Geo log i cal Quar terly, 2019, 63 (3): 478–492 DOI: http://dx.doi.org/10.7306/gq.1488
Rhe nium abun dance in molybdenites: a case study on vein-type Cu-Mo-Au min er al isa tion in the Qarachilar area, Sungun por phyry Cu
and Siah Kamar por phyry Mo de pos its, NW Iran
Vartan SIMMONDS1, *, Ryan MATHUR2 and Da vid SELBY3
1 Uni ver sity of Tabriz, Re search In sti tute for Fun da men tal Sci ences, Tabriz, 51666-16471, Iran
2 Juniata Col lage, De part ment of Ge ol ogy, Huntingdon, 1700 Moore St, PA, 16652 USA
3 Uni ver sity of Dur ham, De part ment of Earth Sci ences, Dur ham, DH1 3LE, UK
Simmonds, V., Mathur, R., Selby, D., 2019. Rhe nium abun dance in molybdenites: a case study on vein-type Cu-Mo-Au min - er al isa tion in the Qarachilar area, Sungun por phyry Cu and Siah Kamar por phyry Mo de pos its, NW Iran. Geo log i cal Quar - terly, 63 (3): 478–492, doi: 10.7306/gq.1488
As so ci ate Ed i tor – Tomasz Bajda
The vein-type Cu-Mo-Au min er al isa tion in Qarachilar, the Sungun por phyry Cu de posit (PCD) and the Siah Kamar por phyry Mo de posit (PMD) are all lo cated at the north west ern end of the Neo Tethys-re lated Urumieh–Dokhtar vol cano-plutonic belt of Iran. Re con tents of mo lyb de nite sam ples from the Qarachilar, Sungun and Siah Kamar de pos its are about 112.67–462 ppm, 53.24–252.29 ppm, and 10.44–41.05 ppm, re spec tively. Re con tents of the first two de pos its fall in the range of PCDs, while those of the lat ter are lower and cor re spond to PMDs. The rel a tively high Re con tent of the Qarachilar and Sungun molybdenites can be ex plained con sid er ing the low abun dance of mo lyb de nite, a man tle-dom i nated source for ore ma te ri als and the in cor po ra tion of ox i dized and acidic hy dro ther mal flu ids with high fCl. The high abun dance of mo lyb de nite in the Siah Kamar PMD has re sulted in vol ume di lu tion of Re. Fur ther more, oc cur rence of the main ore within the potassic al ter ation zone and, hence, the al ka line na ture of the re spon si ble flu ids in this zone have also af fected the Re con tent of molybdenites.
Vari a tions of the Re con tent in dif fer ent veins/veinlets showed a neg a tive re la tion ship with the for ma tion tem per a ture of these veins, and a pos i tive/neg a tive re la tion ship with the acid ity/al ka lin ity of the hy dro ther mal flu ids, while the grain size of molybdenites showed a pos i tive re la tion ship.
Key words: Qarachilar, Sungun, Siah Kamar, Qaradagh Batholith, mo lyb de nite, Re con tent.
INTRODUCTION
Rhe nium is one of the most dis persed el e ments in the Earth’s crust, with an av er age abun dance of 0.7 ppb (Car - darelli, 2008). How ever, this is a chalcophile el e ment and usu - ally con cen trated within Cu-Mo sulphides, and tends to be much more abun dant in mo lyb de nite than other co ex ist ing sulphides (Berzina et al., 2005), which is due to the sim i lar ionic ra dius and va lence of Mo and Re (Sun et al., 2010).
It has been shown that mo lyb de nite is the main host phase for Re in many hy dro ther mal de pos its (McCandless et al., 1993). It in cor po rates con sid er able Re (tens to thou sands of ppm) within its struc ture. This con tent is al most al ways in ppm
range and can reach sev eral per cent (Stein et al., 2001). How - ever, Re con tents of >1 wt.% in molybdenites are rare, al though some pro cesses in the por phyry and some epi ther mal sys tems as so ci ated with the por phyry min er ali sa tion can lead to the ex - treme en rich ment of Re in molybdenites or even for ma tion of rheniite in such de pos its. As a unique ex am ple, molybdenites in the Oligocene por phyry Cu-Mo-Au sys tems of the Pagoni Rachi and Sapes de pos its of north east ern Greece are as so ci ated with pure rheniite, Mo-rich rheniite, as well as with in ter me di ate (Mo,Re)S2 and (Re,Mo)S2 phases, with up to 46 wt.% Re, which oc cur as nanodomains and/or microinclusions in the in ter me di - ate mo lyb de nite-rheniite phases (Voudouris et al., 2013).
Rheniite ap pears ei ther at the rims of mo lyb de nite as a low-tem - per a ture exsolution prod uct of high-Re mo lyb de nite, or as sep - a rate grains.
Ex clud ing the above-men tioned unique cases of ex tremely Re-rich molybdenites, which have been at trib uted to an anom a - lous man tle-wedge source with chem i cal inhomogenities and lo cal-scale pro cesses, Voudouris et al. (2013) have shown that por phyry Cu-Au de pos its con tain the high est Re con tents (case stud ies from Can ada range from 3.858 to 8.170 ppm) and the
* Corresponding author, e-mail: simmonds_vartan@tabrizu.ac.ir Received: August 25, 2018; accepted: May 17, 2019; first published online: October 1, 2019
por phyry Cu de pos its take the sec ond place (>4.000 ppm, with the high est con tent of 15.400 ppm from the Phil ip pines). In ad - di tion, it is well-doc u mented that molybdenites as so ci ated with por phyry Cu-Mo de pos its ex hibit rel a tively higher Re con tents (with the mean of 1.830 ppm and the max i mum con tent of 19.800 ppm, cal cu lated based on the avail able data from 86 por phyry Cu-Mo de pos its; Berzina et al., 2005) com pared to those as so ci ated with por phyry Mo and Mo-Cu de pos its (Giles and Shil ling, 1972; Newberry, 1979b; Stein et al., 1997) with the mean of 42 ppm (ob tained from 19 por phyry Mo-Cu and Mo de - pos its; Berzina et al., 2005). In gen eral, molybdenites of de pos - its with higher Cu/Mo ra tio typ i cally have higher Re con tents and there is a pos i tive cor re la tion be tween these two pa ram e - ters (Stein et al., 1997), as the enor mous quan ti ties of mo lyb de - nite lead to vol ume di lu tion of Re con cen tra tion.
This con tri bu tion aims to de ter mine and com pare the Re abun dances within the molybdenites of three dif fer ent de pos its in north-west Iran with each other: the vein-type Cu-Mo-Au min - er ali sa tion in Qarachilar (cen tral part of the Qaradagh batho - lith), the Sungun por phyry Cu de posit (PCD) and the Siah Kamar por phyry Mo de posit (PMD) (Fig. 1), as well as with other mo lyb de nite-bear ing PCDs in Iran and in the ad ja cent Meghri-Ordubad pluton, north of the study area (south ern Ar - me nia). We also dis cuss po ten tial con trols on Re con cen tra tion in mo lyb de nite, such as the source of pa ren tal magma and ore ma te ri als, con tam i na tion/as sim i la tion ex tent and the physico - -chem i cal con di tions of the ore-bear ing flu ids.
