Fluid Inclusion and Stable Isotope Geochemistry of the Orogenic–Type MARK Zinvinjian Cu–Pb–Zn–Au Deposit in the Sanandaj–Sirjan Metamorphic Belt, Northwest Iran

Journal of Geochemical Exploration 184 (2018) 82–96

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Journal of Geochemical Exploration

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Fluid inclusion and stable isotope geochemistry of the orogenic–type MARK Zinvinjian Cu–Pb–Zn–Au deposit in the Sanandaj–Sirjan metamorphic belt, Northwest Iran

⁎ Sina Asadia, Shojaeddin Niroomandb, , Farid Moorea a Department of Earth Sciences, Faculty of Sciences, Shiraz University, Shiraz 71454, Iran b Department of Geology, Faculty of Science, University of Tehran, Tehran 14155–64155, Iran

ARTICLE INFO ABSTRACT

Keywords: The Zinvinjian polymetallic deposit occurs as veins controlled by a NW–SE trending–structure within the Quartz veins Cretaceous metamorphosed limestone and dolomite, schist, and metavolcanic rocks, northwest of Iran. The Metamorphic fluid retrograde greenschist facies metamorphism was accompanied by large–scale transpressional faulting, crack–- Fluid unmixing seal veins, infiltration of large volumes of hydrous fluid with high XCO2, and is largely overlapped by the main Stable isotopes hydrothermal events. The metamorphism has resulted in two stages of mineralization in the Zinvinjian deposit. Zinvinjian These are early–stage polymetallic sulfides–quartz and late–stage pyrite–quartz veins. The early–stage veins Iran filled fractures and are undeformed, suggesting a tensional shear setting. The late–stage veins are also mainly open–space fissure–fillings that cut or replace earlier veins. Three types of fluid inclusions (FIs), including aqueous (type–I), mixed carbonic–aqueous (type–II), and carbonic (type–III), were identified in ore–related quartz veins. The early–stage quartz contained all three types of primary FIs homogenized at temperatures of range 197–300 °C and salinities of 2.5–15.2 wt% NaCl equivalent. In contrast, the late–stage quartz veins contained only type–I FIs with homogenization temperatures ranging between 192 and 210 °C, and salinities of 0.2–2.7 wt% NaCl equivalent. This indicates that the metallogenic system evolved from a carbonic–rich, metamorphic fluid to a carbonic–poor, one through input of meteoric fluids. All three types of FIs in the early–stage minerals displayed evidence of vein formation during an episode of fluid immiscibility. Quartz δ18O (+15.3 to +19.0‰) and sulfide δ34S(−9.4 to +11.6‰) indicate isotopic equilibrium with host metasediments (rock buffering) and a metasedimentary source of sulfur during early–stage. It is believed that ore mineralization is the result of a decrease in base–metal solubility during an episode of the fluid immiscibility. This study suggests that mineralization at the Zinvinjian deposit is metamorphogenic in style, probably related to a deep–seated orogenic system.

1. Introduction world scale; (2) orebodies occur as vein systems and are structurally controlled by faults including deep–crustal shear zones; (3) ore–forming

Orogenic–type deposits almost provide one–third of the global gold ﬂuids are rich in CO2 and/or CH4; (4) mineralization depths range from production (Goldfarb et al., 2001; Groves et al., 2003; Frimmel, 2008). 5 to 20 km; and (5) they form mainly during a tectonic transition phase The possibility and potential of exploring for Cu, Pb–Zn, Fe, Ag, Au and from compression to strike–slip or extension. other metallic commodities in geologically, geochemically and struc- Retrograde hydration and/or carbonation of metamorphic rocks turally similar orogenic gold deposits have also been proposed (Chen may show a similar spectrum of behavior on scales from local vein–- et al., 2004a, 2004b; Pirajno, 2009; Pirajno et al., 2011; Asadi et al., controlled alteration to more regionally pervasive retrogression (Asadi 2014). The orogenic–type deposits commonly display the following et al., 2013a, 2014). Retrograde alteration is often associated with characteristics (Groves et al., 2003; Goldfarb et al., 2005; Yardley, economic metalliferous mineralization. Base metal– and gold–bearing 2005; Chen, 2006; Pirajno, 2009): (1) an association with active con- vein systems are common to many metamorphic belts worldwide (e.g. tinental margins in orogenic belts and widespread throughout middle Nesbitt, 1991; Robert et al., 1995; Groves et al., 2003; Chen et al., Archean to Tertiary, which are located on the metamorphic belts in the 2004a, 2004b; Yardley, 2005; Deng et al., 2008; Li et al., 2008, 2011;

⁎ ⁎ Corresponding author. E-mail address: [email protected] (S. Niroomand). http://dx.doi.org/10.1016/j.gexplo.2017.10.013 Received 9 February 2017; Received in revised form 6 October 2017; Accepted 16 October 2017 Available online 20 October 2017 0375-6742/ © 2017 Elsevier B.V. All rights reserved. S. Asadi et al. Journal of Geochemical Exploration 184 (2018) 82–96

