# Metal content and P-T evolution of CO2-bearing ore-forming fluids of the Haftcheshmeh Cu-Mo porphyry deposit, NW Iran

N. Zaheri-Abdehvand, A. Tarantola, I. Rasa, S. Hassanpour, C. Peiffert

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N. Zaheri-Abdehvand, A. Tarantola, I. Rasa, S. Hassanpour, C. Peiffert. Metal content and P-T evolution of CO2-bearing ore-forming fluids of the Haftcheshmeh Cu-Mo porphyry deposit, NW Iran. Journal of Asian Earth Sciences, 2020, 190, pp.104166. 10.1016/j.jseaes.2019.104166. hal-02932190

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Metal content and *P-T* evolution of CO₂-bearing ore-forming fluids of the Haftcheshmeh

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Cu-Mo porphyry deposit, NW Iran

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Zaheri-Abdehvand N.¹, Tarantola A.², Rasa I.¹*, Hassanpour S.³ and Peiffert C.²

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¹ Faculty of Earth Sciences, Shahid Beheshti University, Tehran, Iran.

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² Université de Lorraine, CNRS, GeoRessources, Faculté des Sciences et Technologies, F-

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54506 Vandoeuvre-lès-Nancy, France.

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³ Department of Geology, Payame Noor University, Iran.

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* Corresponding Author: I-rasa@sbu.ac.ir

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**Abstract**

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The Haftcheshmeh Cu-Mo porphyry deposit is located in the NW part of the Arasbaran metallogenic-magmatic zone, NW Iran. Ore mineralisation is generally hosted within the gabbro-diorite and granodiorite porphyry stocks, presenting various types of hydrothermal quartz veins and veinlets associated with potassic to sericitic alteration.

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Stage I corresponds to barren quartz-K-feldspar-biotite-anhydrite veins (A veins), with minor metal sulphides (pyrite±chalcopyrite), surrounded by K-feldspar and biotite halos related to potassic alteration. Stage II is described with quartz-molybdenite-chalcopyrite-pyrite-bornite-magnetite-hematite-biotite veins, predominantly occurring in the potassic alteration halos (B veins). Stage III shows pyrite-quartz-chalcopyrite±molybdenite-galena-sphalerite associated with sericitic alteration halos (D veins). The coexistence of halite-saturated aqueous-rich and low-salinity vapour-rich fluid inclusion in the H₂O-NaCl-CO₂ system is evidence of fluid boiling in each alteration/mineralising stages. This process was subsequently followed by meteoric water input, thus decreasing the fO₂ and diluting the CO₂-bearing ore-forming

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fluid.LA-ICPMS data of fluid inclusions associated with the successive stages reveal elevated Na, K, Fe, Mn, Cu and Mo content. The metal content of fluid inclusions of Stages II and III is in large part due to accidentally trapped minerals. Molybdenite and chalcopyrite started precipitating between stages I and II from a metal-poor fluid. The long-duration (> 1 Ma) of the magmatic-hydrothermal activity and associated CO₂ fluxes and repeated fluid boiling events lead to ore deposition at temperatures of 450 to 250 °C and at depths between 3.0 and 1.0 km from near-lithostatic to near-hydrostatic conditions.

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**Keywords:** Haftcheshmeh, Cu-Mo porphyry deposit, CO₂-bearing fluid inclusions, LA-ICPMS analysis, Arasbaran Metallogenic and Magmatic zone

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# 1. Introduction

The Haftcheshmeh Cu-Mo porphyry deposit is located in the Azerbaijan province (NW Iran), in the north-western part of the Cenozoic Arasbaran Metallogenic and Magmatic zone (AMZ) (Fig. 1a, b). It has been recently identified as part of the north-western Iranian metallogenic zone where many Cu-Mo porphyry deposits and occurrences (e.g. Sungun, Haftcheshmeh, Kighal and Niaz deposits) are recognised to have formed during late Oligocene to early Miocene as a result of diorite/gabbrodiorite to granodiorite/quartz-monzonite intrusions (Aghazadeh et al, 2015; Hassanpour et al, 2015). The late Oligocene to early Miocene Cu-Mo porphyries in AMZ including Sungun and Haftcheshmeh Cu-Mo porphyry deposit (Fig. 1b) are located in the southernmost Lesser Caucasus (Fig. 1a, b). The area is the result of the subduction and subsequent syn- to post-collision of the southern margin of the Eurasian Plate and northern margin of the Arabian Plate during the late Eocene to Miocene (United Nations, 2000; Moritz et al., 2016; Hassanpour and Moazen, 2017).
The Haftcheshmeh Cu-Mo porphyry deposit is located about 10 km north of the world-class Sungun Cu-Mo porphyry deposit (Fig. 1b). It was first discovered by the National Iranian Copper Industries (NICICO), in 2006, during the project of investigation and reorganisation of the high potential areas for discovery of Cu-Au-Mo porphyry-epithermal deposits in NW Iran (Hassanpour, 2010). The outcrop surface is approximately 1.8 km². The initial mining operations initiated by NICICO contained detailed geophysical, geochemical and geological surveys. Drilling down to 780 m showed that hypogene mineralisation continues at depths down to 700 m. The proven reserve is of about >180 million tons of disseminated sulphide ore, with an average grade of 0.40 wt. % Cu and 0.035-0.040 wt.% Mo (NICICO, 2010).

Previous studies emphasised the geological characteristics and isotope geochemistry of the Haftcheshmeh Cu-Mo porphyry deposit (Hassanpour, 2010; Adeli, 2012; Aghazadeh et al., 2015; Hassanpour et al., 2015). The petrological and geochemical studies have indicated felsic to intermediate, I-type porphyritic stocks, with high SiO₂ (>50 wt %), enriched in LILE and LREE, Sr, K, Ba and depleted in HFSE, HREE, Y and Yb with an affinity to adakite rocks (Hassanpour et al., 2010; Adeli, 2012; Hassanpour and Moazzen, 2017).

The Haftcheshmeh Cu-Mo porphyry deposit is a long-lived magmatic-hydrothermal system (Aghazadeh et al., 2015; Hassanpour and Moazzen, 2017). Molybdenite Re-Os ages from the quartz-Cu-Mo veins revealed that at least two mineralising events dated at 27.05 ±0.37 Ma and 28.18 ±0.42 Ma (Aghazadeh et al., 2015). The primary magmatic hornblende ⁴⁰Ar/³⁹Ar analyses from the gabbro-diorite host rocks yielded 27.48 ±0.35 Ma (Hassanpour and Moazzen, 2017). Therefore, the late Oligocene Haftcheshmeh Cu-Mo porphyry deposit ore-forming fluids were probably formed from the exsolution of multiple magmatic-hydrothermal pulses during a prolonged period of about 1.13 Ma. This long duration potentially allows significant compositional evolution of hydrothermal fluids by magma differentiation (Spencer, 2015; Klemm et al., 2008).
Recent studies reported CO₂-bearing fluid inclusions in several porphyry deposits from Iran such as Sarcheshmeh Cu-Mo (Etminan, 1977); Meiduk Cu-Au (Asadi et al., 2013; Padyar et al., 2017; Zarasvandi et al., 2018); Keder, Ijo and Sarkuh porphyry Cu deposits (Zarasvandi et al., 2018). However, LA-ICPMS analyses on fluid inclusions have not been conducted on these deposits to describe the metal content of the mineralising fluid and the conditions of metal precipitation.

Fluid inclusions of the identified A and D-type veins in the Haftcheshmeh Cu-Mo porphyry deposit have been studied by microthermometry by Adeli et al. (2014). However, the fluid composition, principally the metal content, the separation and precipitation mechanism of Cu-Mo elements from the CO₂-bearing hydrothermal fluids in quartz veins of the successive stages remained unclear.

The in-situ laser ablation-inductively coupled plasma-mass spectrometry (LA-ICPMS) method has been recently used to constrain the fluid compositions associated with porphyry-type ore deposits (e.g. Heinrich et al. 1992, 1999, 2003; Audôtat et al. 1998, 2000, 2008; Ulrich et al., 1999, 2002; Rusk et al., 2004; Heinrich, 2005; Landtwing et al., 2005, 2010; Williams-Jones and Heinrich, 2005; Klemm et al., 2007, 2008; Catchpole et al., 2011; Spencer, 2015; Chang et al., 2018). Several experimental (e.g. Ulrich and Mavrogenes, 2008; Tattitch et al., 2015; Kokh et al., 2015; Zajacz et al., 2011, 2017) and natural FI studies (Butte (Rusk et al., 2008); Bingham (Landtwing et al., 2005, 2010; Seo et al., 2012); Yulong (Chang et al., 2018); Yuchiling (Li et al., 2012)) related to porphyry deposits have revealed that CO₂-bearing FIs observed in the porphyry Cu-Au-Mo deposits can carry significant concentrations of metals. Mo and Cu decoupled mineralisation during magmatic and hydrothermal processes is best explained by fluid phase separation and metal partitioning into coexisting vapours and brines (e.g. Ulrich et al., 1999; Mavrogenes et al., 2002; Audôtat and Pettke, 2003; Landtwing et al., 2005; Seo et al., 2012; Chang et al., 2018;).
This study reports new petrographic, mineralogical and fluid inclusion investigations, including microthermometry, Raman spectroscopy and LA-ICPMS, of the Haftschechmeh Cu-Mo deposit in order to (i) describe the fluid associated with metal deposition, (ii) estimate the *P* and depth conditions of the successive mineralising stages, (iii) deduce the nature and conditions of circulation of the mineralising fluids, (iv) describe the evolution of the metal content of fluid inclusions during the successive alteration and mineralisation stages, and (v) discuss the physico-chemical conditions, and more particularly the role of CO₂, of molybdenite and chalcopyrite precipitation.

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## 2. Regional geology

The world's major Phanerozoic porphyry systems in the Eurasian continent are part of the Jurassic to Cenozoic Tethyan Metallogenic Belt (TMB) (Mao et al. 2014), extending over approximately 12,000 km from SE Europe, Anatolia, Iran to Indochina and the southwest Pacific (Richards et al., 2012). Various intense magmatism and volcanic activities are exposed in the Cenozoic Arasbaran magmatic Zone (AMZ) as a central segment of the TMB (Richards, 2009; Moritz et al., 2013, 2016) formed in an intracontinental or post-collision setting of the southern lesser Caucasus subduction zone (Moritz et al., 2016; Hassanpour and Moazzen, 2017) (Fig. 1a, b).