The Qarachilar area is lo cated 180 km north of Tabriz and
~6–7 km south of the Arax River, within the cen tral part of the Qaradagh batholith. The Sungun por phyry Cu-Mo de posit is the larg est known PCD in NW Iran and is lo cated 130 km north of Tabriz, which is the sec ond larg est PCD in Iran and rep re sents one of the nu mer ous in tru sive stocks in the Ahar-Jolfa met al lo - gen ic zone. The Siah Kamar por phyry Mo de posit (PMD) is the first re ported de posit of this type in Iran, which is lo cated 175 km south-east of Tabriz and 10 km west of Mianeh (Fig. 2).
All these de pos its are lo cated within the Alborz-Azarbaidjan struc tural zone (Nabavy, 1976) of the Cen tral Ira nian do main (Alavi, 1991; Agha Nabaty, 2004), in the Ce no zoic Urumieh- Dokhtar mag matic arc (UDMA) (Fig. 3). This arc rep re sents the subduction-stage to post-collisional magmatism re sulted from clo sure of the Neo-Tethys Ocean be tween the cen tral Ira nian
and Ara bian plates, which oc curred in the Late Me so zoic–Early Ce no zoic (Berberian and King, 1981; Alavi, 1991). The por - phyry cop per met al lo gen ic belt of Iran com prises three ma jor met al lo gen ic zones in its north west ern (Ahar-Jolfa), cen tral and south east ern (Kerman) parts and hosts many ma jor and small PCDs and pros pects, which are as so ci ated mostly with Oligo - cene and Mio cene in tru sive bod ies.
The ore-host stocks of the stud ied de pos its have a high-K calc-al ka line to shoshonitic and metaluminous to peraluminous na ture and be long to I-type ac tive con ti nen tal mar gin granitoids (Mokhtari, 2008; Zakeri et al., 2011 for Qarachilar; Calagari, 2004a for Sungun; Khaleghi et al., 2013 for Siah Kamar). More - over, based on the avail able age data, these stocks and/or their mineralisations rep re sent the Mid dle Oligocene (in clud ing Qara chilar with the Re-Os age of 31.22 ±0.28 to 25.19
±0.19 Ma, Simmonds and Moazzen, 2015, and Siah Kamar with the U-Pb zir con age of 32.7 ±0.4 to 30.9 ±0.4 Ma and Re-Os age of 29.1 ±0.2 to 28.1 ±0.2 Ma, Simmonds et al., 2019) and the Early Mio cene (Sungun PCD with U-Pb zir con age of 22.5 ±0.4 to 20.5 ±0.15 Ma, Aghazadeh et al., 2015, and Re-Os age of 22.9 ±0.2 to 21.7 ±0.2 Ma, Simmonds et al., 2017), and hence are post-collisional.
GEOLOGIC BACKGROUND
QARACHILAR VEIN-TYPE Cu-Mo-Au MINERALISATION
The Qarachilar area is lo cated in the cen tral part of the Qaradagh batholith. This batholith was formed dur ing sev eral in tru sive pulses of Eocene-Oligocene age. It in trudes the Up per Cre ta ceous and Ce no zoic sed i men tary and mag matic rocks (Fig. 4) and oc cu pies an area of ~350 km2. It in cludes gran ite, granodiorite, diorite, quartz-diorite, syenite, quartz-syenite, mon zo nite, quartz-monzonite, quartz monzodiorite and gab bro, al though granodiorite is its dom i nant con stit u ent (Mokhtari et al., 2013). Its north ern ex ten sion be yond the Arax River is known as the Meghri-Ordubad pluton (south ern Ar me nia), which also hosts sev eral large por phyry Cu-Mo de pos its, such as Agarak and world-class Kadjaran, along with other oc cur - rences of Cu-Mo-Au-Ag min er ali sa tion (Fig. 2).
Fig. 1. Lo ca tion of the stud ied Qarachilar, Sungun and Siah Kamar de pos its in NW Iran Out line of Fig ure 3 is shown by dot ted line
480 Vartan Simmonds, Ryan Mathur and David Selby
Fig. 2. Dis tri bu tion of Ce no zoic (mainly Oligo-Mio cene) granitoids in NW Iran and south ern Ar me nia, in clud ing the ma jor Meghri-Ordubad and Qaradagh plutons and other smaller in tru sive bod ies, as well as the main por phyry Cu-Mo, base and pre cious metal de pos its in the re gion, along with the avail able Re con tents of molybdenites from these de pos its
The rhe nium con tents for the south Ar me nian de pos its are from Magakian et al. (1984) and Moritz et al. (2016), and those of the Haft Cheshmeh PCD are from Aghazadeh et al. (2015)
The granodioritic host rock in Qarachilar is made of plagio - clase (euhedral to subhedral, 40–60 vol.%), K-feld spar (anhe - dral, 5–15 vol.%) and quartz (anhedral and in ter sti tial, 15–25 vol.%), with sub or di nate amounts of bi o tite (euhedral, 5–15 vol.%), am phi bole (euhedral to subhedral, 0–10 vol.%), pyro xene (subhedral, 0–5 vol.%) and opaque min er als (0–5 vol.%). It dis plays het ero-gran u lar tex ture. Ac ces sory min er als are ap a tite, zir con and ti tan ite.
The main hy dro ther mal al ter ation zones ob served in the Qarachilar area are phyllic and potassic. The phyllic al ter ation is rec og nized by the sericitization of feld spars and re place ment of ferro-magnesian min er als by seri cite and chlorite, ac com pa - nied by the for ma tion of quartz and py rite, while the potassic al - ter ation zone is char ac ter ized by the for ma tion of shreddy bi o - tite and fine-grained anhedral and inter gra nu lar orthoclase, along with opaque min er als (mag ne tite, chal co py rite and py - rite). This al ter ation zone is found in the walls of the deeply eroded Qarachilar Val ley. Some dark-col oured veins of less than 5 cm in thick ness are also found in the lower top o graphic lev els, which con tain sec ond ary K-feld spar, quartz and shreddy bi o tite, fur ther man i fest ing the oc cur rence of potassic al ter ation (Mokhtari et al., 2013). The bound ary be tween potassic and phyllic al ter ation zones is tran si tional.
These al ter ations within the Qaradagh batholith are ac com - pa nied by Cu, Mo and Au min er ali sa tion, es pe cially in the Qarachilar area and its en vi rons in Qaradareh, Zarlidareh and Anigh (Fig. 4). Min er ali sa tion in this area oc curs mainly as par - al lel swarms of mono-mineralic and quartz-sul phide veins and veinlets and si lici fied zones, as well as dis sem i na tions within the host rock, while stockwork-type min er ali sa tion is also ev i - dent in the en vi rons of the Qarachilar area. Two ma jor sul - phide-bear ing quartz veins (GV1 and GV2) with the gen eral NW–SE trend oc cur in the area. Their length is about 700 and 400 m, re spec tively, and their thick ness ranges be tween 0.5 and 1 m. Fur ther more, many other par al lel veins and veinlets (less than 2 cm thick) are also pres ent around the main quartz veins. These veins are sur rounded by in tense phyllic al ter ation.