Pirajno, 2009; Zhang et al., 2012; Ni et al., 2012). The mineralization at Kharapeh deposit (3 km South of Zinvinjian) Mineralization is commonly controlled by fold or fault systems, with is described in detail by Niroomand et al. (2011), but this study re- fault movement regulating hydrothermal fluid flow (e.g. Anderson presents the first detailed description of the Zinvinjian Cu–Pb–Zn–Au et al., 2004; Pirajno, 2009; Craw et al., 2010; Zhengjie et al., 2015). The deposit in the northwestern part of the SSMB. majority of fault–hosted base metal– and gold–bearing vein systems are This work tried to better understand the chemical history of flui- believed to have formed late in the orogenic history of the host meta- d–rock interaction at the studied deposit, including the composition morphic complex, with uplift, cooling and subsequent onset of brittle and origin of the ore fluids, as well as the thermal and hydrodynamic fracture conditions promoting the migration of mineralizing fluids regime of ore formation. Also, it focuses on the origin and composition (Schmidt Mumm et al., 1997; Anderson et al., 2004; Craw et al., 2010; of the fluid and its evolution during the mineralization process. In order Goldfarb and Groves, 2015). Groves et al. (1989) believe that or- to achieve the main objective of this study, we report new data obtained ogenic–type deposits include epigenetic, structurally, controlled sulfide from field investigations, ore geology, microthermometry, and Raman ores (e.g. chalcopyrite–sphalerite–galena–pyrite), mostly in siliceous spectroscopy of fluid inclusoins, and stable isotope compositions of vein veins along fault zones (usually strike–slip faults with normal compo- minerals. nent of movement), preferentially hosted in metamorphosed volcano–sedimentary series. According to Waring et al. (1998) and Mateus 2. Geotectonic setting and regional structural evolution et al. (2003), orogenic–type deposits can be grouped into three major types characterized by the following metal associations: 1) Cu (Pb, Zn, The SPMC is located between the Hamedan–Tabriz volcanic arc Ag, Au); 2) Cu (Fe, Zn, Sb, Hg); and 3) Au (Co, Ni, Cu). (HTV) along the eastern boundary of Sanandaj Cretaceous volcanic arc The most prospective region for metalliferous vein systems in Iran is (SCV) and the Sonqor–Baneh volcanic arc (SBV) on the western the Sanandaj–Sirjan metamorphic belt (SSMB), trending NW–SE boundary of Sanandaj–Sirjan metamorphic belt (Azizi and Moinevaziri, (Mohajjel et al., 2003), and affected by metamorphism (greenschist to 2009; Fig. 2). Geodynamically, a crustal thinning episode during Late amphibolite facies) and an obliquely thrusted wedge, with asymme- Paleozoic to Middle Triassic times has been suggested for occurrence of trical structures in the HP–LT metamorphic rocks (Sarkarinejad and volcano–sedimentary sequences in the SSMB (e.g. Rashid et al., 2002; Azizi, 2008). Alavi, 2004; Sheikholeslami et al., 2008). During the Early–Cimmerian The relationship between metalliferous vein systems and tectonic orogeny (Late Triassic), the Tethyan oceanic lithosphere in the south settings will be explored in greater detail with regard to the compre- margin of SSMB created along the accretion axis at SW and started to be hensive review on all aspects of the evolution of the SSMB. The SSMB is consumed by subduction under the central Iranian plate after the Late a highly endowed metallogenic province, hosted several major gold and Triassic (Sheikholeslami et al., 2008). Following the subduction, two base–metal deposits (Table 1) belonging to six main ore deposit types/ main regional metamorphic events and two co–axial stages of folding styles, including; orogenic gold deposits (e.g. Qolqoleh, Kervian, Qa- emerged in the Zinvinjian area (e.g. Niroomand et al., 2011; Ghorbani, baqloujeh, Kharapeh, Alut), epithermal gold–base metal deposits (e.g. 2013). These Mesozoic Barrovian–type metamorphic events Aghdarreh, Sari Gunay, Gozalbolagh), Carlin–type deposits (e.g. Zar- (Houshmandzadeh and Soheili, 1990) range from garnet–amphibolite shuran, Akhtarchi), intrusion-related gold ( ± base–metal) systems to kyanite–quartz–mica schist and greenschist facies (Sheikholeslami (e.g. Muteh, Astaneh–Sarband, Zartorosht), metamorphogenic base–- et al., 2008). The prograde metamorphic event during the Ear- metal deposits (e.g. Bavanat), and gold–rich volcanic–hosted massive ly–Cimmerian discordance recorded the onset of the compression re- sulfide (VMS) deposits (e.g. Barika) (Nezafati et al., 2005; Aliyari et al., lated to the peak of metamorphism (700 °C and 10 kbar; Sheikholeslami 2009, 2012; Fig. 1). The SSMB, with regard to orogenic gold and et al., 2008). Peak regional metamorphic mineral assemblages probably base–metal deposits, is comparable to other Phanerozoic orogens that crystallized during D1 deformation. formed by accretion of continental crust along the complex subduction Uplift and cooling of the metamorphic complex during Late zone of Gondwana, such as New Zealand and South America (Bierlein Cimmerian orogeny (Middle Jurassic time; 159–167 Ma) has resulted in et al., 2001; Goldfarb et al., 2001), and the Lachlan Orogen (Hough development of D2 deformation and associated with large–scale retro- et al., 2007). The spatial distribution of the gold and base–metal de- gressive hydration of amphibolites to greenschist facies assemblage posits of the SSMB related to their formation within a unique tectonic (Sheikholeslami et al., 2008). The exhumation continued during the framework, which, in turn, provides important clues regarding the Late Cimmerian orogeny with two consequences: the first, as high- metallogenesis of these deposits. lighted above, was the progressive cooling of metamorphic minerals A large number of the orogenic–type Cu, Pb–Zn, Au and Ag deposits and infiltration of large volumes of hydrous fluids, which resulted in have been identified in the SSMB including the Zarshuran Au–As (Zn) retrograde metamorphism (Sheikholeslami et al., 2008). The second (Asadi Haroni et al., 1999; Mehrabi et al., 1999), Barika Au–Ag consequence was the coeval development of retrograde metalliferous (Zn–Pb–Cu) (Tajeddin et al., 2004), Agh Dareh Au (Sb–As–Hg) (Daliran, quartz veins in the northwest of SSMB (Niroomand, 2010; Ghorbani, 2007), Chahgaz Zn–Pb–Cu (Mousivand et al., 2010), Kharapeh Au 2013). (Cu–Zn–Ag) (Niroomand, 2010; Niroomand et al., 2011), Bavanat In the SPMC, the folds of the first stage of deformation are tight to Cu–Zn–Pb (Ag) (Asadi et al., 2013b; Asadi and Moore, 2017), Chahgaz isoclinal and recumbent (Niroomand, 2010). Their axes are character- Zn–Pb–Cu (Mousivand et al., 2012), Shamsabad Pb–Zn–Au–Ag (Fe) ized by low to intermediate plunges towards the northwest and are well (Ghorbani, 2013), and Qarachilar (Cu–Mo–Au) deposit (Simmonds and developed in schists. In contrast, the second folding stage is observed as Moazzen, 2016) deposits. In fact, the northern part of SSMB is the most upright and open folds. The axis of this folding has a low plunge to- prospective metallotect for polymetallic lead–zinc–copper–gold ex- wards northwest and is parallel to sub–parallel to the axis of the first ploration in Iran. folding. These folds of the second stage play an important role in the The Zinvinjian Cu–Pb–Zn–Au deposit, located on the northwestern northwestern SSMB, because they are responsible for the localization of edge of the SSMB, northwest Iran, is hosted by a Cretaceous meta- ore–bearing quartz veins. Also both normal and strike–slip faults are morphosed and highly deformed volcano–sedimentary sequence common in the area. The normal faults were developed parallel to the (Sardasht–Piranshar metamorphic complex; SPMC) that have under- axial surface strike of the second stage folds. Normal fault displace- gone greenschist facies metamorphism (Niroomand, 2010). Late– or ment, on the order of meters, and density of these faults are greatest in post–metamorphic metalliferous quartz veins are common in the SPMC. the hinge of the folds relative to the limbs. This type of fault has a Evaluation of the deposit by Geological Survey of Iran (GSI) outlined distinct fault plane characterized by striations; field measurements the reserves around 100,000 t, averaging 1% Cu, 1.75% Zn, 2% Pb, and confirmed the dip–slip nature (Niroomand et al., 2011). The hanging- 0.3 g/t Au (Niroomand et al., 2011). wall of the fault is typically downthrown with offset as great as 20 m. At

83 .Aaie al. et Asadi S.

Table 1 Characteristics of major orogenic type deposits (base metal and gold-bearing vein systems) in the Sanandaj-Sirjan metamorphic belt.

Deposit Geographic Host rocks Ore mineralization Genesis Age of Principal ores Alteration minerals Tonnage References coordination mineralization

Kervian E 36°08′00″ Felsic to mafic metavolcanic and Narrow quartz veins and Orogenic (ductile shear Upper Pyrite, chalcopyrite, Quartz, carbonate, Unknown Heidari et al. (2006) N 46°06′00″ metasedimentary rocks veinlets mineralization; 60 m zone) Cretaceous- arsenian pyrite, realgar sericite, and chlorite wide, 2500 m long Tertiary Barika E 36°11′16″ Cretaceous metaandesite and tuff Quartz sulfide bearing zone; Orogenic gold deposit Lower Electrum, sphalerite, Quartz, sericite, 1Mt Yarmohammadi (2006) N 45°39′03″ (greenschist to lower amphibolites 50 m- wide, 100 m-long. (metamorphosed Cretaceous- pyrite, galena, pyrite, calcite, albite metamorphic facies) massive sulfide?) Tertiary tetrahedrite, tennantite, chalcopyrite Qolqoleh E 36°08′08″ Mafic to interamediate (andesite Narrow quartz –gold-sulfide Orogenic (ductile to Upper Pyrite, chalcopyrite, Quartz, sericite, Up to 3 Mt Aliyari et al. (2009, N 46°06′08″ to andesitic basalt) Metavolcanic zones; 250 m wide, 2500 m- brittle shear zones) Cretaceous- pyrrhotite, sphalerite chlorite, epidote, 2012) rocks and schist long, 280 m-down-dip Tertiary and tourmaline Zartorosht E 57°10′00″ Ma fic to intermediate volcanic Thick gold-bearing quartz- Orogenic and/or Tertiary Pyrite, chalcopyrite, Quartz, carbonate, Unknown Rastgoo Moghadam N 28°12′00″ pyroclastic rocks in greenschist to sulfide veins and veinlets; Intrusion related galena, sphalerite, sericite, and epidote et al. (2008) lower amphibolites metamorphic 10–20 m-wide, 50–100 m- arsenopyrite, pyrrhotite facies length filling the normal faults 84 Muteh E 50°45′00″ Felsic schist, and Metarhyiolite Thick quartz-sulfide veins; Orogenic and/or Eocene Pyrite, chalcopyrite, Quartz, sericite, 14 Mt Rashid Nejad–Omran N 33°42′00″ rocks in greenschist metamorphic 5–10 m-wide and 20–50 m- Intrusion related arsenopyrite, pyrrhotite, carbonate, and (2002), Moritz et al. facies length filling the normal sphalerite, bismutite, kaolinite (2006) faults digenite, and covelite, Kharapeh E 36°42′23″ Limestone, contact between Thick quartz veins and Orogenic (brittle) Upper Pyrite, chalcopyrite, Quartz, carbonate, 70,000 t Niroomand et al. N 45°15′51″ andesite dyke and limestone veinlets; 6 m-wide, 1500 m- Cretaceous- galena, and sphalerite chlorite, sericite, (2011) long Tertiary kaolinite Bavanat E 53°35′40″ Permo-Triassic metabasite and Narrow quartz veins and Epigenetic orogenic-type Early Jurassic Pyrite, chalcopyrite, Quartz, carbonate, 6Mt Asadi et al. (2013a); N 30°27′03″ metasediment rocks, Maficto veinlets; 20–40 m-wide, systems arsenian pyrite sericite, and biotite Asadi and Moore intermediate metavolcanic rocks 800 m-long (2017) in greenschist metamorphic facies Alut E 36°10′50″ Mafic to intermediate volcanic Narrow quartz veins and Orogenic (brittle to Upper Pyrite, chalcopyrite, Quartz, sericite, 150,000 t Tajeddin et al. (2004, N 45°52′49″ rocks, sericite and biotite schist, veinlets ductile shear zone) Cretaceous- sphalerite, and pyrrhotite carbonate, chlorite, 2006)