The WNW-ESE trending and 50-100 km wide AMZ has a distinct geological history and an older mineralisation related to porphyry intrusions than the Cenozoic Urumieh-Dokhtar magmatic-metallogenic belt (UDMB) (Hassanpour, 2010; Hassanpour et al., 2015; Hassanpour and Moazzen, 2017). Porphyry Cu-(Mo-Au) mineralisation in the UDMB formed during the intrusion of Miocene calc-alkaline and adakite-like high Sr/Y porphyritic bodies due to subduction and continent-continent collision related to the closure of the Neo-Tethys in central Iran during Paleogene-Neogene times (Shafiei et al., 2009). Accordingly, the Sungun
granodiorite (dated at 20.69 ±0.37 Ma by $^{206}$Pb/$^{238}$U dating on zircon and 22.14 ±0.18 Ma by $^{40}$Ar/$^{39}$Ar dating on hornblende (Hassanpour et al., 2015; Hassanpour and Moazzen, 2017)), and the Haftcheshmeh gabbro-diorite (dated at 27.47 ±0.17 Ma by $^{40}$Ar/$^{39}$Ar dating on hornblende) (Hassanpour et al., 2015; Hassanpour and Moazzen, 2017) and granodiorite (dated at 27.05 ±0.37 Ma by Re-Os dating on molybdenite (Aghazadeh et al., 2015) in the AMZ are older than the porphyry intrusions of the UDMB with the Sarcheshmeh granodiorite dated at 13.60 ±0.10 Ma and 12.97 ±0.23 Ma by $^{206}$Pb/$^{238}$U dating on zircon (McInnes et al., 2003; Aghazadeh, 2015) and 12.5 ±0.5 Ma by Rb-Sr dating on biotite (Shahabpour, 1982; Shahabpour and Kramers, 1987), and the Meiduk granodiorite dated at 12.5 ±0.1 Ma by $^{206}$Pb/$^{238}$U dating on zircon (McInnes et al., 2003), and 12.4 ±0.2 Ma by Rb-Sr dating on biotite (Hassanzadeh, 1993).

Hassanpour (2010, 2015) and Moritz et al. (2016) have demonstrated that the AMZ, in terms of stratigraphy, magmatism, tectonic setting and mineralisation, is similar to the southernmost Lesser Caucasus subduction zone. The geological and mineralogical studies of the Lesser Caucasus by the United Nations (2000) have indicated that the Kajaran and Agharak Cu-Mo porphyry deposits in Armenia and Mo-bearing quartz veins of the Paragachay deposit in Nakhichevan are related to the composite Meghri-Ordubad and Bargushat plutons (Moritz et al., 2016), with an area of about 1,400 km². The magmatism in the AMZ started with Eocene intermediate to felsic volcanic activity and continued by the intrusion of the subduction, collisional to post-collisional related Oligo-Miocene calc-alkaline to alkaline Andean I-type granitoids, which resulted in extensive hydrothermal alteration and ore deposition (Hassanpour and Moazzen, 2017; Adeli, 2012). The late Oligocene-Miocene porphyry intrusions of Sungun and Haftcheshmeh porphyry stocks are part of the previously mentioned composite Meghri-Ordubad and Bargushat plutonic batholiths in the north-western part of Iran (Hassanpour, 2010; Hassanpour et al., 2015). The intrusions and hydrothermal activity of
150 the Sungun and Haftcheshmeh porphyry stocks into Cretaceous volcano-sedimentary rocks
151 have created widespread alteration halos and extensive porphyry Cu-Mo-Au and Au-Fe skarn
152 mineralisation types. Therefore, the spatially and temporally association of the Cu±Mo
153 mineralisation in the Sungun and Haftcheshmeh Cu-Mo porphyry deposits of NW Iran, AMZ,
154 around 27-20 Ma (Hassanpour, 2010), accompanied by the Kajaran and Agharak Cu±Mo
155 porphyry deposits in Armenia (United Nations, 2000), have occurred during regional
156 compression in a collisional to post-collisional setting between Iran and the Lesser Caucasus
157 (Hassanpour, 2010; Moritz et al., 2016; Hassanpour and Moazzen, 2017).

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159 **3. Local geology of the Haftcheshmeh deposit**

160 The late Oligocene Haftcheshmeh PCD was discovered during the NICICO (2006)
161 exploration activities. Rock units at the 1:5000 scale have been described by NICICO (2008)
162 and Hassanpour (2010). Detailed petrographic descriptions at the 1:1000 scale (NICICO,
163 2010) rock units of the Haftcheshmeh Cu-Mo porphyry deposit are presented here. The
164 simplified geological and alteration map (1:1000 scale) is illustrated in the Figures 1c and 2a.
165 Mineralisation and alteration occurred as a result of porphyritic granodiorite intruding a
166 porphyritic gabbro-diorite. Both these high-K calc-alkaline intrusive magmatic rocks crop out
167 at the surface (Fig. 1c) (Hassanpour and Moazzen, 2017). The Haftcheshmeh porphyry stocks
168 are cross-cut locally by two series of NW-SE and N-S trending dykes varying in composition
169 from early diorite to late andesite (Fig. 2a). The orientation of the NW-SE trending faults
170 corresponds to the general orientation of the deformation within the AMZ. These faults
171 controlled the emplacement of the gabbro-diorite stock and the following alteration activity
172 resulting from the porphyry granodiorite intrusion. Dioritic and andesitic dykes are more
173 distributed and observed in the eastern part of the NW-SE trending main fault of the deposit
174 (Fig. 2a). The NW-SE trending main faults have cut the diorite dykes in the central part of the
175 deposit and created a clear boundary between propylitic and sericitic alteration zones (Fig.

176 2a), indicating that they were active all along the magmatic and hydrothermal events.

177 The E-W trending granodiorite bodies locally outcrop as stocks in the gabbro-diorite in the

178 central and NW parts of the area (Fig. 1c). The gabbrodiorite rocks have a porphyritic texture

179 composed of altered plagioclase (35-60 vol. %), K-feldspar (≥5 vol. %), quartz (≥10 vol. %),

180 primary biotite (5-10 vol. %) and amphibole (7-10 vol. %) phenocrysts (Fig. 2b). These

181 phenocrysts occur in a fine-grained groundmass of quartz, K-feldspar and plagioclase, biotite

182 and hornblende. The granodiorite stock is characterised by porphyritic phenocrysts of

183 sericitised plagioclase (20 to 40 vol. %), orthoclase (about 10 vol. %), quartz (10 to 20 vol. %), biotite and hornblende (about 10 vol. %) set in a fine-grained groundmass mainly composed of plagioclase, quartz, K-feldspar, hornblende, and secondary biotite, epidote and chlorite (Fig. 2c, d). The primary amphibole and biotite are mostly altered to pale-brown to greenish-brown secondary biotite, chlorite, muscovite, and opaque minerals.

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185 composed of plagioclase, quartz, K-feldspar, hornblende, and secondary biotite, epidote and

186 chlorite (Fig. 2c, d). The primary amphibole and biotite are mostly altered to pale-brown to greenish-brown secondary biotite, chlorite, muscovite, and opaque minerals.

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189 **4. Alteration and mineralisation**

190 Earlier published alteration and mineralisation studies of the Haftcheshmeh Cu-Mo porphyry

191 deposit (Hassanpour, 2010; Adeli, 2012; Hassanpour et al., 2015; Hassanpour and Moazzen,

192 2017) have been integrated with our field investigation and petrographic observations.

193 Hydrothermal alteration and mineralisation are broadly developed (Fig. 2a). The emplacement

194 of the granodiorite porphyry into the gabbro-diorite is responsible for abundant Cu-Fe and Mo

195 sulphides-bearing quartz veins and veinlets. On the basis of the detailed geological mapping,

196 field data and petrographic observations of the drill core and outcrop samples, the

197 characteristics and spatial distribution of four widespread hypogene hydrothermal porphyry-

198 style alteration types can be identified from central to external parts (Fig. 2a). They consist of
dominant early potassic and peripheral propylitic alteration, followed by sericitic and locally argillic alteration.

Extensive east-west oriented potassic alteration (Fig. 2a) related to early hydrothermal activity is spatially developed associated with intrusion of the granodiorite into the gabbrodiorite stocks in the central part of the Haftcheshmeh Cu-Mo porphyry deposit (Fig. 1c). The potassic alteration consists of barren quartz, secondary K-feldspar, secondary biotite and anhydrite (Fig. 2b, c), and abundant sulphides in quartz veins and veinlets and disseminated occurrence in the matrix of the gabbrodiorite and granodiorite porphyries including molybdenite, chalcopyrite, pyrite, magnetite, hematite and trace amounts of bornite (Fig. 3c-h). A volumetrically limited quartz-sericite-pyrite alteration complies with the intrusion of the dioritic to gabbro-diorite bodies in the north, north-eastern and central parts of the deposit (Fig. 1c and 2a). The sericitic alteration occurs usually either as nearly complete replacement of original magmatic minerals such as plagioclase, K-feldspar and biotite by fine- to coarse-grained sericite (Fig. 2c and 3j), or as dissemination and continuous veins and veinlets of pyrite, chalcopyrite, and molybdenite, galena, sphalerite and quartz in the groundmass (Fig. 3i-l). The peripheral pale green to grayish propylitic alteration occurs in all rock types of the southern and north-western parts, preferentially in the gabbro-diorite (Fig. 1c and 2a). The propylitic alteration includes mainly veins and veinlets of chlorite and epidote (Fig. 2d) and absence or minor sulphide mineralisation as disseminated pyrite. Field observations indicate that low intense scattered intermediate argillic alteration occurred in the gabbrodiorite rocks, usually controlled by fractures and fault zones in the southern and northeastern parts of the study area (Fig. 2a).

## 4.1. Vein classification and mineralisation stages
The pioneering literature on vein nomenclature of porphyry deposits by Gustafson and Hunt (1975), Gustafson and Quiroga (1995), and Sillitoe (2010) has been widely used in recent years for the description of porphyry deposits to provide a consistent basis for the review of the petrography and FI descriptions. Petrographic observations on more than 100 thin and polished sections revealed that hypogene porphyry Cu-Mo mineralisation is spatially and temporally recognised within the potassic and sericitic alteration of the gabbro-diorite and granodiorite porphyry stocks. Based on cross-cutting and textural relationships of the various barren quartz and sulphide-bearing quartz veins and veinlets, the hydrothermal alteration-mineralisation processes responsible for the hypogene ore formation of the Haftcheshmeh Cu-Mo porphyry deposit can be clearly divided into three main ore-forming stages, from early to late. The early Stage I and middle Stage II are associated with potassic alteration and the late Stage III is associated with sericitic alteration.