The main sul phide min er als are py rite, chal co py rite and mo - lyb de nite with lesser amounts of bornite and digenite. Py rite is the most abun dant sul phide min eral, while chal co py rite is the main hypogene Cu sul phide. Mo lyb de nite is pres ent as flakes (2–3 mm) or ag gre gates of anhedral and tiny crys tals (>2 mm), dis sem i nated within the quartz veins-veinlets, si lici fied zones and/or host rock.
Based on the ana lysed surficial sam ples, the Mo grade ranges from 20 ppm up to 3.6 wt.% and the Cu grade is be - Fig. 3. The Urumieh-Dokhtar mag matic arc (Agha Nabaty, 2004), which also co in cides
with the Cu met al lo gen ic belt of Iran, com prised of the Ahar-Jolfa, Tarom-Hashtjin, Cen tral Iran and Kerman zones
Some of the main por phyry Cu-Mo de pos its with avail able Re con tents are also shown;
AAZ – Alborz-Azarbaidjan struc tural zone (Nabavy, 1976)
tween 0.7 and 5 wt.% (Rezai Aghdam and Sohrabi, 2010;
Zakeri, 2013). More over, based on the geo chem i cal anal y sis of 16 al tered and fresh rock sam ples from the min er al ized zone in the Qarachilar area by Rezai Aghdam and Soharbi (2010), the Cu and Mo con tents range from 50 to 33.594 and from 6 to 529 ppm, re spec tively, where both the high est con tents be long
to a sin gle sam ple. The Cu/Mo ra tio for these data ranges from 4.5 to 96.6, with an av er age of 19.8, and most of the data clus ter be tween 5 and 20. On the other hand, 68 sam ples taken from two main quartz-sul phide veins in the Qarachilar area yielded the av er age Cu/Mo ra tios of 2.87 and 14.94, re spec tively, with the mean Cu con tents of 0.8 and 1.8 wt.%, av er age Mo con cen -
482 Vartan Simmonds, Ryan Mathur and David Selby
Fig. 4. Geo logic map of the Qaradagh batholith and the stud ied Qarachilar area (sim pli fied and mod i fied af ter Mehrpartou et al., 1997)
tra tions of 2.910 and 1.261 ppm, and mean Au con tents of 5.76 and 3.9 ppb, re spec tively (Mokhtari, 2008).
The gen e sis of min er ali sa tion hosted by the Qaradagh batholith is con tro ver sial, be ing pre sented as in tru sion-re lated gold (Mokhtari, 2008; Mokhtari et al., 2013) and vein-type Cu-Mo-Au (Rezai Aghdam and Sohrabi, 2010), as well as por - phyry type Cu-Mo min er ali sa tion (e.g., Amini Fazl, 1994; Zakeri et al., 2011; Zakeri, 2013).
SUNGUN PORPHYRY Cu DEPOSIT (PCD)
A monzonite to quartz-monzonite por phyry stock (Qm – ab - bre vi a tion in Fig. 5) of Early Mio cene age in truded the Up per Cre ta ceous pe lagic lime stone se quence (Klm), Paleocene sand stone (Ps), and Eocene andesitic and dacitic-trachytic rocks (Ea and Edt) in the Sungun area (Fig. 5). The por phyry stock was later in truded by two bar ren por phyry monzonite (Mz) and diorite (Di) stocks, as well as four gen er a tions of post-min - er ali sa tion dykes, rang ing in com po si tion from quartz diorite- quartz monzodiorite through gab bro diorite, microdiorite- micro - tonalite, and latite to trachyandesite and dacite. Fi nally, it is over lain by Plio-Qua ter nary dacitic (PlQda) and trachy andesitic (PlQt) rocks (Fig. 5; Pars Olang, 2004).
The por phy ritic quartz-monzonite stock has pro duced vast hy dro ther mal al ter ations and por phyry-type Cu-Mo min er al isa - tion. It com prises euhedral to subhedral plagioclase (30–45 vol.%; <5 mm), bi o tite (5–10 vol.%) and am phi bole (0–5 vol.%; <2 mm), fine- to me dium-grained quartz (10–20 vol.%), K-feld spar (30–40 vol.%; <0.2 mm) and opaque min er als (0–10 vol.%). It dis plays a por phy ritic tex ture with microgranular to fine-grained groundmass.
The cen tral part of the quartz-monzonite por phyry stock ex - pe ri enced hy dro-frac tur ing and hy dro ther mal al ter ation. The dom i nant al ter ations are phyllic and potassic. The potassic al - ter ation zone is char ac ter ized by the for ma tion of sec ond ary K-feld spar (2–5 vol.%; dis sem i nated within the groundmass or oc cur ring as re plac ing plagioclase and/or overgrowths on pri - mary orthoclase pheno crysts) and shreddy bi o tite (2–10 vol.%;
re plac ing the pri mary ferro-magnesian pheno crysts or oc cur - ring as dis sem i na tions within the groundmass). The phyllic al - ter ation zone is rec og nized by the for ma tion of seri cite (40–50 vol.%), quartz (30–50 vol.%) and sulphides (5–15 vol.%). At the bound ary zone be tween potassic and phyllic al ter ations, the phyllic as sem blage is su per im posed on the potassic as sem blage, cre at ing a potassic-phyllic tran si - tional al ter ation zone.
Hypogene sul phide min er al isa tion in cludes py rite, chal co - py rite and mo lyb de nite, which have mainly oc curred within the potassic and phyllic al ter ation zones as stock-work veinlets and dis sem i na tions. Supergene pro cesses have also pro duced covel lite, chalcocite, and mi nor amounts of bornite, na tive cop - per and cu prite.
Ac cord ing to the data pub lished by Ghodrati (2009, 2010), the av er age con tents of Cu, Mo and Au in the Sungun PCD are 0.6 wt.%, 0.02 wt.% and 0.04 ppm, re spec tively, and the high - est con cen tra tion of mo lyb de nite oc curred in the potassic zone.
Based on 174 sam ples taken from the hypogene zone (Ghodrati, 2009), the av er age grades of Cu and Mo are 6.094 and 276.7 ppm, re spec tively, yield ing a Cu/Mo ra tio of 3.15.
These val ues for the supergene en riched zone (n = 53) are 6.492 and 120.4 ppm, re spec tively, with a mean Cu/Mo ra tio of 53.92. Based on the same sam ples, the av er age Cu, Mo and Cu/Mo val ues for the ox i dized-leached zone (n = 7) are 2.832 ppm, 46.4 ppm and 61.03, re spec tively. Ad di tion ally, the av er age Cu con tents in the potassic (n = 77), tran si tional
potassic-phyllic (n = 33) and phyllic (n = 64) al ter ation zones are 6.568, 7.942 and 6.753 ppm, re spec tively, while the av er age Mo con tents are 330, 187 and 245 ppm, re spec tively, which yield Cu/Mo ra tios of 19.9, 42.47 and 27.56, re spec tively.
SIAH KAMAR PORPHYRY Mo DEPOSIT (PMD)
Ac cord ing to field in ves ti ga tions and the pre vi ous re - searches (e.g., Khaleghi et al., 2013), a quartz-monzonite por - phyry stock was emplaced within the por phy ritic trachybasalt, ba saltic an de site and trachyandesite (Ev), tuffs, ag glom er ates and vol ca nic ashes (Et) of Eocene age dur ing the Oligocene (Fig. 6; Zarnab Ekteshaf, 2009), which hosts the Mo min er ali sa - tion and the re lated hy dro ther mal al ter ations. The south ern and south east ern parts of the area are cov ered by Plio cene sed i - men tary rocks.