and granite intrusion Tertiary and epidote Journal ofGeochemicalExploration184(2018)82–96 Qabaqloujeh E 36°05′35″ Upper Cretaceous metavolcanic Quartz veins and veinlets; Orogenic (ductile to Early Jurassic Chalcopyrite, pyrite, Quartz, carbonate, 6Mt Nosratpoor (2008) N 46°06′59″ phyllite, schist and mylonitic rocks 5–20 m-wide, 100 m-long brittle shear zones) galena, sphalerite, and sericite, chlorite, and in greenschist metamorphic facies pyrrhotite tourmaline, and kaolinite Antaneh E 49°25′50″ Granite, Granodiorite intrusion Narrow to thick veins and Intrusion related gold Early to late Chalcopyrite, pyrite, Quartz, sericite, Unknown Nekouvaght Tak N 33°52′30″ and micro granodiorite dykes veinlets, Eocene arsenopyrite, pyrrhotite, chlorite, tourmaline, (2008) sphalerite, marcasite and kaolinite Zinvinjian E 36°24′54″ Marble, schist, contact between Narrow veinlets to very thick Orogenic (brittle shear Jurassic- chalcopyrite, pyrite, Quartz, carbonate, 100,000 t Niroomand (2010) N 45°17′26″ andesite dyke and marble veins (up to 10 m) zone) Cretaceous sphalerite, galena, chlorite, sericite, chalcocite, and covellite kaolinite with minor bornite S. Asadi et al. Journal of Geochemical Exploration 184 (2018) 82–96

Fig. 1. Main tectonic units of Iran showing the location and broad distribution of various types/styles of the major base–metal and gold deposits/prospects in the northern and southern Sanandaj–Sirjan metamorphic belt, its Mesozoic magmatic assemblage related to Urumieh–Dokhtar magmatic belt, and the location of two cross–sections (a and b) on it (after from Alavi, 2004; Ghasemi and Talbot, 2006). 1 – Kharapeh, 2 – Barika, 3 – Saqez–Sardasht orogenic–type deposits (Qolqoleh, Kervian, Qa- baqloujeh, Hamzeh Qaranein, and Alut), 4 – Agh- darreh–Zarshuran, 5 – Tuzlar, 6 – Sari Gunay, 7 – Akhtarchi, 8 – Astaneh–Sarband, 9 – Muteh, 10 – Bavanat, and 11 – Zartorosht. Orogenic (metamorphogenic); intrusion related; epithermal; Carlin and Carlin–like; and gold–rich VMS deposits/occurrences (after Nezafati et al., 2005; Aliyari et al., 2009, 2012).

the Zinvinjian deposit, the quartz veins are mainly hosted by this type flow due to their brittle character during regional deformation. These of fault along the fold axes. Strike–slip faults cut across the axes of the units have been affected by two stages of folding. The ore–bearing regional folds, as well as across the quartz veins, and associated quartz veins were related to and formed during the last folding stage. shearing locally increases the grade of gold and base–metals within the Ore bearing quartz veins outcropped with lengths between 3 km, Zinvinjian deposit. thickness 10 m (in average) with nearly NW–SE trend and 80o–90o degree dip direction (Fig. 4a). Based on the mineralogical assemblages, 3. Deposit geology geometry, texture, and crosscutting relationships, mineralization at the Zinvinjian system is divided into two different types of quartz veins and – The Zinvinjian Cu–Pb–Zn–Au deposit, located 14 km northeast of hydrothermal stages (Fig. 4b, c). These are early stage polymetallic fi – – – – Piranshahr and 3 km east of Kharapeh orogenic Au (Cu–Zn–Ag) deposit, sul de bearing quartz (type A) and late stage pyrite bearing quartz – is a polymetallic deposit in the SPMC. Geological units in the study area (type B) veins. – fi – are those defined by Khodabandeh and Soltani (2004) for a part of the The early stage polymetallic sul de veins represent the main ore fi northwestern SSMB. Metasedimentary rocks consist of Cretaceous me- stage of sul de mineralization. This indicates that they were formed in tamorphosed limestone and dolomite, schist, slate, and phyllite (Fig. 3). a tensional shear setting and did not undergo compressional deforma- Abundant mafic metavolcanic rocks (omitted for clarity in Fig. 3) tion. The orebodies are along the faults and the associate shear zones – – comprise concordant sills and overlying volcanic rocks. Volcanic rocks, striking 302 312° and dipping to northeast with an angle of 43 55°. – fl with submarine characteristics, outcrop in the Zinvinjian area (Fig. 3). The ore hosting faults chie y developed in the metamorphic rocks of They are mainly flows, with lesser pyroclastic rocks. This lithologic the Zinvinjian area. > 90% of ore mineralization is distributed in – – group is comprised of andesite, trachyandesite, and tuffs with a cal- NW SE striking shear zones hosted in the metasediments. The main ore – c–alkaline composition. The SPMC is overlain by the Eocene and Mio- stage is characterized by medium grained white to creamy quartz cene marl and conglomerate, which in turn are locally covered by (< 0.2 mm; Fig. 4c), having chalcopyrite, pyrite, sphalerite, galena, young Quaternary deposits. chalcocite, and covellite with minor bornite (Fig. 4d, e). These dis- – – The SPMC rock units are considered to constitute favorable sites for cordant ore bearing quartz veins have NW SE trend crosscut bedding fi mineralization, because they provide a preferential conduit for fluid with various thicknesses ranging from few centimeters to ve meters.

85 S. Asadi et al. Journal of Geochemical Exploration 184 (2018) 82–96

Fig. 2. The Sanandaj Cretaceous volcanic arc (SCV) and the Sonqor–Baneh volcanic arc (SBV) on the western boundary of Sanandaj–Sirjan metamorphic belt (modiﬁed after Azizi and Moinevaziri, 2009), and geographical location of the study area in northeast of Piranshahr.

The Zinvinjian metalliferous vein systems are believed to have formed phase transformations. Stage calibration was carried out at −56.6 °C late in the orogenic history of the metamorphic complex host, that is (pure CO2), 0.0 °C (H2O), and 374.14 °C (H2O) using synthetic FIs during uplift, cooling, and subsequent onset of brittle–ductile fracture standards. In addition, FIs with no evidence of necking down were se- conditions promoted the migration of mineralizing fluids (Niroomand lected for microthermometric analyses (Roedder, 1984). et al., 2011). According to Pirajno (2009), breccia and open–space The salinities of H2O–CO2–NaCl and NaCl–H2O systems were cal- filling textures are commonly seen in the brittle–ductile regimes such as culated using the final melting temperatures of CO2–clathrate (Collins, those at the Zinvinjian deposit. 1979) and ice points (Bodnar, 1993), respectively. Because the opaque The late–stage barren quartz veins crosscutting the ore–bearing solid phases do not melt during the heating process, the salinities pre- veins and replacement bodies that formed in the earlier stages. They sented here do not include the contribution of these opaque minerals. mainly consist of milky–white quartz (> 0.2 mm; Fig. 4c), with massive Calculations of pressure range were made using published equations of pyrite (Fig. 4f), and minor amounts of other sulfide minerals (e.g. state: Bowers and Helgeson (1983) for H2O–CO2–NaCl FIs; Holloway chalcopyrite; Fig. 4f). These concordant quartz veins are structurally (1981) for carbonic liquid FIs; and Zhang and Frantz (1987) for deformed, brecciated, and recrystallized, suggesting that they were H2O–NaCl FIs (isochores calculation; lines of equal density) in the formed parallel to layering and foliation with different volume and computer package FLUIDS (Bakker, 2003). Also, calculations of depth thickness within limestone and schist borders in brittle conditions. (km) are based on equation of Shepherd et al. (1985). All abbreviations and terminology of Fls are referred to Diamond (2003). Laser Raman spectroscopic analysis was performed on vapour 4. Fluid inclusion studies phases in selected inclusions using a Jobin–Yvon Labram HR Raman microprobe at the Virginia Tech University (USA). The incident laser 4.1. Sampling and analytical procedures wavelength was 532 nm, and minimum detection limits were 0.01 mol percent for N and CO , and 0.03 mol percent for CH and H S. The Samples for FIs study were collected from the quartz veins of the 2 2 4 2 molar fractions (X) were calculated using the relative Raman scattering Zinvinjian deposit. Fourteen quartz samples from the two different cross–sections for CO ,CH ,N , and H S as suggested by Frezzotti et al. stages were selected to conduct studies of FIs, including petrography, 2 4 2 2 (2012). microthermometry, and Raman spectroscopy. Microthermometric measurements were made using a Linkam THM–600 combined heating–freezing stage with a temperature range of −196 to +600 °C, 4.2. Fluid inclusions petrography attached to a Nikon petrographic microscope with LinkSys software (version 1.83). Precision is ± 0.1 °C between −70 °C and 40 °C, ± 2 °C Fluid inclusion types were identified based on their phases at room below −70 °C, and ± 1 °C above 100 °C. The heating/freezing rate is temperature using the criteria of Van den Kerkhof and Hein (2001). generally 0.2 to 10 °C/min, but was reduced to < 0.2 °C/min near Based on petrographic and microthermometric studies and phases

