than those of hy dro ther mal de pos its but rel a tively lower than those of hydrogenetic de pos its (Ap pen - dix 3 and Ta ble 2). The slight en rich ment of REEs in both re - gions is at trib uted to the sed i men tary cover (ªaºmaz et al., 2014). Chondrite-nor mal ized pat terns of the sam ples are shown in Fig ure 6. In ad di tion, spi der di a grams con structed us - ing av er age val ues of the sam ples are shown in Fig ure 7. These di a grams are com pared with el e ment vari a tion di a grams of sim - i lar man ga nese oc cur rences in Fig ure 7. Based on this, the pat - tern of the ore sam ples stud ied greatly re sem bles those of Phanerozoic Fe-Mn umbers and slightly re sem bles EPR hy dro - ther mal Fe-Mn sed i ments and deep-ma rine ex am ples (Fig. 7A,
C, D). Frac tion ation from LREE to HREE dur ing the man ga - nese ox i da tion pro cess can be con sid ered as ev i dence for pri - mary en rich ment of REE (Xie et al., 2006; ªaºmaz et al., 2014).
In the sam ples stud ied, the LREE/HREE ra tio is 1.92–16.89 ppm (av er age 5.58 ppm) in di cat ing that, since they are more sta ble, LREEs in hy dro ther mal so lu tions are pref er a - bly en riched with re spect to HREEs (Ruhlin and Owen, 1986;
Zarasvandi et al., 2013). Con se quently, it can be con cluded that hy dro ther mal so lu tions played an im por tant role in the for - ma tion of the man ga nese min er al iza tion stud ied. Y/Ho ra tios of the sam ples are 16.81–51.82 (av er age 28.90), high Y/Ho ra tios in di cat ing mul ti ple sources for the min er al iza tion. In other words, in ad di tion to deep ma rine con di tions, ma te rial of ter res - trial or i gin was also in cor po rated dur ing the min er al iza tion Fig. 7A – chondrite-nor mal ized REE pat terns of mod ern sea wa ter; B – MOR hy dro ther mal flu ids; C – EPR (East Pa cific Rise) hy dro ther mal Fe-Mn sed i ments; D – Phanerozoic hy dro ther mal Fe-Mn umbers; E – hydrogenetic Mn crusts (Kato et al., 2006); F
– chondrite-nor mal ized REE di a gram for av er age ore sam ples in the study area (nor mal iza tion val ues are from Evensen, 1978)
(Nayan et al., 1994). LaN/NdN and DyN/YbN ra tios are also use ful for de ter mi na tion of or i gin. The LaN/NdN ra tio in hy dro - ther mal so lu tions is 3.0–7.4, with av er age of 4.5 and the DyN/YbN ra tio is 0.6–2.1 with an av er age of 1.2. These ra tios in man ga nese crusts are 2.7–4.3 and 0.4–1.2 (Fitz ger ald and Gillis, 2006). The LaN/NdN and DyN/YbN ra tios of the sam ples stud ied are 1.45–5.22 (av er age 2.31) and 0.51–1.41 (av er age 0.98). These data in di cate a hy dro ther mal source. In nor mal sea wa ter the Er/Nd ra tio is 0.27 (De Baar et al., 1988), but this ra tio may be <0.1 due to in creas ing amounts of de tri tal ma te rial dur ing min er al iza tion, or a con cen tra tion of Nd which is more eas ily con cen trated than Er dur ing diagenesis (Ger man and Elderfield, 1989; Bellanca et al., 1997). The Er/Nd ra tios of the sam ples stud ied are <0.27, ex cept for five sam ples (D12-13, D15-16-17; 0.05–0.31 and av er age 0.15). This in di cates that the min er al iza tion was ac com pa nied by diagenetic pro cesses, to gether with a de tri tal con tri bu tion.
Eu and Ce are im por tant el e ments for de ter mi na tion of the or i gin and paleoredox po ten tial of the depositional en vi ron ment (Sabatino et al., 2011). The Ce anom aly is cal cu lated from the equa tion Ce* = Cenorm/[2/3Lanorm+1/3Prnorm] while the Eu anom aly is com puted from the equa tion Eu* = Eunorm/[2/3Smnorm+
1/3Gdnorm] (Tay lor and McLennan, 1985). In these for mu lae, chondrite-nor mal ized val ues were used (Evensen et al., 1978).