The por phyry stock con tains plagioclase (20–40 vol.%, both as euhedral to subhedral pheno crysts and microlites), anhedral fine- to me dium-grained K-feld spar (20–35 vol.%) and quartz (5–15 vol.%), and anhedral to subhedral opaque min er - als (<5 vol.%). It shows a por phy ritic tex ture with fine-grained to microlitic groundmass.
Potassic, phyllic, argillic, propylitic and silicic hy dro ther mal al ter ations are ob served within this stock. They show rather reg u lar zonation from the cen tre of the por phyry stock to wards the wall rocks. The potassic al ter ation is de vel oped mainly within the cen tral part of the stock and has af fected the ad ja cent vol ca nic rocks. This al ter ation zone is char ac ter ized by the for - ma tion of shreddy bi o tite (some times up to 40 vol.%), as well as dis sem i nated mag ne tite within the groundmass. The phyllic al - ter ation oc curred both within the por phyry stock and the ad ja - cent vol ca nic and pyroclastic rocks. It is rec og nized by the for - ma tion of quartz, seri cite (up to 50 vol.%), py rite and chlorite.
The main ore min er als are py rite, mo lyb de nite and mag ne - tite. Mo lyb de nite min er al isa tion oc curs mainly within the potassic and tran si tional potassic-phyllic al ter ation zones (the lat ter pro duced by the su per im po si tion of phyllic al ter ation as - sem blage on the potassic zone) of the por phyry stock in the form of stockwork-type quartz-sul phide and/or mono-mineralic mo lyb de nite veinlets, as well as dis sem i na tions. The ore re - serve of the Siah Kamar PMD is about 105.6 Mt, of which 39.2 Mt is the proved re serve at 539 ppm Mo, and 66.4 Mt is the prob a ble re source at 266 ppm Mo.
Based on the re sults of 87 surficial sam ples taken from the por phyry stock and the al tered coun try rocks (ana lysed by the AAS method in the lab o ra tory of the Sarcheshmeh Cu Com - plex; Khaleghi et al., 2013), the av er age Mo grade is above 0.02 wt.%, with a max i mum value of 0.27 wt.%. How ever, sub - surface core sam ples re veal grades up to 0.54 wt.%, with an av - er age of 0.25 wt.%. The Cu con tent in these sam ples ranges from 50 to an ab nor mally high value of 406 ppm, while most of the sam ples show Cu grades of 50–<100 ppm. The av er age Cu/Mo ra tio of these sam ples is about 0.44, with val ues even as low as 0.02.
MATERIALS AND METHODS
Field stud ies and sam pling of mo lyb de nite-bear ing quartz veins-veinlets and the host rocks in the Qarachilar area, Sungun and Siah Kamar de pos its were car ried out dur ing 2012–2016. Sub se quently, petrographic and mineralographic stud ies were com pleted at the Re search In sti tute for Fun da - men tal Sci ences, Uni ver sity of Tabriz (Iran). In the Qarachilar area, in ad di tion to two main quartz-sul phide veins, three other
484 Vartan Simmonds, Ryan Mathur and David Selby
Fig. 5. Geo logic map of the Sungun area (mod i fied af ter Pars Olang, 2004)
silicic veinlets with var i ous wall-rock al ter ations were also sam - pled for Re con tent anal y sis. In the Sungun PCD and the Siah Kamar PMD, mo lyb de nite-bear ing sam ples were se lected from di a mond-drilled cores within the quartz-monzonite stocks.
In or der to sep a rate mo lyb de nite from ac com pa ny ing min - er als, the fine- to me dium-grained (<2 mm) mo lyb de nite-bear - ing sam ples were crushed and the sep a ra tion was done un der a bin oc u lar mi cro scope. For large ag gre gates of mo lyb de nite flakes from the Qarachilar area, they were scraped from the vein sam ple us ing a stain less steel blade and then checked un - der the bin oc u lar mi cro scope. Fi nally, the mo lyb de nite sep a - rates with 99% pu rity were pow dered us ing an ag ate mill.
To de ter mine the pu rity of the Qarachilar mo lyb de nite sep a - rates and its polytype, two rep re sen ta tive sam ples were ana - lysed by a Siemens D500 X-Ray pow der diffractometer with a Ni-fil tered Cu-ka source and a graph ite dif fracted beam mono - chro ma tor in the X-Ray lab o ra tory of the Fac ulty of Phys ics, Uni ver sity of Tabriz.
The Re con tent of five rep re sen ta tive mo lyb de nite sep a - rates from the Qarachilar area was de ter mined at the Key Lab o -
ra tory of Iso tope Geo chron ol ogy and Geo chem is try, Guang - zhou In sti tute of Geo chem is try, Chi nese Acad emy of Sci ences, us ing XSeries-7 quadrupole ICP-MS (Thermo Sci en tific, USA) with a glass spray cham ber and a con cen tric glass nebulizer.
Each sam ple was di gested by means of the Carius tube method us ing con cen trated HNO3, which leads to pre cip i ta tion of Mo as in sol u ble MoO3 and, there fore, ef fec tively re moves the Mo ma - trix, re sult ing in much sim ple sep a ra tion of Re from the mo lyb - de nite sam ple. De tails of the an a lyt i cal pro ce dure are de scribed in Sun et al. (2010). Ac cu racy and pre ci sion of the re sults were val i dated us ing the GBW04435 (HLP-5) mo lyb de nite ref er ence sam ple from the carbonatite vein-type Mo-U de posit in the Jinduicheng-Huanglongpu re gion of the Shaanxi prov ince, China. In gen eral, the pre ci sion for iso to pic mea sure ments is better than 0.2% and the cor rec tion of mass frac tion ation has been ap plied for all re sults.
Four mo lyb de nite sep a rates of the Sungun PCD were ana - lysed at the Uni ver sity of Ar i zona (USA), us ing neg a tive ther mal ion iza tion mass spec trom e try (NTIMS; Creaser et al., 1991) by a VG 54 mass spec trom e ter. Each 30–50 mg sam ple was dis - Fig. 6. Geo logic map of the Siah Kamar area
(1:25 000; sim pli fied and mod i fied af ter Zarnab Ekteshaf, 2009)
solved in heated (180–220°C) Carius tubes loaded with 4ml of re-aqua-regia (3:1 mix ture of ultrapure 16N HNO3:12N HCl) and 2ml of hy dro gen per ox ide (added to en hance the ox i da tion of Os) for >14 hours. Re was sep a rated by a sol vent ex trac tion method us ing car bon tet ra chlo ride, as de scribed in Co hen and Wa ters (1996) and Pearson and Wood land (2000). Re was fur - ther pu ri fied by ion ex change chro ma tog ra phy, as de scribed in Mathur (2000), and mea sured us ing a Far a day col lec tor. An in - ter nal NIST Os stan dard was mea sured through out the study (n
= 3) and the 187Os/188Os of the stan dard re mained con stant at 0.1492 ±0.0002. A Henderson mo lyb de nite stan dard was also mea sured to check the ac cu racy of the data.