86 S. Asadi et al. Journal of Geochemical Exploration 184 (2018) 82–96

Fig. 3. Simpliﬁed geological map of the Zinvinjian Cu–Pb–Zn–Au deposit in the SSMB, and geographical location of the study area in northeast of Piranshahr. present at temperature room, FIs are divided into the following types FIs range from −24 to −30.1 °C and from −21.5 to −32 °C, respec-

(Fig. 5a–d): aqueous (type–I), mixed aqueous–carbonic (type–II), and tively. Homogenization temperatures (Th)ofIA and IB FIs (Fig. 6a, b), carbonic (type–III) inclusions. range from 197 to 225 °C and 192 to 210 °C, respectively, whereas Th Type–I FIs are commonly present in quartz veins of different or- values of type–IIA inclusions range from 255 to 300 °C (Fig. 6a). The e–forming stages (IA and IB), representing 60% of the total population of majority of the inclusions (type–IIA and –IB) homogenized to a liquid FIs (Fig. 5a–d). Two–phase (liquid H2O + vapour) FIs have a degree of phase (LV → L), although some Fls (type–IA) to a vapour phase (LV → fill typically 0.85 vol% liquid, rarely ~0.5 vol% liquid, and show V; Fig. 5a). The type–IA and IB FIs yield final ice melting temperatures variable shapes (negative, elliptical, and irregular). The inclusions are (Tm(Ice)) of −1.5 to −3.4 °C and −0.1 to −1.7 °C, respectively. These usually 3 to 8 μm in size and occur as isolated clusters suggesting a temperatures correspond to salinities of 2.5 to 5.5 wt% NaCl equivalent primary origin. for type–IA inclusions (Fig. 6c) and 0.2 to 2.7 wt% NaCl equivalent for Type–II FIs are typically found in the early–stage (IIA) polymetallic type–IB inclusions (Fig. 6d). The calculated densities for IA and IB FIs sulfide–bearing quartz veins (type–A). These FIs contain three phases vary between 0.82 and 0.98 and 0.77 and 0.94 g/cm3, respectively.

(liquid H2O+CO2–rich fluid + vapour), consisting of 25–50 vol% The final melting temperatures of solid CO2 (Tm (CO2)) in the IIA carbonic phase, up to 12 μm in size and are ellipsoidal in shape and IIIA FIs range from −55.7 to −58.2 °C and −56.4 to −57.6 °C, (Fig. 5b). They occur as trails along healed zones, but do not cross the respectively. These values are in part lower than the triple point for crystal boundaries suggesting that they are primary or pseudosecondary pure CO2 (−56.6 °C), indicating that a significant amount of CH4 and/ in origin. Liquid CO2 at room temperature appears as a dark boundary or N2 is present (Dreher et al., 2007; Volkov et al., 2011; Bodnar et al., in the inner wall. 2014; Zhengjie et al., 2015). Clathrate melting temperatures (Tm(Cla)) Type–III FIs contain as much as 15% of the total FIs in the early–- in the IIA and IIIA FIs range from +0.3 to +1.5 °C and +2.1 to stage (IIIA) of type–A veins, and consist of almost pure liquid CO2 +3.4 °C in these FIs, corresponding to salinities of 13.8–15.2 and (> 60 vol% carbonic phase) or vapour at room temperature (Fig. 5c). 11.3–13.1 wt% NaCl equivalent, respectively (Fig. 6c).

The liquid CO2 FIs are yellow to brown, whereas the vapour CO2 FIs are Homogenization temperatures of CO2 (Th (CO2)), to the liquid black to brown in color. Most type–III FIs are isolated with no planar phase, are between 20.8 and 30.1 °C for type–IIA FIs. The CO2 densities array and typically display regular shape, suggesting a primary origin. range from 0.63 to 0.89 g/cm3 and bulk densities range from 0.8 to 3 The sizes of primary FIs are commonly < 12 μm. 1.12 g/cm . Some type–IIA FIs also decrepitated before reaching homogenization (usually above 260 °C), probably because of increased

internal pressure of CO2 (Roedder, 1984). 4.3. Microthermometric results and laser Raman spectroscopy Melting temperatures of solid CO2 in the type–IIIA inclusions range from −56.9 to −57.6 °C, with densities varying between 0.63 and 3 The microthermometric data of FIs are summarized in Table 2. 0.82 g/cm . Homogenization temperatures of the CO2 phase range from Microthermometric analyses were conducted principally on primary 26.7 to 30.1 °C. These data imply that the carbonic phase contains μ and pseudosecondary inclusions, which were relatively large (> 7 m) signiﬁcant amounts of CH4 or N2 in the early–stage of mineralization. and regular in shape. Laser Raman spectroscopy indicated that aqueous inclusions The ﬁrst ice melting temperature values (Te(Ice)) of type–IA and –IB

87 S. Asadi et al. Journal of Geochemical Exploration 184 (2018) 82–96

Fig. 4. a) Photograph show ore–bearing quartz veined zones in the Zinvinjian system; b) Two different quartz veins (type–A and –B veins) based on the mineralogical assemblages, geometry, texture, and crosscutting relationships; c) Photomicrographs of two different types of quartz veins (early– and late–stage) based on grain size (XPL); d, e) Photomicrographs of an ore–bearing quartz vein (early–- stage) with mineral assemblages of chalcopyrite, pyrite, galena, sphalerite, chalcocite, covellite, and secondary Fe–oxide minerals with minor bornite (RL); f) Photomicrographs of a barren quartz vein (late–stage) with massive pyrite and minor disseminated chalcopyrite in the quartz matrix (RL). Abbreviation: RL = reflected light, XPL = crossed polars, Ccp = chalcopyrite, Py = pyrite, Gn = galena, Sp = sphalerite, Cct = chalcocite, Cv = covellite, and Bn = bornite. All abbreviations and terminology of ore–minerals are referred to Whitney and Evans (2010).

Fig. 5. Photomicrographs of typical FIs in the Zinvinjian

deposit. a) Type–IA FIs, two–phase liquid and gas (aqueous liquid + vapour) with high volatile phase in the black box

within the type–A veins (early–stage); b) Type–IIA FIs (li-

quid H2O+CO2–rich ﬂuid + vapour) in the early–stage; c)

Type–IIIA FIs (carbonic inclusions) in the early–stage; d)

Type–IB FIs, two–phase liquid and gas (aqueous liquid + vapour) in the type–B veins (late–stage).

88 S. Asadi et al. Journal of Geochemical Exploration 184 (2018) 82–96

Table 2 Microthermometric data of primary ﬂuid inclusions in the Zinvinjain quartz veins.

Stage (inclusion types) Te(Ice) (°C) Tm(Ice) (°C) Tm(Cla) (°C) Tm(CO2) (°C) Th(CO2) (°C) Salinity wt% NaCl eqv. Th (°C) Pressure (bars) Depth (km)

Early (IA) –24 to −30.1 −1.5 to −3.4 –– – 2.5 to 5.5 197 to 225 1988 to 2164 7.5 to 8.2

Early (IIA) ––0.3 to 1.5 −55.7 to −58.2 20.8 to 30.1 13.8 to 15.2 255 to 300 2373 to 2829 8.9 to 10.7

Early (IIIA) ––2.1 to 3.4 −56.4 to −57.6 26.7 to 30.1 11.3 to 13.1 –– –

Late (IB) −21.5 to −32 −0.1 to −1.7 –– – 0.2 to 2.7 192 to 210 736 to 1055 2.7 to 3.9

Notes: Te(Ice): eutectic temperature; Tm(Ice): ﬁnal ice melting temperature; Tm(Cla): dissolution temperature of CO2 clathrate; Tm(CO2): melting temperature of CO2 phase; Th(CO2): homogenization temperature of CO2 phase into the carbonic vapour phases; Th: homogenization temperature. The salinities of H2O–CO2–NaCl and NaCl–H2O systems were calculated using the ﬁnal melting temperatures of CO2–clathrate (Tm(Cla); Collins, 1979) and ice points (Tm(Ice); Bodnar, 1993) in the computer package FLUIDS (Bakker, 2003), respectively.