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### 4.1.1. Stage I

Barren quartz-K-feldspar-biotite-anhydrite with sporadic pyrite, chalcopyrite veins represents the earliest recognised hydrothermal stage (Fig. 3 a, b; Table 1). They crosscut the altered gabbro-diorite and granodiorite rocks. These veins and veinlets are surrounded by secondary biotite-K-feldspar and anhydrite alteration halos (Fig. 3b). The discontinuous irregular wall-rock and granular texture characterising these veins witness their plastic nature and formation under a lithostatic regime (Fournier, 1999; Muntean and Einaudi, 2001). More than 80% of the volume of the veins consists of 0.5 to 5 cm wide (Fig. 3.a, b) with granular to equigranular straight-walled coarse-grained quartz crystals without internal symmetry. Sulphide association is commonly lacking, but occasional disseminated grains of chalcopyrite-pyrite assemblages in both veinlets and alteration halos may be found (Fig. 3b). The veins have probably formed as open space filling and are affected by the later alteration-mineralisation stages. These

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248 granular quartz-K-feldspar-biotite-anhydrite veins belong to the pre-ore forming stage and are
249 similar to the A-veins of worldwide porphyry deposits described by Gustafson and Hunt
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252 **4.1.2. Stage II**

253 Stage II, with several mm to >5 cm wide quartz dominated straight veins, is related to the
254 intrusion of granodiorite porphyries into gabbro-diorite. This stage is composed of various
255 sulphide-bearing stockworks either with quartz+molybdenite parallel to the vein margins,
256 associated with biotite alteration halo (Fig. 3c-f; Table 1), or as intergrowths of
257 quartz+chalcopyrite+pyrite+bornite+magnetite+hematite in a narrow discontinuous layer in
258 the centre of the veins (Fig. 3g, h) with weak to occasionally sporadic biotite-stable alteration
259 halos (Fig. 3e, f). These veins are mainly developed in potassic alteration halos. The quartz
260 veins of Stage II are represented by the widespread formation of relatively coarse- to medium-
261 grained quartz. They are centrally (Fig. 3 d, e) or marginally (Fig. 3 c, d, f) infilled by later
262 sulphides, which have similar characteristics to B-veins described by Gustafson and Hunt
263 (1975) and Sillitoe (2010). The Mo mineralisation in the marginal part of veins of Stage II are
264 crosscut by chalcopyrite+pyrite veins of Stage II (Fig. 3c), suggesting that molybdenite
265 precipitated simultaneously with quartz vein formation and formed earlier than chalcopyrite.
266 The occurrence of the B-veins and abundant A-veins are consistent with other porphyry Cu-
267 Mo deposits in the world (Sillitoe, 2010). Both barren quartz and quartz-molybdenite veins,
268 with biotite-K-feldspar alteration halos, are typically crosscut by veins with quartz-
269 chalcopyrite-pyrite-galena-sphalerite and minor molybdenite linked to sericitic alteration
270 halos of Stage III (Fig. 3i, j).

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272 **4.1.3. Stage III**
The late hydrothermal ore-forming stage is marked by 0.5-6 cm wide quartz-pyrite-chalcopyrite (Fig. 3i, j; Table 1) and minor amounts of molybdenite-galena-sphalerite veins and veinlets (Fig. 3k, l) with fine grained green chlorite and sericitic alteration halos along the vein margins (Fig. 3j) similar to D-veins reported by Sillitoe (2010)), that crosscut all the previously formed vein types. The most important characteristics of these veins are the continuous pattern, regular contacts and well-developed sericitic alteration halos (Fig. 3j), which indicate that they dominantly occurred in the sericitic alteration zone. This stage contains traces of molybdenite (Fig. 3k), which may resemble veins from Stage II. However, the increase of pyrite in Stage III relative to Stage II and their crosscutting relationships indicate that Stage III quartz-polymetallic veins formed later than the veins of Stage II.

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## 5. Materials and Methods

### 5.1. Fluid inclusion-bearing samples

About 100 polished thin sections were collected from diamond drill core and outcrop samples of the gabbro-diorite to granodiorite porphyry host-rock units to characterise the mineralisation and hydrothermal alteration stages. About fifty doubly polished 100-200 µm thick sections from euhedral to subhedral quartz crystals from quartz-sulphide veins and veinlets were prepared for fluid inclusions studies. The samples were selected as contemporaneous to the precipitation of the quartz-sulphide veins, located in the euhedral to subhedral quartz crystals. Petrographic observations suggested that the barren quartz-K-feldspar-biotite-anhydrite±pyrite±chalcopyrite veins in Stage I, the quartz-molybdenite-chalcopyrite-pyrite-magnetite-hematite±bornite veins in Stage II, and the quartz-pyrite-chalcopyrite-molybdenite-galena-sphalerite veins in Stage III within the hypogene alteration zones (potassic and sericitic alteration zones) were FI-rich with sizes ranging from 8 to >35 µm.

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297 µm were appropriate for microthermometry, Raman spectroscopy and laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) analyses.
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300 **5.2. Microthermometry**

301 Quartz veins (15 wafers) and their contained fluid inclusions (over 700 primary FIs) were
302 mapped at different scales with a Keyence VHX-1000 digital microscope for petrography and
303 location recognition among the different analytical techniques. After detailed petrographic
304 studies, the smaller chips were cut from the slides and transferred to a Linkam THMS600
305 heating-cooling stage attached to an Olympus BX51 microscope equipped with 10X, 20X,
306 50X and 100X objectives and a monitoring video apparatus in the FIs laboratory of
307 GeoRessources at Université de Lorraine (Vandoeuvre-lès-Nancy, France). The stage was
308 regularly calibrated over a range of temperatures by using the synthetic FIs from quartz
309 samples through calibration against the triple point of CO₂ at –56.6 °C, the freezing point of
310 H₂O at 0.0 °C and the homogenisation temperature of natural inclusions. Heating/cooling
311 rates were adopted to ~10 °C/min and reduced to 1 to 0.1 °C/min near phase transitions. The
312 precision of measurements during the microthermometric experiments was ±0.1 °C for
313 temperatures below 31.0 °C and ±1 °C for high-temperature measurements.

314 The FIs were first cooled to –100 °C and then heated progressively to obtain the temperatures
315 of the successive phase transitions: T<sub>m</sub>(CO<sub>2</sub>), the melting point temperature of the carbonic
316 phase (–56.6 °C for pure CO<sub>2</sub>), T<sub>e</sub>, the first apparent melting temperature of the aqueous
317 phase, T<sub>m</sub>(ice), the final melting temperature of ice, T<sub>m</sub>(cla), the dissociation temperature of
318 the clathrate phase, T<sub>h</sub>(CO<sub>2</sub>), the partial homogenisation of the carbonic phase (L<sub>CO2</sub>V<sub>CO2</sub> to
319 L<sub>CO2</sub> or V<sub>CO2</sub>), T<sub>h(LV->L)</sub> or T<sub>h(LV->V)</sub>, the bulk homogenisation temperature by vapour or liquid
320 disappearance, respectively, and T<sub>m</sub>(syl) and T<sub>m</sub>(hal), the melting temperatures of sylvite and
321 halite, respectively. The salinity of FIs in the NaCl-H<sub>2</sub>O system (L-type and V2-subtype) was
calculated using the final ice melting temperatures with the equations provided by Bodnar (1993).

Daughter minerals (present in all inclusions of an assemblage and with a constant phase volume ratio) and accidentally captured crystals were observed in most inclusions. Their identification was made using a combination of petrography, microthermometry and Raman spectroscopy observations. Halite and sylvite are the most commonly encountered daughter minerals in the FIs. Their melting temperatures are reported as $T_m(\text{hal})$ and $T_m(\text{syl})$, respectively. The salinity of halite and sylvite-bearing FIs (S-type fluid inclusions) was calculated using the AqSo-WHS program (Bakker, 2012) with the equation for the NaCl-KCl-H$_2$O system with the equation of Zhang and Frantz (1987). However, only the salinity as equivalent NaCl weight% (wt.% NaCl$_{eq}$) is reported in Table 2 as this value is used as the internal standard for metal content quantification from LA-ICPMS analyses. The other transparent (calcite and anhydrite) and opaque (chalcopyrite and molybdenite) daughter and accidently trapped minerals did not melt at the conditions of microthermometry experiments conducted up to ~590 °C.

S-type FIs were categorised by their mode of homogenisation, either by halite (S1 subtype) or by vapour disappearance (S2 subtype). The density and pressure at homogenisation of S1 FIs ($T_m(\text{hal}) > T_{h(\text{LV} \to \text{L})}$) were calculated using the ISOC program and Lecumberri-Sanchez et al. (2012). The density and pressure at homogenisation of S2 FIs ($T_m(\text{hal}) < T_{h(\text{LV} \to \text{L})}$) were calculated by the Zhang & Frantz (1987) equation (Bakker, 1998) and Flincor computer program (Brown and Lamb, 1989), respectively. The clathrate dissociation temperature ($T_m(\text{cla})$) was determined after successive heating-cooling runs (cycling method) in V1-subtype FIs (H$_2$O-CO$_2$-NaCl system) (Diamond, 2001). The salinity, molar fraction of CO$_2$ (XCO$_2$), density and pressure at bulk homogenisation of V1-subtype FIs were calculated using the Q2 and ISOC programs (Bakker, 1998, 2003), by using the following parameters:
347 dissociation temperature of clathrate ($T_m$(cla)), partial homogenisation mode and temperature
348 ($T_h$(CO₂)), and estimated volume fraction of CO₂ at room temperature. The uncertainty of
349 volume fraction estimation results in up to 20% errors in density calculations (Roedder,
350 1984). Microthermometric measurement results are summarised in Table 2.

351

352 **5.3. Raman microspectroscopy**

353 Raman microspectroscopy was carried out in order to characterise the vapour and solid phases
354 of selected fluid inclusions after microthermometry experiments. The analyses were
355 performed at GeoRessources laboratory (Université de Lorraine, Vandœuvre-lès-Nancy,
356 France) on a Horiba Jobin Yvon LabRAM HR laser-Raman spectrometer (exciting radiation
357 at 514.532 nm, focal length 800 nm, 1 grating with 1800 grooves per nm, 500 µm confocal
358 hole aperture and 100 µm slit width, spectral resolution of 1.5 cm⁻¹, beam size of about one
359 µm, liquid N₂ cooled CCD). The integration time was 10 to 60 s with ten accumulations in
360 order to reduce the noise/signal ratio.

361

362 **5.4. LA-ICPMS**

363 The in-situ metal content of CO₂-bearing vapour (V1- and V2-subtypes) and high salinity S-
364 type FIs was determined using Laser Ablation-Inductively Coupled Plasma Mass
365 Spectrometry (LA-ICPMS) at the GeoRessources laboratory (Université de Lorraine,
366 Vandœuvre-lès-Nancy, France), using a Agilent 7500c quadrupole ICPMS coupled with a
367 193 nm GeoLas ArF Excimer laser (MicroLas, Göttingen, Germany). Laser ablation was
368 performed with a constant 5 Hz pulse frequency and a constant fluence of 6.20 J/cm² by
369 focussing the beam at the sample surface. Diameter of the ablation sport was 32 µm. Helium
370 was used as carrier gas to transport the laser-generated particles from the ablation cell to the
371 ICPMS and argon was added as an auxiliary gas via a flow adapter before the ICP torch.
Typical flow rates of 0.5 L/min for He and 1 L/min for Ar were used. Each signal was integrated using the salinity of FIs to estimate the Na content as internal standard. The certified reference materials NIST SRM 610 and 612 (concentrations from Jochum et al., 2011) were used as external standards for calibration of all analyses and were analysed twice at the beginning and at the end for each set of samples, following a bracketing standardisation procedure. The following 19 isotopes were measured with a dwell time of 10 ms for each: 7Li (limit of detection of 350 ppm), 23Na (1200 ppm), 24Mg (20 ppm), 39K (820 ppm), 43Ca (140 ppm), 47Ti (390 ppm), 55Mn (270 ppm), 57Fe (190 ppm), 63Cu (160 ppm), 66Zn (290 ppm), 85Rb (40 ppm), 88Sr (15 ppm), 95Mo (60 ppm), 118Sn (40 ppm), 121Sb (20 ppm), 133Cs (15 ppm), 137Ba (40 ppm), 197Au (20 ppm), 208Pb (8 ppm) and 209Bi (0.5 ppm). The element content of the quartz host-mineral was subtracted. All data were reduced off-line with the limits of detection calculated using the commercial version of Iolite (Version 3.71, https://iolite-software.com) data reduction software (Paton et al., 2011) running with Igor Pro. The uncertainty is calculated for each element for each analysis as a function of the uncertainty of the reference standards, the absolute element content and the time of integration (Paton et al., 2011). The resulting value of uncertainty is then varying for a single element between each analysis and is generally higher when the element concentration is measured close to the limit of detection. The uncertainty for Ca was always too high to report the results; Li and Au were always below detection limit. A total of 85 inclusions were ablated. However, due to the small size of the inclusions and low signal intensities, they concentration results of only 33 S- and V-type inclusions are shown on Fig. 8, 9 and Table 3. All attempts of analyses of L-type inclusions failed. The results are reported for each stage for V and L-type fluid inclusions according to four classes of uncertainty, namely below 20 %, between 20 and 50 %, between 50 and 80 % and higher than 80 %.
397 **6. Fluid inclusion petrography**