Four molybdenites sep a rates from the Siah Kamar PMD were ana lysed at the Uni ver sity of Dur ham (UK), us ing a Thermo Sci en tific TRITON mass spec trom e ter. 10–50 mg aliquots of the mo lyb de nite sep a rates and tracer so lu tion (185Re + iso to pi cally nor mal Os) were loaded into a Carius tube with 11N HCl (1 ml) and 15.5N HNO3 (3 ml), sealed and di gested at 220°C for ~24 h. Re was iso lated us ing stan dard NaOH-ac e - tone sol vent ex trac tion and an ion col umn chro ma tog ra phy and mea sured us ing a static Far a day col lec tor. The reproducibility of the iso to pic mea sure ments was checked us ing the RM8599 NIST mo lyb de nite stan dard, which was ana lysed dur ing the same pe riod as that of Li et al. (2017).
RESULTS
Based on the XRD anal y sis data, the Qarachilar mo lyb de - nite sam ples are of 2H polytype with hex ag o nal struc ture. The most in tense picks for the two ana lysed sam ples ap pear at 14.42 and 14.39, 39.65 and 39.59, 49.90 and 49.92, 32.79 and 39.84, re spec tively. This polytype is com mon in por phyry cop - per de pos its (Newberry, 1979a, b).
Re con tents of the mo lyb de nite sep a rates pre pared from the Qarachilar quartz-sul phide veins-veinlets, and the Sungun and Siah Kamar por phyry stocks are pre sented in Ta ble 1. The un cer tain ties for Re con cen tra tion are given as ab so lute amounts at the 2s level. The Re con cen tra tion in molybdenites of the Qarachilar area and the Sungun PCD are in the range of sev eral hun dred ppm (112.67–462.82 ppm for Qarachilar with
an av er age of 262.28 ppm, and 53.24 to 252.29 ppm for Sungun with a mean of 123.82 ppm; Ta ble 1). Ghodrati (2010) also re ported Re con tents of four mo lyb de nite sam ples from the Sungun PCD rang ing from 1.251 to 5.102 ppm, with the av er - age of 2.202 ppm. Al to gether, these val ues are in good agree - ment with the range re ported from por phyry Cu-Mo de pos its and com pa ra ble with sim i lar mineralisations across the world (e.g., Berzina et al., 2005).
Based on the data pub lished to date, the Re val ues ob - tained for the Qarachilar share a sim i lar range with the Re con - tents of most of the Cu-Mo de pos its in China (ex cept Tangshan), Mon go lia, Kazakhstan (ex cept Kounrad), Ar me nia (ex cept Elpin and Dzhindara), Chile (ex cept Los Pelambres) and North Amer ica (ex cept Cas tle Dome, Cop per Creek, and San Manuel in USA) (Berzina et al., 2005 and ref er ences therein). PCDs in Greece, Bul garia and Ser bia have higher ranges com pared to Qarachilar. Among the Cu and Cu-Mo mineralisations in the Meghri-Ordubad pluton with avail able rhe nium data (Fig. 2), the Re con tent of the Qarachilar molybdenites is in the range of those from the por phyry Cu-Mo de pos its of Dastakert, Paragachay, Agarak and world-class Kadjaran (Ta ble 2), al though the Re ranges for the lat ter two de - pos its are much more wider. Such a nar row range for the stud - ied sam ples may re sult from the lim ited num ber of anal y ses and the small sam pling area in the Qaradagh batholith. In the Ira - nian ter ri tory, data re ported from the Haft Cheshmeh, Sarcheshmeh, Sarkuh, Kerver and Now Chun PCDs (Ta ble 2) have sim i lar and/or over lap ping Re ranges, while in the Re ver - sus Cu/Mo plot of Fig ure 7, Qarachilar is plot ted near the Now Chun, Sarcheshmeh, Haft Cheshmeh and Bagh Khoshk de - pos its of Iran and the Dastakert and Kadjaran PCDs of Ar me - nia. All of them fall within the fields of Cu-dom i nated por phyry de pos its.
The to tal range of the Re con tent in the Sungun molybdenites (53.24–5.102 ppm) is com pa ra ble with all the PCDs across the world and the re gion, es pe cially the Agarak and Kadjaran PCDs in south ern Ar me nia (Ta ble 2), which have such a wide range, as well as with El Teniente in Chile, Toquepala in Peru, Bingham, Esperanza and Morenci in the USA and other PCDs in Kazakhstan and Uzbekistan (based on the data pub lished by Berzina et al., 2005). The Re range is also com pa ra ble with the molybdenites of Kahang, Sarcheshmeh,
486 Vartan Simmonds, Ryan Mathur and David Selby
T a b l e 1 Re con tent of the mo lyb de nite sep a rated from the Qarachilar area (Mo1–5),
Sungun PCD (S1–4) and Siah Kamar PMD (K1–4)
Sam ple Bore hole no.
and depth
Re [mg/g]
Mea sured 2s
Mo1 Surficial 288.46 0.93
Mo2 Surficial 462.82 2.34
Mo3 Surficial 244.71 1.24
Mo4 Surficial 202.76 0.96
Mo5 Surficial 112.67 0.50
S1 SUS62-649 m 252.29
S2 SUS61-381 m 53.24
S3 SUS70-183 m 65.95
S4 SUS62-605 m 158.08
K1 10–97 m 41.05 0.22
K2 10–99 m 21.69 0.14
K3 17–33 m 30.17 0.17
K4 17–36 m 10.44 0.05
Miduk, Sarkuh, Iju, Kerver, Abdar, Chah Firouzeh and Kuh Panj in Cen tral Iran and Kerman met al lo gen ic zones (Ta ble 2), which show rel a tively higher Re con tents in the range of thou - sands of ppm. Fur ther more, in the Re ver sus Cu/Mo plot of Fig - ure 7, the Sungun PCD is plot ted near the Kahang and Agarak PCDs, show ing very high sim i lar ity re gard ing the av er ages of Re con tent and Cu/Mo ra tio, while these av er ages are higher than those of the Qarachilar min er ali sa tion. These de pos its are also fall ing within the fields of Cu-dom i nated por phyry de pos its.
The Re con tents of both the Qarachilar min er ali sa tion and the Sungun PCD are higher than those re ported from Mo and Mo-Cu de pos its, as well as the Siah Kamar PMD, in which it var ies be tween 10.44 and 41.05 ppm with an av er age of 25.84 ppm. Con sid er ing the con cen tra tion of sev eral tens of ppm, the Siah Kamar data are com pa ra ble with those of PMDs, such as the typ i cal de pos its of Endako and Max in Can ada (Fig. 7), and Cli max and Urad Henderson in the USA, as well as most of the
mea sured PMDs in Rus sia (ex cept Amudzhikan and Davenda) and Cen tral Asia. How ever, the Siah Kamar val ues are a lit tle lower than those re ported from Boss Moun tain and Lime Creek in Can ada and Questa in the USA (Berzina et al., 2005 and ref - er ences therein). The av er age Re con tent of the Siah Kamar sam ples is also slightly lower than the av er age of 42 ppm cal cu - lated based on 19 PMDs and por phyry Mo-Cu de pos its across the world (Berzina et al., 2005). As shown in Fig ure 7, the Siah Kamar data point plot in the field of PMDs, hav ing very low Cu/Mo ra tio and Re con tent in com par i son with the stud ied and plot ted por phyry Cu-Mo de pos its of Iran and Ar me nia.