Calculations of pressure range were made using published equations of state: Bowers and Helgeson (1983) for H2O–CO2–NaCl FIs (IIA); Holloway (1981) for carbonic liquid FIs (IIIA); and

Zhang and Frantz (1987) for H2O–NaCl FIs (IA) in the computer package FLUIDS (Bakker, 2003). Calculations of depth (km) are based on equation of Shepherd et al. (1985). Fluid inclusion terminology and symbols according to Diamond (2003).

Fig. 6. Histograms of homogenization temperatures (Th) and salinities (wt% NaCl equivalent) of FIs from early to late–stages of mineralization.

Fig. 7. Representative Raman spectra of FIs. a)

Spectrum for aqueous inclusions (type–IA) in the ear-

ly–stage; b) Spectrum for aqueous inclusions (type–IB) in the late–stage; c) Spectrum for aqueous inclusions

(type–IIA), containing variable CO2 in the early–stage;

d) Carbonic inclusions (type–IIIA) in the early–stage of

quartz veins, containing variable CO2,N2, and CH4.

89 S. Asadi et al. Journal of Geochemical Exploration 184 (2018) 82–96

(type–IA and –IB; Fig. 7a, b) from early and late–stage samples contain 5.2. Results of stable isotope analysis no clathrate phases; however, they consist of variable traces of CO2 within volatile components. During the early–stage of mineralization, The δ18O values for sixteen analyzed quartz samples, collected from both mixed aqueous–carbonic (type–IIA; Fig. 7c) and carbonic (type–- diﬀerent ore–forming quartz veins (type–A) of the Zinvinjian deposit, IIIA; Fig. 7d) phases generally contains variable contents of CO2,CH4, fall in a narrow range from +15.3 to +19.0‰ (V–SMOW), with an and/or N2 (Zhang et al., 2016; Fig. 7d). This is in agreement with the average of +17.0‰ (Table 3). Oxygen isotopic composition of hy- microthermometric results that the melting temperatures of solid CO2 drothermal water in equilibrium with quartz was calculated using the are lower than −56.6 °C. This inference can be supported by the fact mean homogenization temperature of the samples using the fractiona- that the aqueous inclusions formed by heterogeneous trapping of a tion equation of Ligang et al. (1989). The δ18O values of the ﬂuids

H2O–CO2–rich fluid system during early–stage. In the late–stage of calculated from the Zinvinjian quartz samples range from +6.5 to 18 mineralization, the samples have no nonaqueous volatile components +10.2‰ (mean = +8.2‰) for type–A veins. The δ Oquartz values at other than CO2, although no carbonic phase can be observed in the all localities falls within the range displayed by their host rocks heating–cooling runs. However, neither the microthermometric mea- (Niroomand, 2010; Niroomand et al., 2011), indicating that vein fluids surement, nor the Laser Raman spectroscopic detection show the ex- were isotopically buffered by exchange with the Zinvinjian metasedi- istence of CO2 in any of the late–stage FIs, strongly suggesting that the mentary host rocks. fluid system evolved to an end–member aqueous solution. This unique Sulfur isotope values of twelve sulfide separates (pyrite and chal- evolution is well reported in orogenic base–metal deposits (Chen et al., copyrite) collected from powdered polymetallic sulfides–quartz veins 2005; Zhang et al., 2012; Asadi, 2013; Asadi et al., 2014). (type–A) by hand–picking are given in Table 4. The δ34S values of pyrite in quartz veins range from −7.6 to +11.6‰ (V–CDT), with a mean value of +2.4‰. Chalcopyrite has δ34S values of −9.4 to +2.1‰ 5. Stable isotope systematics (V–CDT), with a mean value of −2.7‰ (Table 4). Assuming that sulfur 34 was predominant as H2S in the ore fluids, δ SH2S values −9.6 to 5.1. Analytical methods +10.2‰, mean − 0.65‰ (Table 4). These values are not consistent with unmodified magmatic sulfur, which would give δ34S grouped close Stable isotope studies were conducted to help determine ore–fluid to zero (Ohmoto, 1986). The absence of any large plutonic rocks in the source reservoirs. Oxygen isotope analyses were completed at the area (Fig. 3) and the wide range of relatively light δ34S values of sulfide Goettingen University, Germany, with some additional analyses at the minerals suggest that a primary magmatic source for sulfur (δ34S=−3

USGS laboratories in Denver, CO. A CO2–laser fluorination method was to +3‰; Hoefs, 2009) is unlikely. Sulfide minerals in porphyry gran- used to analyze oxygen isotopes at the Goettingen University, along itoids have a mean δ34S of +0.4 ± l.0‰ (n = 136; Lowry et al., with a Finnegan Delta Plus mass spectrometer in continuous flow–- 1994). mode. The external precision and accuracy per sample is ± 0.2 permil. Sulfur isotope analyses were carried out at the Muenster University, 6. Discussion Germany. The samples were measured via EA–IRMS also using a Finningan Delta Plus mass spectrometer. Reproducibility, as de- 6.1. Fluid evolution system via interpretation of the Fls data termined from replicate measurement, was better than 0.2 permil. Samples were then prepared for isotopic analyses following standard Based on FIs data, some regularities of fluid evolution are sum- techniques similar to those described in Hall et al. (1991). All data are marized below. The early–stage of mineralization contain the aqueous reported in standard delta permil (δ–‰) notation relative to Vienna (type–IA), mixed aqueous–carbonic (type–IIA), and carbonic (type–IIIA) 18 Standard Mean Ocean Water (V–SMOW) for δ O, and the Vienna inclusions, whereas the late–stage quartz contains the aqueous (type–IB) Canyon Diablo Troilite (V–CDT) for δ34S, respectively. FIs only, indicating that the metallogenic fluid system evolved from

CO2–rich, to late CO2–poor, through input of meteoric fluids. Table 3 According to Shepherd et al. (1985), the eutectic temperature values The oxygen isotopic composition from the Zinvinjian deposit. + + 2+ 2+ 2+ (Te(Ice)) suggest various amounts of Na ,K ,Fe ,Ca , and Mg – – 18 18 a cations in the inclusions (type IA and IB). This compositional sys- Sample no. Location UTM δ O (‰) δ Ofl (‰) quartz V- uid V- tematics are typical of major ore fluid in many base–metal sulfide de- (WGS84) SMOW SMOW posits worldwide (Roedder, 1984). Fluid inclusion and laser Raman ZT3-SII 525,722E, 4,063,065N +16.5 +7.7 studies indicated a high content of CO2 in the ore–bearing fluid of ZT7-SII 525,726E, 4,036,103N +15.3 +6.5 type–A veins, which is typical of orogenic–type deposits. However, the ZT8-SII 525,777E, 4,063,452N +15.7 +6.9 ZT9-SII 525,935E, 4,063,276N +16.6 +7.8 salinities of 11.3 to 15.2 wt% NaCl equivalent for the IIA and IIIA in- ZT10-SII 526,051E, 4,063,165N +17.9 +9.1 clusions are unusually high. The high salinity probably reflect a retro- ZT12-SII 526,163E, 4,063,067N +15.7 +6.9 grade greenschist facies metamorphism that was accompanied by lar- ZT13-SII 526,775E, 4,062,632N +18.6 +9.8 ge–scale transpressional faulting (mainly NE–trending structure), ZT2A-SII 525,800E, 4,063,044N +16.7 +7.9 crack–seal veins, and infiltration of large volumes of hydrous fluid with ZT3A-SII 525,901E, 4,063,021N +15.8 +7.0 – ZT4-SII 525,843E, 4,063,386N +19.0 +10.2 high XCO2. Moritz et al. (2006) indicated that saline and CO2 rich ZT8A-SII 525,966E, 4,063,212N +16.8 +8.0 fluids of the orogenic–type deposits are not related to the gold–forming ZT3B-SII 525,894E, 4,063,024N +15.4 +6.6 events in the Sanandaj–Sirjan metamorphic belt. These conditions lar- ZT2B-SII 526,128E, 4,062,952N +18.9 +10.1 gely overlap with the main hydrothermal event that led to the forma- ZT7A-SII 525,724E, 4,062,336N +17.1 +8.3 – ZT2B-SII 526,128E, 4,062,952N +18.9 +10.1 tion of silica veins (Götze et al., 2012), and base metal ore miner- ZT7A-SII 525,724E, 4,062,336N +17.1 +8.3 alization in the SPMC (Azizi and Moinevaziri, 2009; Niroomand et al., 2011). a δ18 The Ofluid values for quartz samples (type-A veins) calculated by using the equa- The total homogenization temperatures of FIs decreased from 197 to α 6 2 − δ18 tion: 1000 ln quartz-fluid = 3.306(10 /T ) 2.71 (Ligang et al., 1989) from Oquartz 300 °C during early, and 192–210 °C during late events. The salinities of values (The quartz-water curve is between 180 and 550 °C). 1000 ln α (the isotope – – fl FIs also evolved from 2.5 15.2 wt% NaCl equivalent in the early stage fractionation factor) = 8.8 at mean Th 263 °C [mean uid inclusions (type-IA and -IIA) – – that intimately associated with sulfides–quartz veins (type-A)]. V-SMOW = Vienna to 0.2 2.7 wt% NaCl equivalent in the late stage, strongly suggesting Standard Mean Ocean Water is a water standard defining the isotopic composition of that volatile escape and ore mineralization occurred in the early–stage. fresh water. Type–IA inclusions display a nearly linear trend of moderately

90 S. Asadi et al. Journal of Geochemical Exploration 184 (2018) 82–96

Table 4 The S isotopic composition of sulﬁde minerals (pyrite and chalcopyrite) from the Zinvinjian deposit.