398 **6.1. Fluid inclusion types**

399 Prior to microthermometry analyses, detailed petrography was performed on the FIs within
400 single quartz crystals, which are either surrounded by or directly adjacent to the sulphides in
401 the quartz veinlets (Fig. 4a, c, d). Undulose extinction of quartz is evidence of plastic
deformation during vein formation. Most of the inclusions are found as isolated individuals or
402 groups (Fig. 4a, c, d). Only rare inclusions are aligned along intergranular healed fractures
403 and along transgranular trails crosscutting quartz grain boundaries (Fig. 4b). This suggests a
404 continuous entrapment of mineralising fluid mainly during quartz growth (Roedder, 1984;
405 Van den Kerkhof and Hein, 2001). The early trapped inclusions may be affected by post-
406 entrapment modification (Bodnar, 2003).
407

408 According to the phase state at room temperature, three types of FIs have been distinguished
409 in the quartz samples: liquid-rich two-phase (L-type), vapour-rich two-phase (V-type) and
410 daughter mineral-bearing multiphase (S-type). These three types were divided into subtypes
411 according to phase transitions during heating and cooling runs, and Raman microspectroscopy
412 investigations.

413 **Liquid-rich two-phase FIs (L-type):** At room temperature, they consist of a dominant liquid
414 phase and a variable vapour bubble, which occupies 10-45 % of apparent total volume. These
415 inclusions generally have a size <35 µm. In Stage I veins, irregular to rounded L-type FIs (<5
416 µm) occur mainly as secondary inclusion trails along healed fracture planes (Fig. 4b). They
417 occur with negative crystal shape scattered in the growth zones of quartz crystals in veinlets
418 of Stage II and Stage III, suggesting entrapment during quartz growth. L-type inclusions are
419 about 10 % of the total inclusion types and their relative proportion within quartz veins
420 increases from Stage I to Stage III. No visible phase transitions within the gas phase and no
421 clathrate were observed during microthermometric experiments indicating that L-type
422 inclusions do not contain significant amount of CO₂. This was confirmed by Raman

423 spectroscopy that only revealed trace amounts of CO₂ in the vapour phase of isolated L-type

424 FIs from all stages.

425 **Vapour-rich FIs (V-type)** consist of two- to three-phase inclusions at room temperature with

426 a generally dominating carbonic phase, which occupies 40 to 80% of the apparent inclusion

427 volume. These inclusions typically exhibit rounded isometric, elongated and negative-crystal

428 shapes and are normally in the range 5 to 35 µm in diameter. They are distributed in isolated

429 groups or alone in quartz (Fig. 4a, c, d). V-type inclusions might contain transparent (mainly

430 calcite) (Fig. 5b), and chalcopyrite (Fig. 5c-f) minerals with different phase ratios, suggesting

431 that they were accidently trapped. V-type FIs coexist with other inclusion types, especially

432 with daughter mineral-bearing FIs (S-type) in the inner parts of the same quartz crystal.

433 Based on optical observations at room temperature and clathrate formation and dissociation

434 during cooling and heating runs, these inclusions can be subdivided into two subtypes, V1-

435 subtype, which show phase transitions in the gas phase during cooling runs and V2-subtype,

436 which only show ice melting during low-temperature microthermometric investigations. V1-

437 subtype may consist of VCO₂+LCO₂+Laq or VCO₂+Laq at room temperature (Fig. 5a-c).

438 Dissociation temperature of the clathrate (Tm(cla)) and homogenisation of the carbonic phase

439 to CO₂ vapour (Th(CO₂)) were measured during microthermometric runs with distinctive

440 Tm(CO₂) (–56.6 °C) in V1-subtype FIs. In V2-subtype, although no phase transition was

441 observed in the vapour phase (no homogenisation or melting, no clathrate dissociation), CO₂

442 was revealed by Raman spectroscopy. V-type inclusions are the most common in all

443 mineralised quartz veins of all stages and account for approximately 60% of the total number

444 of inclusions. The relative proportion of V1 inclusions however decreases from Stage I to

445 Stage III.
446 **Daughter mineral-bearing multi-phase FIs (S-type)** consist of a liquid phase and a vapour bubble that occupies 20-60 vol. % of the inclusion and one, or more, transparent and opaque daughter minerals with the same phase ratio, which occupies 50-20 vol.% of the inclusion. S-type inclusions have ellipsoidal or negative crystal forms varying in size from 5 to >35 µm.
447
448
449
450 These inclusions account for approximately 15 to 30% of the observed FI populations. They are randomly distributed within each stage and coexist with V-type FIs as clusters or isolated (Fig. 5b- e). Raman spectroscopy analyses have revealed that the vapour bubble of the S-type FIs is composed of CO2. Transparent daughter minerals include cubic halite crystals (Fig. 5b-e), sylvite (Fig. 5b, c) with rounded edges, rod-shape calcite (Fig. 5b and 7h) and opaque minerals are mainly chalcopyrite as recognised by its characteristic triangular shape (Fig. 5d-f) and Raman spectra (Fig. 7k). S-type FIs occur in all vein types from early to late stage, but differ according to their homogenisation mode and contained daughter minerals. S-type FIs display two different homogenisation modes during heating: S1-subtype FIs ($T_m$(hal) > $T_{h(LV->L)}$), homogenising by halite and S2-subtype ($T_m$(hal) < $T_{h(LV->L)}$) FIs, homogenising by vapour.
451
452
453
454
455
456
457
458
459
460 The number of S-type FIs homogenising by vapour disappearance ($T_m$(hal) < $T_{h(LV->L)}$) increases from Stage II to III (S2-subtype > S1-subtype) and their daughter minerals are mainly halite and sylvite, but also chalcopyrite.
461
462
463
464

# 7. Results

## 7.1. Microthermometry

465
466
467
468
469
470 Microthermometry measurements (summarised in Table 2 and illustrated in Fig. 6) were conducted on 714 isolated/randomly distributed intergranular primary FIs, ranging from 5 to ~35 µm in size. When several inclusions could be indubitably identified as part of an assemblage, their microthermometric characteristics were comparable. However, because of the high density of inclusions in the quartz, the inclusions were considered independently and
not attributed to an assemblage. Therefore, the results below show the phase transition temperatures for all inclusions of a certain type and not of specific assemblages. The microthermometric characteristics of each of the FI types are separately described according to their distribution in the quartz veins of the three mineralisation stages.

Because of the high density of fluid inclusions in quartz crystals, the distinction of the temporal relationship between fluid inclusions is not always clearly possible. The measurements were restricted to isolated inclusions or fluid inclusion assemblages that were obviously not secondary. To avoid having to deal with post-entrapment modification effect, the FIs with obvious features such as deformation or decrepitating halos were not analysed.

480

## 7.1. Stage I

In Stage I, the temperature of first apparent ($T_e$) and last ($T_m(ice)$) ice melting of the L-type FIs were measured from -48 to -23 °C and from -9.5 to -4.3 °C (n=12), respectively, yielding salinities between 6.8 and 13.4 wt.% NaCl$_{eq}$. They homogenised into liquid at temperatures from 324 to 399 °C (Fig. 6a).

$T_m(CO_2)$ of V1-subtype FIs was always measured at -56.6 °C. Clathrate dissociation ($T_m(cla)$) at Q2 transition, i.e. $Cla-L_{aq}-L_{CO_2}-V_{CO_2}$) was measured between 3.2 and 7.3 °C and $T_h(CO_2)$ was measured from 11.2 to 29.2 °C. The corresponding salinity ranges from 5.5 to 12.0 wt. % NaCl$_{eq.}$ (n=77). The total homogenisation temperature, into carbonic vapour, of the V1-type FIs ranges from 410 to >600 °C (Fig. 6a). During these experiments, the $CO_2$ vapour bubble expanded slowly upon heating and homogenisation showed pseudocritical or critical behaviour. The V2-subtype FIs of Stage I showed $T_e$ ranging from -46 to -24 °C, and $T_m(ice)$ ranged from -7.6 to -2.5 °C (n=28), corresponding to a salinity from 4.1 to 11.0 wt. % NaCl$_{eq}$. The homogenisation temperature into vapour of the V-type FIs ranged from 400 to 496 °C (Fig. 6a).

482

483

484

485

486

487

488

489

490

491

492

493

494

495
496 S1-type FIs ($T_m$(hal) > $T_{h(LV->L)}$) homogenised by halite disappearance from 398 to 498 °C,
497 while $T_{h(LV->L)}$ occurred between 310 and 466 °C (n=69), indicating a salinity from 43.5 to
498 59.4 wt. % NaCl$_{eq.}$ (n=69). S2-type FIs ($T_m$(hal) < $T_{h(LV->L)}$) homogenised by vapour
disappearance with $T_{h(LV->L)}$ measured between 383 and 569 °C and $T_m$(hal) between 302 and
500 425 °C. The corresponding salinity ranges from 27.3 to 49.9 wt. % NaCl$_{eq.}$ (n=66) (Fig. 6a).
501 Temperature of sylvite disappearance $T_m$(syl) in S-type FIs of Stage I occurred from 110 to
502 338 °C (n=33). Transparent daughter minerals (calcite) did not dissolve until 600 °C (n=4).

503

504

## 7.2. Stage II

505 $T_e$ of L-type FIs was observed at temperatures from -38 to -23 °C and $T_m$(ice) at temperatures
506 from -6.9 to -4.1 °C (n=11), indicating a salinity of 6.5-10.0 wt.% NaCl$_{eq.}$ (Fig. 6b). Total
507 homogenisation of L-type into liquid occurred between 331 and 375 °C (n=11) (Fig. 6b).