On a re gional scale of north-west and cen tral Iran and south ern Ar me nia (mineralisations of the lat ter are stud ied in de tail by Moritz et al., 2016), the Siah Kamar de posit is the only PMD dis cov ered to date and there fore, there is no other coun - ter part to make com par i son. When com par ing it with por phyry Cu-Mo de pos its across the re gion, it is clearly seen that the T a b l e 2 Re con tents of molybdenites in por phyry Cu de pos its of the south ern Ar me nia and the Cu met al lo gen ic zones across
the UDMA (Iran); lo ca tions of these de pos its are shown in Fig ure 3
PCDs
and pros pects Lo ca tion Re [ppm] Sam ple
num ber Ref er ences
Agarak SAB 538.8 1 Moritz et al. (2016)
57–6310 (mean = 820) 820 Magakian et al. (1984)
Aygedzor SAB 727.5–1141 2 Moritz et al. (2016)
Kadjaran SAB 104.3–368.3 (mean = 229.3) 6 Moritz et al. (2016)
33–2620 (mean = 245) 237 Magakian et al. (1984)
Dastakert SAB 207.9–315.8 (mean = 242.8) 4 Moritz et al. (2016)
130–300 (mean = 220) 8 Magakian et al. (1984)
Hankasar SAB 45.1–76.3 2 Moritz et al. (2016)
Paragachay SAB 258.6 1 Moritz et al. (2016)
Haft
Chashmeh Ahar–Jolfa 111.7–241 2 Aghazadeh et al. (2015)
Kahang Cen tral Iran 1332 1 Aghazadeh et al. (2015)
Sarcheshmeh Kerman 10.8–631 (mean = 292.8) 20 Aminzadeh et al. (2011)
418–987 (mean = 607.5) 6 Aghazadeh et al. (2015)
Bagh Khoshk Kerman 451–657 (mean = 545.5) 6 Aghazadeh et al. (2015)
Sarkuh Kerman 302.21 1 Mirnejad et al. (2013)
164.6–1904 (mean = 832.1) 4 Aghazadeh et al. (2015)
Iju Kerman 1715.4 1 Mirnejad et al. (2013)
938–945 2 Aghazadeh et al. (2015)
Miduk Kerman 1221.8–1229.9 2 Taghipour et al. (2008)
Kerver Kerman 304–1490 2 Aghazadeh et al. (2015)
Abdar Kerman 4247–4467 2 Aghazadeh et al. (2015)
Bondar Hanza Kerman 527–690 2 Aghazadeh et al. (2015)
Now Chun Kerman 200.5 1 Aghazadeh et al. (2015)
Darreh Zar Kerman 944.4 1 Aghazadeh et al. (2015)
Dar Alu Kerman 817 1 Aghazadeh et al. (2015)
Chah Firouzeh Kerman 3273 1 Aghazadeh et al. (2015)
Kuh Panj Kerman 1699 1 Aghazadeh et al. (2015)
mea sured val ues of the Siah Kamar PMD are much lower than those of the PCDs (Fig. 7). The ex cep tions are two sam ples from the Sarcheshmeh PCD with val ues of 10.85 and 21.30 ppm re ported by Aminzadeh et al. (2011), and a few sam ples from the Kadjaran PCD (Magakian et al., 1984), which show an over lap with the Siah Kamar val ues.
DISCUSSION
In ves ti ga tions car ried out on molybdenites of por phyry Cu and Mo de pos its show that Re con tent vari a tions may be re - lated to the com po si tion of pa ren tal mag mas and/or frac tion - ation, re ac tions be tween crustal rocks and mag mas (con tam i - na tion), depth of the sub-vol ca nic stocks, sources of the ore ma te ri als, vari a tions in phys i cal and chem i cal con di tions of crystallisation (fO2, ac tiv ity of Cl, P, T), to tal amount of mo lyb - de nite in a given de posit, and the polytype of mo lyb de nite (2H or 3R) (Giles and Shil ling, 1972; Newberry, 1979b; Todorov and Staikov, 1985; Ishi hara, 1988; Economou-Eliopoulos and Elio - poulos, 1996; Melfos et al., 2001; Xiong and Wood, 2001, 2002;
Berzina et al., 2005).
In re cent years, Re con tent of molybdenites is used to de - tect the source of ore ma te ri als (e.g., Mao et al., 1999, 2003, 2006; Stein et al., 2001; Delibaº and Genc, 2012). Mao et al.
(1999) sug gested that the metal source may af fect the Re con - tent, so that it grad u ally de creases from the man tle source (sev - eral hun dred ppm) through a mixed source of man tle and crustal ma te ri als (tens of ppm) to wards the crustal source (sev - eral ppm) (Mao et al., 1999, 2003, 2006; Stein et al., 2001;
Selby and Creaser, 2001; Berzina et al., 2005; Dai et al., 2009;
Delibaê and Genc, 2012). In other words, Re con cen tra tion de - creases from the man tle to wards the de pos its re lated to I-type and then to S-type gran ites (Berzina et al., 2005). In this re gard, for the ultrahigh- and high-Re molybdenites in the Pagoni Rachi and Konos de pos its (Greece), a LILE- and LREE-en riched sub-con ti nen tal man tle is pro posed as a magma source with min i mal con tri bu tion of the con ti nen tal crust (Del Moro et al., 1988), where the man tle wedge had some chem i cal inho - mogenities, which trig gered post-subduction metasomatism (Voudouris et al., 2013). It is while por phyry Mo and Mo-W de - pos its with ei ther crustal or i gin or a ma jor con tri bu tion of crustal ma te ri als in Greece con tain Re-poor molybdenites (Voudouris et al., 2013).
488 Vartan Simmonds, Ryan Mathur and David Selby
Fig. 7. Re con tent of molybdenites ver sus Cu/Mo ra tios of the por phyry de pos its in Iran and south ern Ar me nia, with fields de fined by Voudouris et al. (2013) for por phyry Cu, Cu-Mo, Cu-Au, Mo and Re-rich de pos its world wide and some well-known ex am ples 1 – Siah Kamar (Khaleghi et al., 2013), 2 – Kadjaran (U.S. Geo log i cal Sur vey, 2019), 3 – Now Chun (Daneshvar Saein, 2017), 4 – Haft Cheshmeh (Hassanpour et al., 2010), 5 – Qarachilar (Mokhtari, 2008; Rezai Aghdam and Soharbi, 2010), 6 – Dastakert (U.S. Geo log i cal Sur vey, 2019), 7 – Sarcheshmeh (Shafiei and Shahabpour, 2008), 8 – Bagh Khoshk (Khakzad and Shaban, 2006), 9 – Agarak (U.S. Geo - log i cal Sur vey, 2019), 10 – Sungun (Ghodrati, 2009), 11 – Kahang (Komeili et al., 2016), 12 – Iju (Mirnejad et al., 2013), 13 – Chah Firouzeh (Karimi et al., 2011), 14 – Abdar, 15 – Daralu, 16 – Darreh Zar, 17 – Miduk, 18 – Sarkuh (14–18 – Shafiei and Shahabpour, 2008)
The Re con tents of the Qarachilar and Sungun molybde - nites, as well as those of the Siah Kamar PMD, are rel a tively high within the ranges de fined for PCDs and PMDs, re spec - tively, which most likely in di cate a mixed (man tle+crustal) source for ore ma te ri als with the more pre dom i nant role of the man tle source com pared to the crustal com po nent. The I-type char ac ter is tics of the granitoid host rocks and the other in tru - sive rocks in the stud ied ar eas and gen er ally in NW Iran also prove a man tle-de rived source for these rocks and con se - quently for the min er ali sa tion re lated to them. More over, Zakeri (2013) has re ported very low ini tial 87Sr/86Sr val ues for sam ples taken from the Qaradagh in tru sive com plex, rang ing be tween 0.7037 and 0.7041, which are very close to the man tle val ues and in di cate a magma source with the high con tri bu tion of man - tle com po nent and in sig nif i cant con tri bu tion or as sim i la tion by up per crustal rocks. This fea ture can be gen er al ized to two other de pos its stud ied, es pe cially the Sungun PCD which is about 30 km south-east of it and shares many petro gen etic and geodynamic fea tures with the Qaradagh batholith.