34 34 34 34 Sample no. Mineral Location UTM (WGS84) δ S V-CDT (‰) δ SH2S ﬂuid (‰) δ SPy- δ SCcp Temperature (°C)

ZTj-1S Py 525,722E, 4,063,065N +3.5 +2.1 1.5 277 ZTj-7S Ccp 525,722E, 4,063,065N +2.0 +1.8 −− ZTj-5S Py 526,775E, 4,062,630N −1.2 −2.6 1.4 295 ZTj-6S Ccp 526,775E, 4,062,630N −2.6 −2.8 −− ZTj-3S Py 525,777E, 4,063,452N +3.4 +2.0 −− ZTj-12S Ccp 525,775E, 4,063,326N −5.8 −6.0 −− ZTj-10S Py 526,753E, 4,063,452N −7.6 −9.0 1.8 227 ZTj-11S Ccp 526753E, 4,063,452 N −9.4 −9.6 −− ZTj-4S Py 526,775E, 4,062,632N +3.2 +1.8 −− ZTj-9S Py 526,764E, 4,062,634N +11.6 +10.2 −− ZTj-2S Py 525,726E, 4,036,103N +3.7 +2.3 1.6 262 ZTj-8S Ccp 525,726E, 4,036,103N +2.1 +1.9 −−

34 Isotopic delta measurements of sulfur are made relative to Vienna Cañon Diablo troilite (V-CDT). Calculations of δ SH2S fluid (‰) are based on fractionation equations of Ohmoto and Rye (1979) for pyrite (Py) and Li and Liu (2006) for chalcopyrite (Ccp) at a temperature of 263 °C. 1σ is estimated as 0.19‰ for pyrite and chalcopyrite. Temperature of formation based 34 34 on the mean fluid inclusions (type-IA and -IIA) intimately associated with sulfides–quartz veins (type-A). Temperature values (°C) based on δ SPy- δ SCcp calculated using equation of Kajiwara and Krouse (1971). Uncertainties due to equation accuracy ± 10 °C.

decreasing salinity (2.5 to 5.5 wt% NaCl equivalent), while type–IIA different types of FIs (Fig. 5b and Table 2) that are divergently homo- inclusions display a trend of increasing salinity (> 13.8 wt% NaCl genized at nearly similar temperatures and yield contrasting salinities equivalent). Fluid inclusions in the type–IA with pressure > 2000 bars during early–stage of mineralization (Kreuzer, 2005; Fig. 8). Unmixing may be trapped from a homogeneous H2O–CO2 fluid, prior to volatile of H2O–CO2–NaCl fluids between these solvi at temperatures of 200 to escape. However, a pressure of between 2000 and 3000 bars will trigger 350 °C would produce CO2–rich fluids (IIA and IIIA), such as the ones rapid volatile escape (Shelton et al., 1988). A situation apparently very observed in the Zinvinjian polymetallic sulfides–quartz veins (e.g. similar to that which has occurred in the type–IIA inclusions at Zin- Kreuzer, 2005; Qi et al., 2007; Yoo et al., 2011; Asadi et al., 2013a; Xu vinjian deposit. et al., 2016). These trends cannot be explained by a simple boiling and volatile Therefore, the fluid immiscibility is episodic, reflecting wide fluc- escape model. Hedenquist and Henley (1985) indicated that increase in tuations in fluid pressure during regional uplift, due to hydraulic frac- salinity as a result of boiling is relatively small compared with the turing (Cox et al., 1995). These characteristics are typical of retrograde salinity variations documented in Table 2 and Fig. 8 (Wilkinson, 2001). metamorphic fluids at greenschist facies metamorphic conditions Seemingly, boiling process cannot explain the observed temperature–- (Roedder, 1984; Wilkinson et al., 1999; Barker et al., 2000; Anderson salinity trends, while fluid unmixing or CO2 effervescence (Kreuzer, et al., 2004) and indicate that primary vein mineralization occurred 2005; Huff and Nabelek, 2007) and cooling may well explain the two below the pressures and temperatures suggested by Sheikholeslami observed trends seen in Fig. 8. The intimate occurrence of the three et al. (2008), for the peak of metamorphism (P = ~10 kbar and distinct type–IA, −IIA, and –IIIA FIs (Fig. 6a–d) in the polymetallic T = ~700 °C). sulfide–bearing quartz veins (type–A) is believed to be the result of Fluid compositions and homogenization temperatures of the unmixing of an initially homogenous fluid into two immiscible fluid Zinvinjian deposit are very similar to those of many orogenic–type phases (a high XCO2 (> 0.05) fluid [type–IIA and –IIIA] and a low XCO2 systems in metamorphic belts (e.g. Roedder, 1984; Nesbitt, 1991; (< 0.01), or aqueous fluid [type–IA]; Fig. 7a; Kreuzer, 2005). Fur- Robert et al., 1995, 2005; Pirajno, 2009). Furthermore, the importance thermore, the salinities of the type–IIA and –IIIA inclusions are ob- of CO2 effervescence and metamorphic fluids in the generation of such viously higher than those of the type–IA and–IB, and display two distinct deposits is well established (McKeag and Craw, 1989; Kerrich and populations (Table 2; Fig. 8), which can be interpreted by fluid un- Wyman, 1990; Nesbitt, 1991). According to Craw et al. (2010), late mixing (Dugdale and Hagemann, 2001; Diamond, 2001; Hagemann and metamorphic retrograde fluids and fluid immiscibility responsible for Luders, 2003; Kreuzer, 2005; Evans et al., 2008; Jaguin et al., 2014; formation of metalliferous (Cu–Pb–Zn–Au) quartz veins in greenschist Hao et al., 2015). Fluid unmixing was also evidenced by coexistence of facies rocks of the southern Scottish Highlands were broadly similar in

composition (3–14 wt% NaCl equivalent; XCO2 > 0.05) and temperature (mean = 260 ± 50 °C) to those described here. Fluid unmixing in early–stage provides a possible mechanism for the

fluid evolution in the H2O–CO2–NaCl system in the Zinvinjian deposit and have been reported in studies of the other orogenic–type deposits (e.g. Wen et al., 1996, metamorphogenic Cu–bearing quartz veins at SW County Cork, Ireland; Mateus et al., 2003, metamorphic Cu–ores in quartz–carbonate veins at Estremoz–Alandroal and Barrancos–Sto Aleixo regions (Portugal); Hagemann and Luders (2003), the Wiluna Au–Sb deposit in western Australia; Chen et al. (2012), Sawayardun Au deposit in the southern Tianshan, China; Qi et al. (2007), Leng- shuibeigou Pb–Zn deposit in Qinling, China; and Zhang et al. (2012), the Tiemurt Pb–Zn–Cu deposit). In the late–stage, the decreasing pressure (< 1055 bars) is consistent with the decreasing temperatures (< 210 °C) and salinities (mean = 0.9 wt% NaCl equivalent), indicating cooling and dilution of the fluids that probably occurred during the waning stage of lateral Fig. 8. Homogenization temperature (°C) versus salinity (wt% NaCl equivalent) diagram, compression in the SPMC (Fig. 8). A decrease of salinity, temperature, showing fluid evolution at the Zinvinjian deposit. The dashed lines showing densities (g/ and pressure from the early to late–stages resembles the fluid–mixing cm3) of FIs (after Wilkinson, 2001).