508 The V1-subtype FIs showed the following temperatures during freezing and heating runs:
509 $T_m$(CO$_2$) of -56.6 °C, $T_m$(cla) (Q2 transition) from +2.9 to 8.9 °C (n=87), and $T_h$(CO$_2$) to $V_{CO2}$
510 from 11.3 to 30.0 °C, corresponding to a salinity ranging from 1.7 to 12.1 wt.% NaCl$_{eq}$.
511 (n=87). Total homogenisation into carbonic vapour was observed at temperatures from 318 to
512 500 °C (n=87) (Fig. 6b). $T_e$ and $T_m$(ice) of the V2-subtype FIs were between -40 and -22 °C
513 and from -5.8 to -1.2 °C (n=46), respectively, corresponding to a salinity of 2.0 to 8.9 wt. %
514 NaCl$_{eq}$. Temperature of total homogenisation into vapour is from 266 to 464 °C (n=46) (Fig.
515 6b).

516 Temperature of sylvite disappearance $T_m$(syl) in S-type FIs of Stage II occurred from 110 to
517 365 °C (n=32). The total homogenisation to liquid by halite disappearance $T_m$(hal) of S1-type
518 ($T_m$(hal) > $T_{h(LV->L)}$) occurred from 322 to 399 °C and $T_{h(LV->L)}$ from 399 to 282 °C (n=41),
519 indicating a salinity in the range 47.3 to 39.1 wt. % NaCl$_{eq.}$ (Fig. 6b). Total homogenisation
520
into liquid by vapour disappearance ($T_{h(LV->L)}$) of S2-type ($T_m(\text{hal}) < T_{h(LV->L)}$) occurred from 323 to 399 °C and $T_m(\text{hal})$ from 267 to 365 °C (n=68), corresponding to a salinity ranging from 23.3 to 43.4 wt. % NaCl$_{eq.}$ (n=68) (Fig. 6b).

524

## 7.3. Stage III

The temperatures of $T_c$ and $T_m(\text{ice})$ of the of L-type FIs were measured from -30 to -22 °C and from -7.8 to 2.3 °C (n=18), respectively, yielding salinity of 3.8 to 11.0 wt.% NaCl$_{eq.}$.

Total homogenisation into liquid occurred from 316 to 200 °C (Fig. 6c).

All measured V1-subtype FIs showed $T_m(\text{CO}_2)$ of -56.6 °C. $T_m(\text{cla})$ (at Q2) in V1-subtype FIs was measured from 4.9 to 8.9 °C and $T_h(\text{CO}_2)$ to $V_{\text{CO}_2}$ occurred from 23 to 30 °C (n=27), corresponding to a salinity from 1.8 to 9.8 wt. %. NaCl$_{eq.}$. Total homogenisation temperatures of V1-subtype FIs into carbonic vapour ranged from 257 to 384 °C (Fig. 6c). V2-subtype FIs showed $T_c$ from -48 to -26 °C and $T_m(\text{ice})$ from -3.2 to -1.1 °C (n=31), corresponding to a salinity in the range 1.8 to 5.2 wt% NaCl$_{eq.}$. Total homogenisation into vapour ranged between 244 and 317 °C (Fig. 6c).

Temperature of sylvite disappearance $T_m(\text{syl})$ in S-type FIs of Stage III occurred from 82 to 199 °C (n=19). The majority of S-type FIs homogenised by vapour phase disappearance (S2-type ($T_m(\text{hal}) < T_{h(LV->L)}$) after halite disappeared (n=113) whereas a few inclusions homogenised by halite melting (S1-type ($T_m(\text{hal}) > T_{h(LV->L)}$; n=8)). Halite disappearance ($T_m(\text{hal})$) and total homogenisation to the liquid ($T_{h(LV->L)}$) of S1-type FIs ranged from 291 to 360 °C and from 260 to 290 °C (n=8), respectively, corresponding to salinity between 35.0 and 43.1 wt.% NaCl$_{eq.}$ (Fig. 6c). $T_{h(LV->L)}$ and $T_m(\text{hal})$ of S2-type FIs ($T_m(\text{hal}) < T_{h(LV->L)}$) are from 235 to 396 °C and from 145 to 279 °C (n=113), respectively, corresponding to a salinity between 17.5 and 36.5 wt. % NaCl$_{eq.}$ (Fig. 6c).

545
## 7.2. Raman spectroscopy analyses

Raman spectroscopic analyses were conducted on the gas and solid phases of representative FIs of each type and of each stage. Phase transitions observed during microthermometric experiments of V2-subtype, L-type and S-type inclusions did not reveal the presence of CO₂ in any of the mineralising stages. Nevertheless, CO₂ was detected by Raman spectroscopic analyses made at room temperature by the typical bands at 1280 and 1383 cm⁻¹ (Fig. 7a-c).

The absence of visible phase transitions during heating-freezing runs suggests that the CO₂ content in these fluid inclusions is significantly lower than in V1-type. The vapour phase of the V1-subtype FIs in Stage I is dominated by CO₂ with minor amounts of N₂ (2326 cm⁻¹) and H₂S (2606 cm⁻¹) (Fig. 7d). In Stages II and III, only CO₂ was detected in the vapour phase of V1 subtype FIs (Fig. 7i-k), in agreement with the measured Tₘ(CO₂) at -56.6 °C (Table 2). Moreover, the relative amount of V1-type inclusions has decreased from Stage I to Stage III, indicating that the CO₂ content is decreasing. Transparent daughter minerals are mainly cubic halite (Fig. 5.c, d) and sylvite (Fig. 5c), which did not show any signal during Raman spectroscopy analyses. Calcite (typical bands at 280 and 1082 cm⁻¹) was identified in L-type, S-type and V-type FIs in Stage I (Fig. 7e, g, h). In Stage I, anatase (characteristic bands at 391, 509 and 634 cm⁻¹) was observed in V1-subtype FIs (Fig. 7f). In Stages II and III, opaque crystals contained in V1-type FIs showed the characteristic spectra of chalcopyrite (283, 312 and 378 cm⁻¹; Fig. 7j, k), suggesting the possibility of metal transport by the CO₂-bearing vapour phase. This presumption will be quantitatively asserted in the LA-ICPMS analysis of FIs. Moreover, as identified by petrography, in Stages II and III, the most commonly observed triangle or round opaque daughter minerals in V and S-types FIs have been determined as chalcopyrite and molybdenite by their characteristic Raman bands at 285-378 cm⁻¹ (Fig. 7k) and 921-1010 cm⁻¹ (Fig. 7l), respectively.
7.3. LA-ICPMS analyses of fluid inclusions

Results from LA-ICPMS microanalyses were obtained from 33 primary CO₂-bearing V- and S-type FIs, concentrated as isolated individuals with size 10 to 30 µm in the three mineralisation stages (Table 3). Due to the small size of the inclusions, element concentration derived from LA-ICPMS peak integration, might result in large uncertainty. LA-ICPMS analyses of FIs show that the compositions of all FI types are dominated by Na, K, Fe, Mn and Cu which provide the better uncertainties. (Fig. 9; Table 3). The results are presented thereafter element by element to describe their content in each stage in V- and S-inclusions.

K and Fe are the dominant cations besides Na in all types of fluid inclusions in each stage.
The values are given with a good uncertainty (generally <20 % for K and <50 % for Fe).

These elements are more concentrated in S-type inclusions and their concentration increases
towards Stage III. The elevated amounts of K in inclusions of Stages II and III are compatible
with the presence of sylvite suspected during microthermometric experiments. Some values of
Fe are extremely high, above 400,000 ppm and point to the presence of hematite or magnetite,
and/or chalcopyrite when associated with high amounts of Cu.

Mn, Zn, Pb and Cu are present in all analyses with uncertainties generally below 50 % for
Mn, Pb and Cu and below 80% for Zn. Their contents increase from Stage I to Stage III (up to
90,000 ppm for Mn, 25,000 ppm for Zn, 8,000 ppm for Pb and 40,000 ppm for Cu). These
elements are more concentrated in S-type inclusions and all inclusions of a given type are in
the same order in a given stage, except Cu, large variation of which is compatible with the
presence of chalcopyrite. Some values of Mn are exceptionally high. Because these values are
also associated with abnormal contents of Fe and Ti, they could point to the presence of
hematite or magnetite in the fluid inclusions. Fluid inclusions of Stage III show exceptionally
high contents of Zn, compatible with the presence of sphalerite.
The analyses of Ti and Mg are given with large uncertainties often higher than 80 %. 595

Moreover, these elements are extremely variable among the analysed inclusions of a given 596 type. This points to accidentally trapped minerals in fluid inclusions, hematite or magnetite, 597 anatase and very likely chlorite and/or phlogopite. 598

Mo is barely detected in inclusions of Stage I but is detected in comparable amounts in Stages 599 II and III up to 1,200 ppm, mainly in S-type inclusions. These values of Mo are attributed to 600 the presence of molybdenite daughter or accidentally trapped minerals in the fluid inclusions. 601

Bi is found in comparable amounts in all stages below 300 ppm (except an outlier at 910 602 ppm), mainly in S-type inclusions. Rb, Sr and Ba are generally more present in S-type 603 inclusions with an increasing concentration from Stage I to Stage III up to 2,400 ppm for Rb 604 (except one value at 7,900 ppm), 400 ppm for Sr (except two values) and 1000 ppm for Ba 605 (except one value at 1,600 ppm). Sn was never detected in V-type inclusions and only in S- 606 type inclusions of Stages II and III. Cs also was never observed in V-type inclusions; its 607 content increases from Stage II to III. Sb was only found sporadically close to the limit of 608 detection and with elevated uncertainties always higher than 80 %. 609

610

## 8. Discussion
---

The Haftcheshmeh Cu-Mo porphyry deposit shows three successive stages of alteration and 612 mineralisation from potassic to sericitic. The associated fluid inclusions all show the presence 613 of CO₂ in the gas phase. As for the Haftcheshmeh porphyry deposit, the occurrence of the 614 CO₂-bearing FIs was already reported in some Iranian porphyry type deposits as the 615 Sarcheshmeh Cu-Mo deposit (Etminan, 1977), the Meiduk porphyry Cu deposit (Asadi et al., 616 2013; Padyar et al., 2017), the Dalli porphyry Cu-Au (Zarasvandi et al., 2015), and the Keder, 617 Ijo and Sarkuh porphyry Cu deposits (Zarasvandi et al., 2018). As in Iran, CO₂ was also 618 shown in porphyry deposits worldwide for example at the El Teniente Cu-Mo deposit, Chile 619
620 (Klemm et al. 2007), or in China at the Yulong Cu-Mo deposit (Chang et al., 2018), the
621 Luoboling Cu-Mo deposit, (Zhong et al., 2014), the Dexing Cu-Mo-Au deposit (Liu et al.,
622 2016), and the Wulasigou Cu deposit (Zheng et al., 2012). The presence of CO₂ in the gas
623 phase of porphyry deposits is thus a common feature in Iran and worldwide. It is thus
624 suspected that CO₂-bearing inclusions, as in Butte deposit (Rusk et al, 2008) and Yuchiling
625 porphyry Mo deposit (Li et al, 2012), play an important role in molybdenite mineralisation
626 and precipitation.
627