Fur ther more, U-Pb and Re-Os age re ports of the stud ied de pos its show a Mid dle Oligocene-Early Mio cene time span. It con firms that magmatism and min er ali sa tion in these ar eas were post-collisional, post-dat ing the clo sure of the Neo- Tethyan ba sin (e.g., Berberian and King, 1981; Alavi, 1991;
Agard et al., 2006). Ow ing to the emer gence of extensional tec - ton ics af ter the pre vi ously pre vail ing compressional con di tions, they can be re spon si ble for the low in cor po ra tion of con ti nen tal crust in sup ply ing the ore ma te ri als and the dom i nance of man - tle source for them. On the other hand, in post-subduction and post-collisional en vi ron ments, par tial melt ing of the pre vi ously metasomatized man tle by the flu ids re leased from the subducted slab and the as so ci ated sed i ments could be the key to metal en rich ment, lead ing to the for ma tion of Re- and/or Te-en riched por phyry Cu-Mo-Au de pos its (Voudouris, 2006;
Voudouris et al., 2009). Both these con di tions will lead to a rel a - tively higher Re con tent of molybdenites in the re sult ing ores.
On the other hand, by tak ing into ac count the I-type and ox i - diz ing na ture of the stud ied granitoid host rocks, it can be con - ceived that the mag matic-hy dro ther mal flu ids de rived from these intrusives were also ox i diz ing in na ture. They had fa vour - able con di tions for Re trans por ta tion and sub se quent de po si - tion within the mo lyb de nite struc ture (Xiong and Wood, 1999, 2001, 2002), whereas sul phur-con tain ing re duc ing flu ids have a lower ca pac ity for trans port ing rhe nium and are not fa vour - able for the for ma tion of Re-rich molybdenites.
Ev i dence like vein-type and dis sem i nated min er ali sa tion of py rite and chal co py rite in ad di tion to mo lyb de nite in the Qarachilar and Sungun de pos its, as well as the pres ence of abun dant multi-phase fluid in clu sions con tain ing ha lite and sylvite daugh ter min er als within the sul phide-bear ing quartz veins-veinlets in these de pos its (up to 65 wt.% NaClequiv.; Simmonds and Moazzen, 2016 for Qarachilar; Calagari, 2004b, for Sungun) tes tify to the high ac tiv ity of Cl and its role as a metal trans port ing com plex in the mag matic-hy dro ther mal flu - ids. On this ba sis, the rel a tively high Re con tents of the stud ied mo lyb de nite sam ples may also be at trib uted to the high fugacity of rhe nium chlo ride within these flu ids (Berzina et al., 2005).
This is in a good agree ment with the ex per i men tal data ob - tained by Xiong and Wood (2001, 2002), which showed that chlo ride com plexes can have an im por tant role in hy dro ther mal trans por ta tion of Re at tem per a tures be tween 400 and 500°C.
For the Siah Kamar PMD, such multi-phase in clu sions are scarce and the over all sa lin ity, and thus the fCl in the ore-bear - ing flu ids, was rel a tively low (2.63–26.2 wt.% NaClequiv.; Khaleghi et al., 2013), which may have af fected the Re con tent of the re sult ing molybdenites.
In each por phyry Cu-Mo de posit, the Re con tent of molybde nites pre cip i tated from acidic hy dro ther mal flu ids (i.e. in the phyllic al ter ation zone) is higher than those pre cip i tated from al kali flu ids (i.e. in the potassic al ter ation zone) (Filimonova et al., 1984; Ivanov and Yushko-Zakharova, 1989; Berzina et al., 2005). In this re gard, in the potassic al ter ation zones formed by dom i nantly al kali so lu tions, which have high ca pac ity for Re dis - so lu tion and trans por ta tion, the Re con tent of molybdenites will be low, whereas it in creases to wards the phyllic al ter ation zone.
Sam ples No. 4 and No. 5 of the Qarachilar area, as well as the ana lysed sam ples of the Siah Kamar PMD, were taken from veinlets with potassic al ter ation in their wall rocks and there fore, they show rel a tively low Re con cen tra tion, while other Qarachilar sam ples were col lected from veinlets sur rounded by dom i nant phyllic al ter ation and have higher val ues. Sim i larly, all the sam ples from the Sungun PCD are col lected from the potassic-phyllic al ter ation zone, where acidic flu ids of the later - -stage phyllic al ter ation have left their fin ger print by pre cip i tat ing molybdenites with a rel a tively higher Re con tent. In this re gard, sam ple No. S2, which has the low est Re, shows mod er ate to in - tense potassic and weak later-stage phyllic al ter ation. In the other sam ples, the phyllic al ter ation is more in tense, jus ti fy ing their rel a tively higher Re con tents. There fore, the acid ity-al ka - lin ity of the ore-form ing flu ids can be used, to gether with other fac tors, to ex plain the Re vari a tions in these sam ples.
The Re con tent of molybdenites can also be af fected by fluid tem per a ture or the de po si tion stage (Giles and Shil ling, 1972; Newberry, 1979b; Filimonova et al., 1984; Todorov and Staikov, 1985). Ex per i men tal stud ies show that there is a neg a - tive cor re la tion be tween the tem per a ture of mo lyb de nite de po - si tion and its Re con tent (Giles and Shil ling, 1972; Newberry, 1979b; Filimonova et al., 1984; Todorov and Staikov, 1985), al - though Popov (1977) sug gested that this re la tion ship is not ap - pli ca ble for all Cu-Mo de pos its across the world.