91 S. Asadi et al. Journal of Geochemical Exploration 184 (2018) 82–96

values (mean = +8.2‰), the mineralizing fluid probably originated from a single source (Dubinina et al., 2011; Goldfarb and Groves, 18 2015). The δ Ofluid values lie tightly within the metamorphic water box (Hoefs, 2009)reflecting the metamorphic character of hydrothermal fluids responsible for the generation of the type–A veins 18 (Fig. 10a). Our constraints on the δ Ofluid values of the Zinvinjian deposit are also consistent with some published orogenic–type deposits (e.g. Heinrich et al., 1989; Wilkinson et al., 1999; Parnell et al., 2000; Anderson et al., 2004; Zacharias and Novak, 2009; Zhai et al., 2014; Wen et al., 2015; Goldfarb and Groves, 2015). Compared with 18 Anderson et al. (2004) data, δ Oquartz values of polymetallic sulfide–- quartz veins in the Zinvinjian deposit fall within the greenschist facies in metamorphosed sedimentary sequences (Fig. 10b). High δ18O values also indicate a lack of significant meteoric water input to the Zinvinjian metamorphic system at deep levels during ore mineralization (Zheng, 1993) during early–stage of mineralization (Fig. 8). Therefore, the δ18 fl Fig. 9. Plot of Ofluid vs. temperature for uids in equilibrium with quartz, calculated 18O–enriched quartz veins (early–stage) probably precipitated under using oxygen isotope fractionation factors from Longstaffe (1989), δ18O values of quartz retrograde greenschist facies conditions from fluids probably derived by veins and temperature estimates from FIs studies (mean T = 263 °C (type–I and –II )]. h A A – Also shown for comparison are δ18O values of typical metamorphic fluids after Sheppard metamorphic dehydration of deeper volcano sedimentary rocks and 6 2 18 fl (1986). 1000lnαquartz–fluid = 3.306(10 /T )–2.71 (Ligang et al., 1989) from δ Oquartz reacted extensively with wall rocks along the entire extent of their ow values [sulfides–quartz veins (type–A), the quartz–water curve is between 180 and paths. α fl 550 °C]. 1000 ln (the isotope fractionation factor) = 8.8 at mean Th 263 °C [mean uid Sulfur isotope signatures are extremely variable for orogenic–type – – fi – inclusions (type IA and IIA) that intimately associated with sul des quartz veins deposits; much of the reported data for all ages of deposits range be- (type–A)]. tween about −20 and +10‰ (Nesbitt, 1991; Partington and Williams, 2000; Sibson, 2004). In the Zinvinjian deposits, the wide range of trend proposed by Kreuzer (2005). This unique evolution is well dis- measured δ34S values (−9.4 to +11.6‰) of sulfide minerals (chalco- cussed for several orogenic–type deposits (e.g. Goldfarb et al., 2005; Li pyrite and pyrite) suggests non–uniform of the source region (Ohmoto et al., 2005; Chen et al., 2007; Asadi et al., 2013a; Akyildiza et al., and Rye, 1979; Canals and Cardellach, 1997). The most likely source 2015; Tomkins, 2015). for sulfur and metal species is therefore metasediment rocks in the Zinvinjian (Fig. 11a). Also, δ34S values were calculated from the sulfide – 6.2. Isotopic data and source of fluids minerals and the mineral H2S fractionation factors of Ohmoto and Rye (1979) and Li and Liu (2006), assuming H2S as the main sulfur species 18 fl fi δ34 − The δ Ofluid at temperatures of 197–300 °C (early–stage) calculated in the uid. The calculated sul de SH2S equilibrium values 9.6 to 18 ‰ fl from δ Oquartz is in the range of approximately +6.5 to +10.2‰, +10.2 , may refer to a variable redox state of sulfur in the ore uids within the range of metamorphic waters (Sheppard, 1986; Hoefs, for the early–stage of mineralization. The absence of any clustering or 34 2009). Early vein fluids were isotopically buffered by metasedimentary outlier of the δ S data (Table 4; Fig. 11b) may emphasize on sulfur host rocks in the area, consistent with moderate temperatures and a metamorphic source (Fig. 9). Also, in view of the narrow range of the 18 18 measured δ Oquartz (+15.3 to +19.0‰) and calculated δ Ofluid

Fig. 11. a) δ34S–values of some geologically important sulfur reservoirs, indicating a non–uniform of the source region (after Hoefs, 2009); b) Measured δ34S and calculated 34 fluid δ SH2S values of sulfide minerals of the Zinvinjian deposit (fractionation equations 18 18 Fig. 10. a) Plot of δ Ofluid (‰) V–SMOW in type–A veins) δ Ofluid = 6.5–10.2‰; gray of Ohmoto and Rye, 1979 for pyrite (Py) and Li and Liu, 2006 for chalcopyrite (Ccp) at a 18 box). δ O values of important geological reservoirs are from Hoefs (2009); b) Summary temperature of 263 °C (mean type–IA and –IIA FIs); c) The sulfur isotope geothermometric 18 34 bar diagram showing δ Oquartz (‰) V–SMOW values for type–A veins in comparison with temperature values, calculated from the δ S values of pyrite–chalcopyrite pairs from 18 34 34 Anderson et al. (2004) data (see Table 3). δ O values of quartz veins (type–A) are type–A veins. Temperature values (°C) based on δ Spyrite–δ Schalcopyrite calculated using 15.3–19.0‰ comparable with the greenschist facies of the metasediments. equation of Kajiwara and Krouse (1971). Uncertainties due to equation accuracy ± 10 °C.

92 S. Asadi et al. Journal of Geochemical Exploration 184 (2018) 82–96 source heterogeneity under reduced conditions during mineral deposi- estimated from the alteration and ore mineral assemblages and are tion (i.e. T, fO2, pH: cf. Ohmoto and Rye, 1979). This assumption is consistent with the P–T conditions of regional greenschist facies me- based on the lack of oxidized phases, such as hematite and sulfate tamorphism in the Zinvinjian deposit (Niroomand et al., 2011). minerals, in the Zinvinjian mineral assemblage, which indicate that the Therefore, the Zinvinjian deposit was formed at a depth of 7.5–10.7 km ore–bearing fluid had relatively low pH and fO2, and that sulfide spe- (type–A; Table 2), formed at a level comparable with the depth of cies, such as H2S prevailed during the formation of the sulfide minerals mesozonal orogenic deposits (~6–12 km; Groves et al., 1998, 2003; in the early–stage of mineralization (Hoefs, 2009; Asadi et al., 2015). Goldfarb et al., 2005; Chen, 2006). According to Ohmoto and Rye (1979) and Ohmoto (1986), fluid unmixing (Fig. 5b and Tables 2–4) would also lead to relatively 34S–de- 6.4. Metallogenic system pleted H2S in the residual ore fluid, and results in the precipitation of sulfide minerals with more negative δ34S values in the Zinvinjian de- The northwestern Sanandaj–Sirjan metamorphic belt is dominated posit (Fig. 11 a, b; Table 4). Therefore, evolution of lighter sulfur iso- by Triassic–Jurassic rocks but in places Cretaceous turbidities, de- tope ratios in the early–stage of mineralization (Fig. 11b) may be at- posited in deep submarine fans, are preserved and intruded by plutonic tributed to preferential partitioning of reduced gas phases from the ore activity (Alavi, 2007). Late Jurassic–Early Cretaceous events in the fluid by fluid–pressure fluctuations during faulting. The δ34S value of SSMB were followed by the deposition of continental clastic rocks the pyrite–chalcopyrite pairs from the same samples are in accordance (Berberian and King, 1981) overlain by Early to Middle Cretaceous with the expected fractionation trends of this mineral pair. The sulfur carbonate rocks. During the Late Oligocene–Early Miocene marine isotope geothermometric temperature values, calculated from the δ34S carbonates accumulated along the northwestern SSMB. In the SPMC values of this mineral pair, are in a reasonable range, 227 and 295 °C area, regional deformation of the SSMB in the Late Jurassic produced (mean = 265 °C; Table 4), which is comparable to data from relevant pervasive southwest–verging, northwesterly trending fold structures Fls (Fig. 11c). These equilibrium temperatures are taken to confirm that and accompanying greenschist facies metamorphism (Mohajjel and the main ore–bearing quartz veins (type–A) deposited by progressive Fergusson, 2000; Mohajjel et al., 2003). This convergent deformation is