627

628 **8.1. Fluid boiling and mixing**

629 Three types of fluid inclusions were reported in the three successive alteration and
630 mineralisation stages of the Haftcheshmeh Cu-Mo porphyry deposit. Interestingly all these
631 inclusions contain CO2 in their gas phase at varying density. The inclusions with a low
632 salinity and a small vapour bubble (L-type inclusions) are restricted to late fluid inclusion
633 trails and are considered as secondary with regard to the mineralising events (Fig. 4b). The
634 two other types of fluid inclusions, halite-saturated aqueous-rich S-type and CO2-bearing V
type, are always found in close association within their host quartz crystals (Fig. 4a, c, d; 5a,
635 d, e) of the three mineralisation stages. S-type inclusions homogenising by halite melting (S1-
636 subtype) could indicate post-entrapment modification (Audôtat and Gunther, 1999; Bodnar,
637 2003) as suggested by undulose extinction and recrystallisation of the quartz. When
638 considering only the S2 and V-types fluid inclusions, we can clearly see that their
639 homogenisation temperatures fall in the same range in each of the mineralising stages, i.e.
640 around 400-550 °C, 300-450 °C and 250-350 °C from Stage I to III (Fig. 6; Table 2). Fluid
641 inclusions outside these ranges may also point to post-entrapment modification. Altogether,
642 the textural (close association in quartz crystals), petrographic (coexistence of vapour-rich V-
643 type and halite-saturated water-rich S-type fluid inclusions) and microthermometric
644
645 (homogenisation by liquid or vapour disappearance, respectively, within the same range of temperature) observations point to continuous entrapment of a boiling fluid from Stage I to III
646 as described in other porphyry mineralised systems (e.g., Hezarkhani and Williams-Jones,
647 1998; Rusk et al., 2008; Hezarkhani and Williams-Jones, 1998; Voudouris et al., 2009). The
648 presence of L-type inclusions probably indicates a local late opening of the system to surface
649 fluids.
650

651 Stage I is mainly characterised by coexisting S- and V-type FIs (Fig. 5b, e; Table 2),
652 homogenising in different modes (vapour and liquid disappearance, respectively, when not
653 considering S1 inclusions) at a similar temperature range of 400 to 550 °C (Fig. 6; Table 2).
654

655 Although this temperature range might be large, probably reflecting (i) the fact that it is very
difficult to clearly identify fluid inclusion assemblages due to the high density of fluid
656 inclusions in the quartz and (ii) very probably post-entrapment modification as suggested by
657 quartz undulose extinction and local recrystallisation, fluid inclusions of Stage I indicate
658 heterogeneous trapping and fluid separation during boiling. The coexistence over a large
659 range of temperature of S-type and V-type FIs containing CO2, H2S and N2 suggests
660 continuous entrapment at a high temperature of a CO2-bearing, oxidising (high fO2), saline
661 ore-forming fluid below the solvus in the H2O-CO2-NaCl system. Only anhydrite in quartz
662 veins and calcite as a daughter or accessory mineral within the S- and V-type FIs are observed
663 in Stage I, which is considered as barren. Despite fluid boiling and the associated element
fractionation, sulphide minerals have not precipitated.
664

665 Various sulphide-bearing stockworks including molybdenite and chalcopyrite-bearing quartz
666 veins were formed in Stages II and III, associated with the transition from potassic to sericitic
667 alterations (Fig. 3c-k). As for Stage I, the petrographic and microthermometric observations
668 (Fig. 5 and 6) point to heterogeneous entrapment and fluid separation during boiling in a
669 temperature range of 300 to 450 °C. During the transition from Stage I to Stage II,
670 molybdenite is the first sulphide phase that precipitated, probably due to decreasing temperature, followed by chalcopyrite. Our observations showed that the quartz of Stage II is characterised by a decreasing amount of the CO₂-bearing V1-subtype FIs coexisting with S-type FIs containing halite, sylvite and chalcopyrite as daughter minerals (Fig. 5c, d). Although molybdenite precipitated in Stage II, the amount of Mo is generally higher in fluid inclusions of Stage II than in Stage I. This is explained by the presence of small molybdenite daughter minerals in fluid inclusions of Stage II. The same goes for the higher amount of metals (Cu, Ti and Fe mainly) detected by LA-ICPMS in fluid inclusions of Stage II, which can be explained by the presence of chalcopyrite and titanite or anatase.

679 Therefore, fluid boiling in Stage II led to the gradual decrease of the volume proportions of the V1-type FIs due to large-scale CO₂ escaping associated with pH and fS²-increase, and fO₂ decrease (Hezarkhani and Williams-Jones, 1998; Seo et al., 2012). On the other hand, CO₂ degassing would also cause Cu-Cl complexes to be less soluble and could directly precipitate considerable sulphide mineralisation in the hydrothermal system (Gammons and Williams-Jones, 1997; Robb, 2005). Thus, CO₂ differential degassing together with cooling of the system could be considered as the main processes of sulphate reduction; causing the formation of reduced sulphur species and main ore stage sulphide mineralisation.

687 Decreasing fO₂ is evidenced by the detection of chalcopyrite as daughter mineral (Fig. 5c, d), the absence of anhydrite in Stage II veins and calcite accidentally trapped minerals in the FIs of Stages II and III. Fluid boiling at lower temperature and fO₂ conditions than in Stage I facilitated the precipitation of molybdenite and chalcopyrite. Mineralisation was associated with hydraulic fractures and stockwork veins.

692 The Stage III veins are characterised by sericitic alteration halos (Fig. 3j), the increasing number of V2-subtype and L-type FIs, and the absence of V1-subtype inclusions. As for Stages I and II, fluid inclusions point to heterogeneous entrapment due to boiling in Stage III.
This event however occurred at lower temperatures of around 250-350 °C. The salinity measured in the fluid inclusions is also slightly lower than in the previous stages.

Temperature and salinity gradually decrease from Stage I to Stage III. The decrease of CO2 content, salinity and temperature and the increasing number of L-type fluid inclusions could indicate a gradual mixing of the oxidised high temperature, high salinity and CO2-bearing early magmatic fluids with circulating low temperature, low salinity and CO2-poor meteoric or basin fluids (Voudouris et al. 2009). The presence of chalcopyrite-bearing S-type FIs, besides halite and sylvite daughter mineral however indicates that Cu-rich magmatic- hydrothermal fluids are still dominant during sericitic alteration of Stage III (Harris and Golding 2002). The widespread ore deposition related to Stage III is probably attributed to temperature decrease, fluid boiling and associated element partitioning. Mixing of magmatic fluid with low-temperature/salinity meteoric water is possible but not clearly supported by our data. However, such a mixing would trigger reducing temperature, salinity, fO2, fH2S, SO4²⁻ and CO2 content and increasing of fS²⁻ (Muntean and Einaudi, 2001; Simmons et al., 2007) leading to precipitation of sulphide minerals in the widespread hydrothermally fractures and stockwork veins (Fournier, 1999).

711

## 8.2. Pressure and depth estimation of the mineralising events

In the case of heterogeneous entrapment of coexisting aqueous- and vapour-rich fluid inclusions during boiling or immiscibility below the solvus, the temperature and pressure conditions measured at homogenisation are representative of the true entrapment conditions (Diamond 2001; Rusk et al. 2008). In such cases, the pressure is generally derived from the fluid inclusions dominated by the volatile phases, for which the equations of state are more accurate at homogenisation (e.g. Tarantola et al., 2007). This approach was followed in our case where liquid-rich S-type fluid inclusions provided very large variations in pressure
estimation. Many of the S-type FIs during Stages I and II homogenised by halite dissolution ($T_m$(hal) > $T_{h(LV>L)}$; S₁-subtype), which was interpreted in other porphyry and magmatic-hydrothermal ore deposits as the result of direct exsolution of a halite-saturated magmatic fluid from the parent magma and saturation beside the liquid-vapour-halite curve (Cline and Bodnar, 1994; Lecumberri-Sanchez et al., 2015), heterogeneous trapping from a NaCl-saturated fluid at high pressure (Lecumberri-Sanchez et al., 2012), or post-entrapment modification as supported by quartz undulose extinction and local recrystallisation (Audôtat and Gunther, 1998).

As Becker et al. (2008) suggested, homogenisation by halite dissolution would cause underestimation or overestimation in entrapment pressure estimation and correlated mineralisation depth. Therefore, the unreliable pressure given from the supersaturated S₁-subtype inclusions (Table 2) is normally greater than truly estimated pressures. Therefore, the actual pressure of the CO₂-bearing fluids in the three mineralisation stages of the Haftcheshmeh Cu-Mo porphyry deposit can be constrained by regarding the trapping pressure of the V1- and S2-types end-member inclusions that were trapped nearest to the solvus (Diamond et al., 2001) (Fig. 10). According to the minimum densities and trapping pressures estimated by the CO₂-H₂O system (Bakker, 1998; Bakker, 2003) for V1-subtype in the quartz veins of Stages I to III (Table 2), and assuming the rock density to be 2.85 g/cm³, we concluded that the barren quartz veins of Stage I, have probably formed at estimated trapping pressure between 92 and 42 MPa, corresponding to a trapping depth of 1.5 to 3.2 km assuming lithostatic conditions (Fig. 10; Table 2). The Stage II FIs were trapped at pressures in the range 74-30 MPa, corresponding to a depth of 1.1 to 2.6 km assuming lithostatic conditions or 3.0 to 7.4 km assuming hydrostatic conditions (Fig. 10; Table 2). Stage III is formed at atrapping pressure of 42-19 MPa, corresponding to entrapment at 1.94-2 km at hydrostatic conditions (Fig. 10; Table 2).
Overall, mineralisation in the Haftcheshmeh Cu-Mo porphyry deposit occurred at depths comparable to other porphyry deposits in the world (Seedorff et al. 2005). It should not exceed 3.2 km as indicated by V-type inclusions of Stage I. The pressure then slightly decreases in Stages II and III while the system evolves to the surface to hydrostatic conditions at a depth recorded by V-type inclusions of 1.9 km.

750

## 8.3. Nature and evolution of magmatic-hydrothermal ore forming fluids at Haftcheshmeh Cu-Mo porphyry deposit

The magmatic-hydrothermal fluid evolution associated with the Haftcheshmeh Cu-Mo porphyry deposit is schematically represented in the H₂O-NaCl system (Fig. 10). However, the influence of the CO₂ content on extending the P-T conditions of the fluid immiscibility field in the NaCl-H₂O system is important (Lowenstern, 2001; Bakker, 2009). Similar to the Stage I of the Haftcheshmeh Cu-Mo porphyry deposit, the transition from CO₂-rich single-phase to two-phase (coexisting hypersaline liquid and vapour-rich inclusions) conditions has been observed for example in early quartz of Butte (Rusk et al., 2008; Bennett et al., 2014), Bingham Canyon (Redmond et al., 2004; Landtwing et al., 2010), Çöpler (Skewes, 2016), Elatsite (Stefanova et al., 2014), El Teniente (Klemm et al., 2007), Far Southeast (Hedenquist et al., 1998; Bennett et al., 2014), Nevados de Famatina (Pudack et al., 2009), and Pebble (Gregory, 2017) porphyry deposits. All of these studies evidenced that early quartz veins, associated with potassic alteration, were formed as the result of the cooling and pressure drop of the ascending magmatic-hydrothermal fluids under open-system conditions within the two-phase field of the H₂O-NaCl system at lithostatic pressure.