Neg a tive or pos i tive anom a lies of these el e ments may de fine the or i gin of for ma tion. For ex am ple, a weak neg a tive Ce anom - aly in di cates vol ca nic in put (Fleet et al., 1976) or vol ca nic con tri - bu tion to the sea wa ter. In ad di tion, it may also point to a high growth rate of hy dro ther mal crusts (Hein et al., 1997). By con - trast, a strong neg a tive Ce anom aly char ac ter izes low-tem per - a ture hy dro ther mal de pos its of a con ti nen tal arc in spread ing cen tres and in the vi cin ity of mid-ocean ridge hot points (Decarlo and Mcmurtry, 1992; Hodkinson et al., 1994). Pos i tive Ce anom a lies are char ac ter is tic of mod ern sub ma rine man ga - nese oxyhydroxide de pos its and nod ules (Kunzendorf and Glasby, 1994). All sam ples from the Cihanpasa and Buyukmahal ar eas dem on strate a neg a tive Ce anom aly and re - sem ble low-tem per a ture hy dro ther mal de pos its (Ap pen dix 3 and Fig. 6). Sam ples from other min er al iza tion oc cur rences (Derbent, Baltasarilar, Eymir and Tarhana) show both pos i tive and neg a tive Ce anom a lies (Ap pen dix 3 and Fig. 6). Based on these re sults, it can be in ferred that both hy dro ther mal and
hydrogenetic pro cesses were ef fec tive in the for ma tion of the AOC min er al iza tion (Shah and Moon, 2007). Pos i tive Eu anom - a lies in hy dro ther mal de pos its are in dic a tive of high-tem per a - ture hy dro ther mal flu ids (Michard, 1989) and high Eu con cen - tra tions dur ing cir cu la tion re flects the in ter ac tion be tween sub - strate vol ca nic rocks and hot wa ters (Usui and Mita, 1995).
Neg a tive Eu anom a lies in di cate rel a tively lit tle in ter ac tion be - tween vol ca nic rocks and ther mal wa ters (Usui and Mita, 1995).
These anom a lies also im ply crustal con tam i na tion and/or sed i - ment con tri bu tion (Öksüz, 2011a). Ex cept for some sam ples from the Derbent area, all other sam ples from the study area are rep re sented by neg a tive Eu anom a lies (Ap pen dix 3 and Fig. 6). Al though these val ues in di cate rel a tively lit tle in ter ac tion with vol ca nic rocks dur ing the min er al iza tion, both pos i tive and neg a tive anom a lies were re corded in the Derbent area and show that hy dro ther mal flu ids were in volved in hy dro ther mal min er al iza tion at times, thus in creas ing the tem per a ture. The neg a tive Eu anom aly might show that the hy dro ther mal source was in the dis tal part of the min er al iza tion area or it was greatly mixed with sea wa ter (Sabatino et al., 2011).
Ceanom val ues (Ceanom = log[3CeN/(2LaN+NdN)] re flect ox y - gen fugacity dur ing the pri mary min er al iza tion pro cess. Ceanom
val ues >–0.1 re flect Ce en rich ment that is in dic a tive of an anoxic char ac ter of the sed i ment Ceanom val ues <–0.1 re flect a Ce anom aly that in di cates an oxic char ac ter for the sed i ment (Wright et al., 1987; Xie et al., 2013; Koçak, 2020). With the ex - cep tion of the Eymir and Tarhana ar eas, sam ples from all other re gions yielded Ceanom <–0.1. In ad di tion, re gard ing Eymir area, 5 sam ples are rep re sented by Ceanom <–0.1 and 10 sam ples are rep re sented by Ceanom >–0.1. For the Tarhana area, 2 sam ples are rep re sented by Ceanom<-0.1 and 3 sam ples are rep re - sented by Ceanom >-0.1. In this re spect, data on the Eymir and Tarhana man ga nese min er al iza tion oc cur rences in di cate that the sed i ment was both oxic and anoxic in char ac ter, whilst other min er al iza tion oc cur rences are rep re sented by Ce de ple tion (neg a tive Ce anom aly) and an oxic wa ter. The oxic ver sus anoxic char ac ter of wa ter is re lated to re dox con di tions. In sed i - men ta tion in a re duc ing en vi ron ment, re dox con di tions may change as a re sult of fresh wa ter ad di tion (e.g., via sub ma rine cur rents). In many de pos its, the co ex is tence of ox y gen ated and sul phur-bear ing min er als is at trib uted to such changes.
Fig. 8. A sketch model show ing the tec tonic re la tion be tween Permo-Tri as sic and Lower Paleocene rocks in the Cankiri Basin (Tüysüz and DellaoÈlu, 1992)
DISCUSSION
Al most all man ga nese-ferro manga nese min er al iza tion as - so ci ated with ophiolites com prises hy dro ther mal oc cur rences as ex ha la tive or fault-con trolled de pos its that formed fol low ing the obduction of oce anic crust onto con ti nen tal crust (Roy, 1992). It is in ferred that min er al iza tion in the study area had three dif fer ent for ma tion mod els. Ac cord ing to the hydrogenetic model, pri mary min er al iza tion takes place by slow de po si tion of el e ments dis solved from sur round ing ma te ri als un der suit able Eh and pH con di tions (Fig. 8A). The hy dro ther mal model in - volves ei ther a sed i men tary-ex ha la tive type oc cur rence on the sea floor or a fault-con trolled epigenetic stage de vel op ing on oce anic crust (Fig. 8A, B). In the hy dro ther mal min er al iza tion model, sea wa ter pen e trates down wards through frac tures in the oce anic crust. Changes in sea wa ter pH are in ev i ta ble as it en coun ters hot oce anic crust (Roy, 1992). Mod i fied sea wa ter in cor po rates el e ments from the sur round ing ba saltic oce anic crust. Con se quently, ore-form ing so lu tions are de vel oped which re move up wards to form hy dro ther mal man ga nese-ferro - manga nese de pos its. The third model in volves diagenesis which takes place by al ter ation of pre vi ously formed min er als un der chang ing physicochemical con di tions (Fig. 8B).