CO2 effervescence and cooling of the early fluid associated with poly- related to crustal thickening along the active margin of the northeastern metallic sulfide mineralization (Fig. 8). SSMB. The complexities in adjoining low grade metamorphic rocks in the SPMC region indicate that this deformation was produced during an 6.3. P–T conditions of mineralization episode of dextral transpression with low obliquity (Mohajjel and Fergusson, 2000). The dextral transpression of the belt could define a Pressures and temperatures of mineralization can be referred from more favorable metal source reservoir for later hydrothermal fluids and geologic setting, ore mineral assemblage, isotopic and Fls data. The thus suggest a higher prospectivity for world–class orogenic deposits in brittle–ductile regime and greenschist facies metamorphism related to the SPMC. the ore formation suggest that maximum P–T values of mineralization The Zinvinjian and the other Sardasht–Piranshahr base–metal oc- are ~310 °C and 3000 bars (John et al., 1999). The ore mineral as- currences are located in a highly deformed area, close to the eastern semblage of Au–bearing Cu–Fe–Pb–Zn sulfide minerals places a max- edge of the Zagros Shear Zone and along the structurally complex imum temperature constraint of 350 °C for mineralization in meta- contact between the Precambrian basement and the Cretaceous ac- morphic terranes (Hünken, 1995). The ore mineral assemblage of creted oceanic rocks. The regional folds, which host the Zinvinjian pyrite ± chalcopyrite ± sphalerite ± galena within metamorphic base–metals represent a target. The mineralization is controlled by host rocks suggests that the mineralization took place at temperatures brittle to brittle–ductile deformation of the volcano–sedimentary rocks of 225 to 350 °C and pressures of 1500 to 3000 bars (McCuaig and and developed within structurally–controlled dilational fractures Kerrich, 1998), similar to Zinvinjian vein system during early–stage of (Niroomand et al., 2011). Fold geometry and hinge zone attitude have mineralization (Table 2). clearly infl uenced fault geometry. Structural analysis of folds in the

The coexisting CO2 effervescence fluid inclusion assemblage (FIA) in Zinvinjian area reveals two co–axial folding stages in the Cretaceous early–stage quartz veins permits a reliable estimation of trapping metamorphic rocks (Sarmad et al., 2014). During the first–stage, tight pressure conditions of fluid trapping during ore formation in the to isoclinal recumbent folds were co–axially refolded by the second–- Zinvinjian deposit (e.g. Hagemann and Brown, 1996; Groves et al., stage upright open folds. The mentioned structural observations imply 1998; Diamond, 2001; Chen, 2006). The procedure to estimate the that extensional event was synchronous with folding, and perpendicular pressure are as follows: (A) the range of isochores of type–I and –II FIs to the fold axis, during the second folding stage. By the tangential of the CO2 effervescence FIA are defined on the P–T diagram using longitudinal strain folding mechanism, tension along the outer part of FLUIDS software (Bakker, 2003) and the minimum and maximum the Zinvinjian antiform opened fractures host quartz veins in the fold densities, and (B) from CO2 effervescence FIA, the type–I and –II FIs hinge areas. Finally, the metamorphosed host rocks characterized by with homogenization temperatures of 197–300 °C were selected to syn–collisional deformation, metamorphism, fluid flow, and develop- constrain the trapping pressure. Intersections of isochores and fluid ment of orogenic–type mineral systems in the SPMC. The location of the unmixing temperature range indicate the trapping pressure range of SPMC polymetallic belt, including the Zinvinjian deposit, is a typical 1988–2829 bars (Table 2; Fig. 8). The fluctuation of the estimated hydrothermal deposit zone in the terrane–scale CMF (collisional or- pressure correlates well with an alternating lithostatic–hydrostatic fluid ogeny, metallogeny, and fluid flow) model (Chen et al., 2004a, 2004b; system. We believe this result is acceptable considering that it is con- Pirajno, 2009). Metamorphic devolatilization of the subducted consistent with previous estimations for the neighboring Kharapeh Au tinental slab could generate carbonic–rich ore–forming fluids that mi- (Cu–Zn–Ag) deposit using carbonic FIs (Niroomand et al., 2011). grated upward along shear zones and faults. These fluids mobilized ore Taken 2.7 g/cm3 as the density of upper continental crust rocks elements from the metamorphosed host rocks. When the fluids reached (Shepherd et al., 1985), the estimated trapping pressures for the ear- the brittle–ductile to brittle zones, the ore–forming components pre- ly–stage fluids are 1988–2829 bars, suggesting an alternating lithosta- cipitated due to fracturing and pressure drops. Fluid immiscibility re- tic–hydrostatic fluid system, controlled by fault–valve activity (see sulted in unmixing of gases (e.g. CO2) and host–rock hydraulic frac- Drummond and Ohmoto, 1985) at a depth of 7.5 to 10.7 km (Table 2). turing that provided conduits for inflow and circulation of the 18 These values along with oxygen isotopic signatures (δ Ofluid: +6.5 to metamorphic water. Along with the evolving collisional orogeny, the 18 +10.2‰; this study and δ Ofluid: +6.0 to +11.2‰ for orogenic–type hydrothermal mineralization at the Zinvinjian deposit experienced a deposits, Yu et al., 1984; McCuaig and Kerrich, 1998; Bierlein and two stage hydrothermal process, in which the early–stage is the base Crowe, 2000; Sun et al., 2010) agree with mesothermal P–T constrains metal–forming stage, and the ore–forming fluid system has been

93 S. Asadi et al. Journal of Geochemical Exploration 184 (2018) 82–96

evolved from carbonic–rich to carbonic–poor, due to CO2 eﬀervescence and mixing of deep metamorphic ﬂuids with shallow meteoric waters. Some of characteristics of the Zinvinjian deposit, such as host rocks, 18 textures, ore and gangue minerals, range of δ O, Th, salinity and age of carboniferous ‑ mineralization are compared with other orogenic–type deposits in the world in Table 5. Upper-Devonian Age of mineralization

7. Conclusions 2.8 Jurassic-Cretaceous 2.5 Mid-Proterozoic 3.1 Jurassic 3 Permo – – – – The Zinvinjian polymetallic deposit is a shear zone–controlled lode 3 – 1 0.8 Pressure (kbars) system. Ore–forming process involves the formation of early–stage polymetallic sulﬁdes–quartz and late–stage pyrite–quartz veins, respectively. The early–stage quartz veins were strongly deformed and tectonically brecciated. The aqueous, mixed aqueous–carbonic, and 15.2 0.7 16.2 0.9 – ﬂ 20 0.6 carbonic bearing inclusions indicative of metamorphic uids occurred – – – 14 12.7 – – – NaCl equiv) at Zinvinjian system. Main ore quartz veins are the result of progressive

CO2 effervescence and cooling of an early fluid associated with poly- 300 2.5 400 8 320 2.3 350 10 360 4 fi – – – – – metallic sul de mineralization. The coexistence of saline carbonic and (°C) Salinity (wt%

h – 300 T aqueous bearing FIs with similar homogenization temperatures in or- – ﬂ – ) e bearing quartz veins reveals that uid unmixing occurred in early - ‰

( stage and resulted in rapid precipitation of ore minerals. Early fluids approached oxygen and sulfur isotope equilibrium with host metase- 19 200 17 240 quartz 21.3 190 17.8 270 – O ff – 20 diments (rock bu ering), and sulfur isotope data indicate a metasedi- – 18 15.3 – 9 9.5 δ mentary source for sulfur. The obtained data reinforce the petrographic indications and δ18O values of the fluids calculated from the Zinvinjian quartz samples show that metamorphic fluids were capable of dissol- ving and precipitating the sulfide minerals. The ore–forming fluid system evolved from early carbonic–rich, metamorphic to late carbonic–poor, and input of meteoric fluids during the waning stage of the mineralization. All geochemical data, homogenization temperature, salinity and trapping pressure of FIs and stable isotope systematics in- Quartz, dolomite, calcite, ankerite, sericite, chlorite Quartz, chlorite, sericite, calcite, ankerite, sericite Quartz, dolomite, sericite, ankerite, chlorite Quartz, dolomite, ankerite 11.7 – dicate that the Zinvinjian deposit is an orogenic–type deposit.

Acknowledgments

This study was ﬁnancially supported by research funds from the GSI (Geological Survey of Iran) Grant Council (79252/34). Thanks are also extended to the Shiraz University research committee for various sup- ports. Thanks are extended to Professor R.J. Goldfarb and Dr. R. Taylor in the United States Geological Survey (USGS) for ﬂuid inclusion and stable isotope analyses. We gratefully acknowledge to Professor D. Chalcopyrite, pyrite, sphalerite, galena Chalcopyrite, pyrite, pyrrhotiteChalcopyrite, bornite, chalcocite, Quartz, dolomite,arsenopyrite, talc galena 12 galena, arsenopyrite, tetrahedrite galena Craw, Professor D. Lentz, and an anonymous reviewer for constructive and helpful reviews, and we appreciate the very helpful suggestions and

des – – ﬁ comments by the Editor in Chief Professor S. Albanese. ber ﬁ

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