The ore-forming quartz of Stage I with potassic alteration halos (Fig. 3b) shows evidence of boiling and heterogeneous entrapment by the coexistence of NaCl-poor V- and NaCl-rich S-type FIs with a similar range of homogenisation temperatures (Table 2). In Stage I, V1-type
FIsexpanded slowly upon heating experiments and homogenised by pseudocritical or critical behaviour. This feature displays the formation in the early near-critical vapour-like magmatic-hydrothermal fluids from magma from a single-phase field (Monecke et al., 2018). The upward-moving single-phase magmatic-hydrothermal fluids will drop into the L+V coexistence field of the H₂O-NaCl system (Fig. 10) and will form the Stage I quartz veins containing high salinity S-type and V-type FIs through rocks at lithostatic conditions. In the Haftcheshmeh Cu-Mo porphyry deposit following the transition from lithostatic to hydrostatic conditions (Fig. 10), earlier-formed quartz veins could be dissolved and reopened by the magmatic-hydrothermal fluids and then healed by Stage II quartz veins.

As for Stage I, the ore-forming fluid of Stage II shows the coexistence of V- and S-type FIs, with elevated CO₂ and metal content (Tables 2 and 3). Therefore, the significant molybdenite mineralisation in Stage II has precipitated either along the margin or filling centrelines of the veins during continuing ascending and boiling of the liquid-like magmatic-hydrothermal fluids at temperatures of about 300 to 450 °C, accompanied by pressure fluctuation conditions between lithostatic and hydrostatic, and the change of wall-rock behaviour from ductile to brittle conditions within the two-phase field of the H₂O-NaCl system (Fournier, 1999; Monecke et al., 2018).

The ore-forming fluids of Stage III are dominated by S2-, V2- and L-type FIs and rare V1-subtype FIs. The inclusions have high metal content but are largely depleted in CO₂ (Tables 2 and 3). The late Stage III quartz veinlets are accompanied by sericite alteration (Fig. 3j) of the wall rocks and were formed as a result of exsolving and continuing cooling of the near-critical or critical single-phase magmatic-hydrothermal fluids originating from fractionated magma chamber to shallow depths (Monecke et al., 2018), at temperatures below 350 °C close to the ductile-brittle transition in hydrostatic conditions. Entrapment of the coexisting CO₂-bearing high-salinity S- and V-type FIs at low-pressure conditions of Stage III, evidenced by
occurrence of the S2-subtype FIs homogenising by vapour disappearance ($T_{h(LV->L)} > T_m(hal)$)
and V2-subtype FIs containing halite and sylvite daughter minerals, have indicated that the
L+V coexistence field extended by shifting near the L+V+H coexistence curve of the H₂O-
NaCl system (Fig. 10) (Muntean and Einaudi, 2000; Monecke et al., 2018). Moreover, the
possible dilution of the magmatic hydrothermal fluids by surface fluids is not unlikely.

800

## 8.4. Compositional variations of fluid inclusions during alteration-mineralisation

Element concentrations of FIs of Stage I to III change gradually indicating that the
composition of hydrothermal fluids evolved in association with potassic to sericitic alteration
(Fig. 9). This evolution may be complicated by the ablation and analysis of accidentally
trapped minerals within the fluid inclusions.

The K concentration shows a strong variation in inclusions of Stage I, leading to unrealistic
Na/K concentration ratio, and suggesting the presence of accidentally trapped K-bearing
minerals besides sylvite. When not considering these abnormal values, the Na/K
concentration of CO₂-rich V- and S-type FIs of Stage I (Na/K~ from 1 to 2) are nonetheless
higher than those in Stage II where the Na/K ratio is around 1 and tends to be generally below
1 in Stage III (Fig. 9). Moreover, the raw K concentration gradually increases from Stage I to
Stage III. Post-entrapment modification of fluid inclusions in the ductile domain of
deformation does not result in salt/gas variation (Diamond et al. 2010). Hence it is unlikely
that the elevated Na/K ratio of Stage I is the result of elemental fractionation during
reequilibration of inclusions. This goes more in favour of heterogeneous entrapment of halite
saturated fluid during Stage I (Lecumberri-Sanchez et al., 2012). The Na/K ratios of
Haftcheshmeh Cu-Mo porphyry deposit are similar to the Grasberg porphyry (Na/K=~1;
Heinrich et al., 1999), Bajo de la Alumbrera porphyry (Na/K=~1.3; Heinrich et al., 1999), the
Mole Granite (Na/K=~1.6; Audôtat et al., 2000) and the Butte porphyry deposits (Na/K=~1.6;

795

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797

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819
Rusk et al, 2008). The Na/K ratios of fluid inclusions associated with potassic alteration are generally higher (Stage I and II) than with sericitic alteration (Stage III). This suggests that potassic alteration progressively reduced from Stage I to III, as related by vein petrography and gradual increase of K in the fluid inclusions. The depleted K-values are related to the formation of secondary K-feldspars and biotite. Interestingly, Rb and Sr concentration in fluid inclusions are positively correlated with K increase from Stage I to III. As for K, these elements are consumed by secondary K-feldspar during alteration. LA-ICPMS data of Stage I, mainly, show that fluid inclusions trapped the spent fluid during potassic alteration together with some accidental minerals. With one exception, Cu and Mo are found in comparable concentration between each analysed inclusions of Stage I (in the range 2,000 to 4,000 ppm for Cu and below 200 ppm for Mo), with a slight tendency to higher concentration values in V-type inclusions. On the contrary, in Stages II and III, Cu and Mo concentrations are highly variable among the different analysed inclusions with higher values generally in S-type inclusions. This suggests that these analyses correspond to accidentally trapped chalcopyrite and molybdenite minerals that were already present while fluid of Stages II and III were circulating through the rocks of the Haftcheshmeh deposit. Therefore, LA-ICPMS analyses of fluid inclusions indicate that precipitation of chalcopyrite and molybdenite occurred between Stage I and Stage II. The low Cu- and Mo-bearing fluid inclusions of Stage I trapped the parental fluid of the mineralisation. In the same way, Fe concentration is almost constant in Stage I, generally between 10,000 and 50,000 ppm with a preference for S-type fluid inclusions. There is a noticeable increase in Stage II that could be correlated with chalcopyrite precipitation. The values of Fe concentration increase even significantly in Stage III whereas Cu remains constant. This observation, correlated with the same behaviour for Mn concentration, suggests the presence of magnetite or hematite as entrapped minerals in fluid inclusions. The precipitation of Fe-oxides thus happened between Stage II and III. The
concentrations of Zn and Pb are of the same order between all analysed inclusions with a preference in L-type inclusions. The values gradually increase from Stage I to III (Table 3), indicating continuous fluid-rock reactions during the evolution of hydrothermal fluids from potassic to sericitic alteration. The result is the precipitation of sphalerite and galena in Stage III.

## 8.5. Chalcopyrite and molybdenite precipitation

Although the presence of accidentally trapped molybdenite and chalcopyrite minerals in fluid inclusions of Stages II and III points to precipitation of both minerals between Stage I and II, petrographic observations indicate that molybdenite was deposited prior to chalcopyrite.

Various quartz vein samples suggest that molybdenite precipitation mainly occurred in Stage II and rarely in Stage III. On the contrary, chalcopyrite precipitation occurred rarely during Stage II and mainly in Stage III. Therefore, molybdenite and chalcopyrite are commonly separated in Stages II and III quartz veins (Fig. 3b, c), although they can be present with each other at smaller scales in individual veins (Fig. 3k). Based on the obviously temporal and spatial separation of Cu and Mo mineralisation in separate quartz veins and previous FIs studies, it has been suggested that long-lived magmatic-hydrothermal activity and evolution of the magma chemistry by fractionation is accompanied by phase separation, significantly control the different physico-chemical conditions and the vapour-brine partition behaviour of decoupling Mo and Cu mineralisation in porphyry deposits (Audôtat and Pettke, 2003; Landtwing et al, 2010; Vry, 2010; Spencer, 2015).

At the CO₂-rich Haftcheshmeh Cu-Mo porphyry deposit system, metals such as Cu and Mo were derived from the same magmatic fluid exsolved from the underlying magma chamber. The concentration of these metals can still be observed in fluid inclusions of Stage I. Based on fluid inclusion and petrographic observations, the precipitation of molybdenite and
870 chalcopyrite happened continuously from the end of Stage I to Stage III. Molybdenite seems to have precipitated earlier and at a slightly higher temperature than chalcopyrite during fluid ascent.

871 In Stage I, Cu and Mo concentrations in partitioned CO₂-bearing V-type FIs (Cu up to 5,100 ppm; Mo up to 200 ppm) and high-salinity S-type FIs (Cu up to 4,100 ppm; Mo up to 140 ppm) were not enough for molybdenite and chalcopyrite precipitation at these elevated temperatures (Klemm et al., 2008; 2007; Hezarkhani et al., 1999). The presence of accidentally trapped chalcopyrite and molybdenite shows that Mo and Cu depositions occurred continuously during Stage II as in other Mo-rich porphyries (e.g. Questa: Klemm et al., 2008; Bingham Canyon, Utah: Landtwing et al., 2005; and Endako, British Colombia: Selby et al., 2000). No obvious relationship with Mo and Cu concentration of fluid inclusions and temperature has been noticed. Precipitation of molybdenite and chalcopyrite started when the concentration/temperature conditions were met between Stage I and II, at around 450-400 °C. These conditions of temperature are in agreement with the thermodynamic analysis of the Cu complex stability of the Sungun porphyry made by Hezarkhani et al. (1999) and natural FIs studies of Cu-Mo porphyry deposits (Bingham, Landtwing et al, (2005), Seo et al, (2012); and El Teniente, Klemm et al, (2007), Vry, (2010)), that documented Cu sulphides precipitation in the range 220-490 °C. Fluid inclusions of Stage I thus represent the fluid composition prior to deposition and the variable concentration of Mo and Li in fluid inclusions of subsequent stages can only be attributed to accidentally trapped minerals.

890 Despite recent experimental and natural sample studies (Kokh et al., 2017; Zajacz et al., 2017; Chang et al., 2018), it is not so clear if Cu and Mo fractionate preferentially into the high-salinity or the vapour phase of fluid inclusions of Stage I. Mo concentration was generally close to detection limit (60 ppm). Rempel et al. (2006) suggested that low Mo concentration has the potential to form porphyry Mo deposits if fluid regimes operate over a long period of
895 time higher than 1 Ma. Therefore, the long period of ~1.13 ±0.65 Ma of magmatism and
896 hydrothermal alteration (Re-Os on molybdenite; Aghazadeh et al., 2015) of the Haftcheshmeh
897 Cu-Mo porphyry deposit was key for economic molybdenite deposition.