At low Eh and/or pH con di tions, Mn is more mo bile than Fe (Roy, 1992). Iron is the first el e ment de pos ited, whilst man ga - nese can stay in so lu tion for lon ger. In or der for iron and man ga - nese to sep a rate, pH must change grad u ally (Hem, 1972). Con - se quently, since iron-rich min er als are slightly im mo bile they are pre cip i tated in ar eas close to ac tive sub ma rine hy dro ther - mal cen ters, while man ga nese ox ides are de pos ited far from these cen ters (Choi and Hariya, 1992). Nearly all ore sam ples of the AOC man ga nese min er al iza tion (ex cept for sam ple T1) are char ac ter ized by low Fe2O3 (0.04–4.44 wt.%; av er age 4.05 wt.%) con tents. This is re flected in the scar city of Fe-bear - ing min er als in the ore sam ples and also sup ported by strong neg a tive cor re la tion be tween Fe2O3 and MnO (r = –0.82; Ap - pen dix 1) and the ab sence of a pos i tive Eu anom aly with the ex - cep tion of a few sam ples from the Derbent (D9, D10, D11, D15, D16) and Tarhana (T1) ar eas. Ac cord ing to Sabatino et al.
(2011), prox i mal hy dro ther mal Fe-Mn de pos its gen er ally dis - play a pos i tive Eu anom aly. Eu con cen tra tions are grad u ally de - pleted as hy dro ther mal so lu tions travel. Dur ing ore de po si tion and Fe-Mn sep a ra tion, Eu grad u ally in creases. Eu anom a lies are also in dic a tive of high- (>300°C) or low-tem per a ture (<200°C) hy dro ther mal al ter ation of oce anic crust (Michard et al., 1993). There fore, so lu tions that are pro duced by high-tem - per a ture hy dro ther mal al ter ation are rep re sented by a strongly pos i tive Eu anom aly, whilst so lu tions that are pro duced by low-tem per a ture al ter ation are char ac ter is tic of a weak or ab - sent Eu anom aly (Michard et al., 1993).
Ex cept for sam ples from the Cihanpasa and Buyukmahal ar eas, high Mn/Fe ra tios (0.38–2245.10 and av er age 779.44) in all other sam ples in di cate that the com po si tion of the flu ids was quite ho mo ge neous and that the man ga nese de pos its stud ied are of hy dro ther mal type (Nichol son, 1992a; Karakuº et al., 2010). Hy dro ther mal man ga nese de pos its are also char ac ter - ized by high sil ica con tents (Jach and Dudek, 2005). The SiO2
con tents of the sam ples stud ied are 1.76–55.92 wt.% (av er age 17.24 wt.%; Ap pen dix 1), in di cat ing that the de pos its were formed from hy dro ther mal so lu tions (Karakuº et al., 2010).
Trace el e ment con tents of the AOC sam ples are dif fer ent from those of other hy dro ther mal de pos its. In par tic u lar, there are high con cen tra tions of Ba, Co, Cu and Sr (Ap pen dix 1). This dif fer ence in trace el e ment con cen tra tions is due to diagenesis.
Sep a ra tion of iron from man ga nese is an other char ac ter is tic of diagenetic man ga nese de pos its (Dymond et al., 1984; Jach and Dudek, 2005). Co/Zn and Co/Ni ra tios have been suc cess - fully used for un der stand ing ore-form ing pro cesses in man ga - nese de pos its (Delian, 1994; Fernandez and Moro, 1998;
Öksüz, 2011a). A Co/Zn ra tio of 0.15 is in dic a tive of hy dro ther - mal de pos its and if this ra tio is 2.5 or higher, Fe and Mn that form hydrogenetic de pos its are ac cepted to be non-unique (Toth, 1980; Öksüz, 2011a).
Low trace el e ment con cen tra tions also in di cate diagenetic pro cesses, trace el e ment con tents of hydrogenetic Fe-Mn crusts be ing rel a tively higher (Zarasvandi et al., 2016). Trace el e ment con cen tra tions in the AOC (As, Ni, Pb and Zn) are lower than those of hydrogenetic de pos its, but sig nif i cantly higher than in hy dro ther mal de pos its (Ap pen dix 2 and Ta ble 2).