Microthermometry of 2-phase (L–V) and multiphase fluid in - clu sions within the ore-bear ing quartz veins-veinlets yielded tem per a ture ranges of 220–540°C for Qarachilar, with most of the data clus ter ing be tween 240 and 420°C and show ing boil ing ev i dence (Simmonds and Moazzen, 2016), 160–600°C for Sungun, where the evolved mag matic flu ids in volved at the on - set of phyllic al ter ation and sul phide min er ali sa tion had tem per - a tures ~560–580°C and ex pe ri enced con tin u ous boil ing (Calagari, 2004b), and 211–300°C for Siah Kamar (Khaleghi et al., 2013), which re veals that at least some of these veins - -veinlets are formed at a rel a tively high tem per a ture and this fac tor may in flu ence the Re con tent of the sam pled molybde - nites. For ex am ple, sam ples No. 4 and No. 5 from the Qarachilar area are taken from high tem per a ture quartz-sul - phide veins-veinlets and their lower Re con tent may also re sult from their higher for ma tion tem per a ture. For the Siah Kamar PMD, the re sult ing molybdenites have low Re con tent due to their al kali na ture and the di lu tion ef fect, al though the ore-form - ing flu ids were rel a tively low-tem per a ture.
Faramazian (1961) sug gested that molybdenites of the same gen er a tion show a di rect re la tion ship be tween their grain size and the Re con tent. Among the sam ples ana lysed in this study, sam ple No. 2 from Qarachilar, with the high est Re value, was ex tracted through scrap ing by a stain less steel blade from rel a tively coarse-grained as sem blages, while other sam ples of the stud ied de pos its were col lected from veinlets con tain ing fine-grained mo lyb de nite (<2 mm). Mean while, the ex tremely high Re val ues of up to 5.102 ppm re ported by Ghodrati (2010) were mea sured on mo lyb de nite sep a rates ex tracted us ing a hand drill form large-grained ag gre gates. There fore, the pos i - tive re la tion ship be tween the mo lyb de nite grain size and its Re
con tent, as well as the cause of such high con tents in the lat ter sam ples, is clearly per ceiv able from the data pre sented herein.
To con clude, the Re abun dances in the molybdenites are af fected by the mu tual and com plex in ter ac tion of sev eral fac - tors, as was ear lier pos tu lated by Berzina et al. (2005 and ref er - ences therein). The fac tors in clude the source of pa ren tal magma and ore ma te ri als, the to tal mo lyb de nite abun dance, Eh–pH, fCl and tem per a ture of ore-form ing flu ids, al though the vol ume di lu tion ef fect seems to have the dom i nant con trol on the global dis tri bu tion of Re be tween Mo-dom i nated and Cu-dom i nated de pos its. How ever, Stein et al. (2005) have pre - sented an other ex pla na tion for low-mod er ate Re con tents in molybdenites of the Myszków Mo-Cu-W de posit in Po land, al - though it is not the case for the stud ied de pos its. Mo lyb de nite in Myszków is gen er ally as so ci ated with quartz veins and patches in granodiorite, al though these ill-de fined and scat tered veins do not con sti tute stockwork in the clas si cal sense. More over, while the potassic al ter ation is prev a lent, sec ond ary bi o tite, mag ne tite and sig nif i cant py rite are con spic u ously sparse (Stein et al., 2005). The low-mod er ate and fairly con sis tent Re con tents of molybdenites rang ing from 40 to 75 ppm in Myszków do not sup port a subduction-re lated por phyry-style or i gin (Stein et al., 2001), and a better al ter na tive would be a mod er ately lo cal der i va tion from a crustal res er voir rather than orig i na tion of the ma te ri als from dif fer ent res er voirs, mix ing and sys tem-wide fluid sep a ra tion (por phyry model). In other words, de vel op ment of veins likely de pended on lo cal sep a ra tion and vol a tile en hance ment of hy dro ther mal flu ids that were not far-trav elled. On this ba sis, au thors sug gest that the Myszków Mo-Cu-W de posit is the prod uct of rapid orogenic up lift and ex - hu ma tion melt ing, which have lim ited the de vel op ment of a clas sic por phyry-style min er ali sa tion.
CONCLUSIONS
The Re con tents of five mo lyb de nite sep a rates ex tracted from quartz-sul phide veins-veinlets in the Qarachilar area and four mo lyb de nite sep a rates from the Sungun de posit are in the range of PCDs across the world, while those of the Siah Kamar de posit (n = 4) are ob vi ously dis tin guish able from por phyry Cu de pos its with their lower val ues and cor re spond to the range de fined for por phyry mo lyb de num de pos its. This dif fer ence can be re lated pre dom i nantly to the vol ume di lu tion of Re with the pres ence of large vol umes of mo lyb de nite in PMDs, while in the Cu-dom i nated mineralisations, the low mo lyb de nite abun dance leads to the con cen tra tion of Re within it as its main host (e.g., Berzina et al., 2005 and ref er ences therein).
The rel a tively high Re con tents in the stud ied de pos its com - pared to the ranges pro posed for each type can be ex plained by con sid er ing a mixed man tle + crust source for the ore ma te ri als with a more dom i nant role of the man tle source com pared to the crustal com po nent. The I-type char ac ter is tics of the host rocks and the post-collisional set ting of the magmatism and min er al - isa tion un der the extensional tec tonic re gime con firm this as - sump tion.
Mean while, vari a tions of Re con tent in dif fer ent sam ples taken from these ar eas and from dif fer ent veins can be ex - plained by tak ing into ac count the for ma tion tem per a ture of these veins, acid ity/al ka lin ity of hy dro ther mal flu ids or, in other words, the type of al ter ation ac com pa ny ing the min er al isa tion, as well as the grain size of molybdenites. Thus, molybdenites formed in higher tem per a tures or within the potassic al ter ation zone were found to have lower Re con tents com pared to those formed in lower tem per a tures or within the phyllic al ter ation zone. Ad di tion ally, it is clearly ev i dent that a pos i tive cor re la tion ex ists be tween the grain size of molybdenites and their Re con - tent in the stud ied sam ples.
On the re gional scale and based on the Re con tents, the Qarachilar and Sungun molybdenites are com pa ra ble with the Dastakert, Agarak and world-class Kadjaran por phyry Cu-Mo de pos its in the Meghri-Ordubad pluton (south ern Ar me nia), which is con sid ered as the north ern ex ten sion of the Qaradagh batholith. These sim i lar Re ranges fur ther con firm sim i lar i ties re gard ing the tec tonic set ting and min er al isa tion con di tions be - tween both batholiths. Ad di tion ally, the Re con tents of molybdenites in these two de pos its are in the range of those from the Haft Cheshmeh (NW Iran), Sarcheshmeh, Sarkuh and other PCDs and pros pects in the Kerman Cu met al lo gen ic zone, which are also lo cated on the UDMA and share sim i lar tec tonic and petro gen etic fea tures with the stud ied de pos its.
How ever, as the Siah Kamar de posit is the first por phyry Mo min er al isa tion dis cov ered in Iran and the south ern Lesser Cau - ca sus, it has no coun ter part to com pare with, while its Re con - tent is lower than all the PCDs in these re gions.
Ac knowl edge ments. This study was fi nan cially sup ported by the Dep uty Dean of the Re search Bu reau of Tabriz Uni ver - sity through the grants Nos: 90208, 27/3570-8 and 6814.
There fore, the au thors would like to ex press their thanks and ap pre ci a tion to the au thor i ties in this bu reau. DS also ac knowl - edges the To tal En dow ment Fund. Thanks are fur ther ex tended to two anon y mous re view ers, whose con struc tive com ments and sug ges tions helped to im prove the manu script.
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