Mn(II) ox i da tion by some bac te ria may in crease trace el e ment (e.g. Co) con tents of man ga nese de pos its (Moffett and Ho, 1996; Polgári et al., 2012b). Co balt con cen tra tions in the sam - ples stud ied are rel a tively high in some ar eas (Buyukmahal 134.60–1432.10 ppm, av er age 621.50 ppm; Derbent 48.70–1327.80 ppm and av er age 367.64 ppm). As a whole, trace el e ment con cen tra tions in man ga nese ores de crease from hydrogenetic to diagenetic and hy dro ther mal ox ide de pos - its (Takahashi et al., 2007; Sabatino et al., 2011). In the tri an gu - lar di a gram of Choi and Hariya (1992), most of the ore sam ples stud ied clus ter in the hydrogenetic field al though some plot in the hy dro ther mal field (Fig. 5C). Al though this di a gram shows that trace el e ment con cen tra tions of the ore sam ples stud ied are con sis tent with a hy dro ther mal-hydrogenetic for ma tion, some sam ples have no tice ably high Co con tents, and tend to shift to wards the hydrogenetic field (Fig. 5C). Co balt is an im - por tant bioessential el e ment (Moffett and Ho, 1996; Mor gan, 2005) and microbially me di ated re ac tions may in crease con - cen tra tions of this el e ment (Polgári et al., 2012b; Zarasvandi et al., 2013). The role of mi cro bial pro cesses in the en rich ment of bioessential el e ments (e.g., Mn, Fe, As, Ba, Sr, Co, Ce) has been clearly shown in the Nasirabad man ga nese oc cur rence (Zarasvandi et al., 2013) and other man ga nese ox ide de pos its (Zarasvandi et al., 2016) such as non-sul phide de pos its in Urkut, Hun gary (Polgári et al., 2012b).
CONCLUSIONS
1. AOC man ga nese min er al iza tion formed at three dif fer ent stages: syngenetic, diagenetic and epigenetic.
2. A neg a tive Eu anom aly re corded in most sam ples may in di cate rel a tively lit tle in ter ac tion with vol ca nic rocks dur ing the min er al iza tion, whilst both neg a tive and pos i tive anom a lies ob - served in sam ples from the Derbent area might be in dic a tive of tem per a ture in crease in duced by con tri bu tion from hot hy dro - ther mal flu ids at times. The neg a tive Eu anom aly may also show that the hy dro ther mal source was dis tant from the min er - al ized area or it was greatly mixed with sea wa ter (Sabatino et al., 2011). All sam ples from the Cihanpasa and Buyukmahal ar - eas are char ac ter ized by a neg a tive Ce anom aly and sim ply re - sem ble low-tem per a ture hy dro ther mal min er al iza tion. Sam ples from other min er al iza tion oc cur rences (Derbent, BaltasarÏlar, Eymir and Tarhana) dis play both neg a tive and pos i tive Ce anom a lies.
3. High con cen tra tions of Ba, Co, Cu and Sr may be at trib - uted to diagenesis. Iron sep a ra tion from man ga nese, as typ i cal of hy dro ther mal man ga nese oc cur rences, is an other char ac ter - is tic of diagenetic man ga nese de pos its (Dymond et al., 1984;
Jach and Dudek, 2005). Low con cen tra tions of trace el e ments such as As, Ni, Pb and Zn point to diagenetic pro cesses (Zarasvandi et al., 2016). Trace el e ment con cen tra tions in the AOC min er al iza tion are lower than those of hydrogenetic de - pos its, but no ta bly higher than those of hy dro ther mal de pos its.
4. High Ba con tents, el e ment pat terns de creas ing from LREE to HREE and the neg a tive Ce anom a lies im ply that the ore de pos its in the study area are de rived from a pri mary hy dro - ther mal source. How ever, the role of diagenetic and epigenetic pro cesses can not be ruled out.
Ac knowl edge ments. This study was sup ported by The Sci en tific and Tech ni cal Re search Coun cil of Tur key (TUBITAK Pro ject no. 109Y167) and Bozok Uni ver sity (Grant no.
B.F.F.M/2009-06) greatly ac knowl edged for fi nan cial sup port.
The au thors thank to Prof. S.Z. Mikulski, Prof. N. Hanilçi and Prof. K. Szama³ek for help ful com ments on this manu script. Dr.
I. Uysal is kindly thanked for his help in EPMhyA anal y sis. The au thors also thank ful to Prof. Y.K. KadÏoÈlu and C.O. Kilic, An - kara Uni ver sity Geo log i cal En gi neer ing De part ment, for Raman spec tros copy anal y sis.
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