898 In fluid inclusions of Stage I, the LA-ICPMS data indicate the presence of Cu up to about
899 5,000 ppm. In Stages II and III, the analyses show that chalcopyrite has already precipitated
900 and Cu is found in accidentally trapped minerals in the fluid inclusions. As a consequence, no
901 clear positive correlation can be established between Cu and Na concentration in coexisting
902 high-salinity S- and V-type FIs. It is thus impossible to state with the provided data that
903 salinity and the formation of Cl-rich Mo and Cu complexes control Mo and Cu solubility and
904 transport (Tattich et al, 2015; Ulrich and Mavrogenes, 2008). However, CO2 is present in all
905 S- and V-type inclusions, even with the typical double CO2 bubbles at room temperature, of
906 the Haftcheshmeh deposit. Previous natural fluid inclusion studies on porphyry type deposits
907 (Butte deposit, Rusk et al. (2008) and Yuchiling porphyry Mo deposit, Li et al. (2012))
908 considered that CO2-bearing fluids play an important role in molybdenite mineralisation and
909 precipitation. The experiments of Tattitch et al. (2015) suggested that copper partitioning
910 from the melt into hydrothermal fluids is controlled by the changes in the salinity of the
911 vapour and brine, which are functions of XCO2. Their model predicts that CO2-rich (XCO2=
912 0.38) magmatic vapour may remove half of the available copper from the melt, without a
913 contribution from the brine, compared to lower XCO2. Altogether, when considering the three
914 mineralising stages, the CO2-bearing V1-subtype inclusions of the Haftcheshmeh PCD have
915 XCO2 in the range 0.11-0.52 (Table 2).

916 It was demonstrated that the presence of CO2 in magmatic systems may lead to a dramatic
917 decrease in metal solubility within the associated vapours (Phillips and Evans, 2004; Van
918 Hinsberg et al., 2016; Kokh et al., 2017). Metals such as Cu fractionate preferentially in the
919 aqueous vapour phase because of the ability of water molecules to form hydrogen-bonded
clusters that incorporate metal-bearing molecules. The dilution of water-rich vapour with a non-polar gas such as CO₂ results in a drop in the partial pressure of water (pH₂O), and hence destabilisation of hydrated metal-bearing clusters. As a result, metal solubility can decrease up to a factor of 10,000 for Cu (Van Hinsberg et al. 2016). Pressure drop in the system thus leads to two processes that favored Cu precipitation: (i) boiling and metal partitioning either in the liquid or vapour phase, and (ii) CO₂ exsolution from the magma that decreased the pH₂O of the metal-bearing fluid. Thus, CO₂ degassing together with cooling of the system would also increase the pH in the remaining fluids, Cu-Cl complexes solubility and sulphate reduction and causing considerable sulphide precipitation and mineralisation in the hydrothermal system (Gammons and Williams-Jones, 1997; Robb, 2005).

Many studies suggested that mineralisation and alteration zones of the porphyry deposits developed in response to compositional evolution and variation of the multiple pulses of exsolution from crystallising magma chamber (e.g., Candela and Holland, 1986). At Questa porphyry Mo deposit and El Teniente porphyry Cu-Mo deposit, high Cs concentrations in FIs were interpreted to be the product of the high crystal fractionation of the parental magma chamber (Spencer, 2015). At Haftcheshmeh Cu-Mo porphyry deposit, Cs content of high salinity S-type FIs of the three stages are commonly higher than coexisting CO₂-bearing V-type FIs and increase from Stage I to III (Fig. 9). Therefore, the evolved Mo and Cs contents of the high salinity S-type FIs (Fig. 9) from Stages I to III suggest that the more evolved and high salinity magmatic-hydrothermal fluids pulses exsolved either from an extremely fractionated magma source (Zajacz et al., 2017) or by fluids originating from middle to lower crust (Klemm et al. 2007).

## 9. Conclusions
The long-lived gabbrodioritic to granodioritic intrusive episodes associated with repeated fracturing and magmatic-hydrothermal fluid activities at Haftcheshmeh Cu-Mo porphyry deposit are characterised by the superposition of multiple generations of crosscutting quartz-bearing veins. Crosscutting relationships between mineralised veins show that the Cu-Fe sulphide-rich veins cut molybdenite-rich vein, indicating a later introduction of Cu with respect to Mo into the porphyry system. The ore-forming processes of the Haftcheshmeh Cu-Mo porphyry deposit are the result of the long duration of the magmatic activity associated with CO₂ fluxes that favoured metal precipitation during the successive alteration stages.

The repeated fluid boiling in H₂O-NaCl-CO₂ ore forming fluids of Haftcheshmeh Cu-Mo porphyry deposit took place at depths of 3.0 to 1.0 km, when the primary magma inherited both CO₂- and NaCl either by a deep magma source (Baker, 2002), or by incorporation of the shallow crustal assimilation (Lowenstern, 2001). Metal deposition occurred at temperatures between 450 and 250 °C.

Our fluid chemical data show that the gradual evolution of the fractionated magma, accompanied by phase separation and dramatic fluctuation of physico-chemical (P-T-pH₂O) conditions of the magmatic-hydrothermal fluid system from near-lithostatic to near-hydrostatic conditions, controls molybdenite and chalcopyrite mineralisation contemporaneous to transition from Stages I to III at Haftcheshmeh Cu-Mo porphyry deposit.

## Acknowledgements

This work is a part of the first author's Ph.D. thesis at Shahid Beheshti University (SBU), Iran. The first author expresses her appreciation to the Iranian Ministry of Science Research and Technology and the GeoRessources laboratory of the University of Lorraine (France) for providing an opportunity for a 9 month sabbatical stay. The TRIGGER programme is thanked for supporting collaboration between Iran and France and part of the analyses of the present
work. Particular thanks go to Dr. M-C. Caumon (GeoRessources laboratory, Nancy, France)
for assistance during Raman spectroscopy. Two journal reviewers are warmly acknowledged
for their constructive comments and suggestions for the first version of the manuscript. Prof.
Khin Zaw is thanked for manuscript handling and editorial input.

974

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Figure captions:

Figure 1. (a) Schematic geological map of Iran showing major tectonic elements (modified after Hassanpour, 2015; Moritz et al. (2016)) and location of the Arasbaran Magmatic Zone (AMZ). (b) Regional geological map of the AMZ in NW Iran, Southern Armenia and Azerbaijan (after Hassanpour et al., 2015). (c) Geological map of the Haftcheshmeh Cu-Mo porphyry deposit (NICICO, 2010).

Figure 2. (a) Alteration map of the Haftcheshmeh Cu-Mo porphyry deposit (NICICO, 2010). (b) Plagioclase phenocryst, with polysynthetic twining, replaced by feldspar (Kfs); the subhedral primary amphibole and biotite phenocrysts are altered to chlorite and opaque minerals. (c) Formation of tiny flakes of secondary biotite and K-feldspar indicate intensive potassic alteration. (d) Sericitic alteration with alteration assemblage made of sericite, chlorite, quartz and opaque minerals. (e) Disseminated chlorite, epidote and sericite in propylitic alteration zone. Photomicrographs are in cross-polarised light.

Abbreviations: Bt=biotite, Chl=chlorite, Ep=epidote, Hb=hornblende, Kfs=K-feldspar, Opa=opaque minerals, Qtz=quartz, Ser=sericite.

Figure 3. Representative photographs of the host rock and photomicrographs illustrating vein-veinlets crosscutting relationships and sulphides mineralisation in different quartz-sulphide vein-veinlets of Haftcheshmeh Cu-Mo porphyry deposit. (a) Barren quartz vein-veinlets (A-type) of the altered gabbro-diorite porphyry. The absence of sulphides is a characteristic feature of these veins. (b) Quartz veins of Stage I (A-type) surrounded by potassic alteration characterised by disseminated secondary biotite, K-feldspar and anhydrite alteration halo. (c) Molybdenite in
margin of quartz veins of Stage II in the altered granodiorite porphyry crosscut by later quartz-chalcopyrite-pyrite±molybdenite veins. (d) Molybdenite in margin of quartz veins in Stage II, infilled by chalcopyrite and pyrite. (e) Centre line of chalcopyrite-pyrite in a quartz vein of Stage II, surrounded by K-feldspar, biotite and muscovite alteration halos. (f) Molybdenite as film-shaped coating cracks in margin of quartz, biotite and K-feldspars of Stage II. (g) Euhedral magnetite±hematite with chalcopyrite in Stage II. (h) Bornite in the margin of chalcopyrite along with magnetite and molybdenite in quartz veins of Stage II. (i) Pyrite and chalcopyrite, with minor quartz, veins of Stage III overprinting the barren quartz of Stage I hosted in granodiorite porphyry. (j) Quartz veins of Stage III surrounded by intense sericitic alteration halo (D-type). (k) Lamellar molybdenite along with galena and chalcopyrite in Stage III veins. (l) Chalcopyrite, galena, sphalerite in quartz veins of Stage III.

Abbreviations: Bn=bornite, Bt=biotite, Ccp=chalcopyrite, Gn=galena, Hem=hematite, Kfs=K-feldspar, Mo=molybdenite, Mt=magnetite, Py=pyrite, Qtz=quartz, Ser=sericite, Sp=sphalerite.

Figure 4. Microphotographs of different primary and secondary FIs observed in the Haftcheshmeh quartz veins from Stage I to III. (a) Primary FIs trapped along growth zones in euhedral quartz from Stage I veins. (b) Secondary trail of crosscutting L-type FIs trapped along healed fractures in Stage II. (c) Primary FIs trapped along growth zones in euhedral quartz from Stage II veins. (d) Primary FIs trapped along growth zones in euhedral quartz from Stage III veins, containing chalcopyrite, pyrite and sphalerite.

Figure 5. Microphotographs of different types of FIs observed in the Haftcheshmeh quartz veins from Stage I to III. (a) V1 FIs in Stage I. (b) Coexistence of S1 ($T_m(\text{hal})>T_h(\text{LV->L})$) containing
calcite entrapped mineral and V1 (VCO2L) FIs in Stage I. (c) Coexistence of V1 and S2 subtype FIs in Stage I. (d) Coexistence of S1 ($T_{m(hal)} > T_{h(LV->L)}$), V1 and V2 FIs containing chalcopyrite entrapped minerals from Stage II. (e) Coexistence of V2-, S2 ($T_{m(hal)} < T_{h(LV->L)}$) and S1 FIs, containing chalcopyrite entrapped minerals in Stage III. (f) Coexisting of L, V1, V2 and S2 FIs from Stage II.

Abbreviations: Cc: calcite, Ccp: chalcopyrite, Hal: halite, LCO2: CO2 liquid, LH2O: H2O liquid, Syl: sylvite, Sp: sphalerite, Py: pyrite, VCO2: CO2 vapor.

Figure 6. Homogenisation temperature (°C) versus salinity (wt. % NaCleq.) diagrams for FIs from veins of the successive mineralising stages I (a), II (b) and III (c). The critical and halite saturation curves correspond to the H2O-NaCl system, without considering the presence of CO2 in the fluid inclusions.

Figure 7. Representative Raman spectra of fluid inclusions in the Haftcheshmeh Cu-Mo deposit. (a-c) CO2 from the vapour phase of L, V2 and S1 FIs in the barren quartz veins of Stage I. (d) N2 and H2S spectra of the vapour phase of the V1-subtype inclusion in the barren quartz veins of Stage I. (e) Calcite in L-type inclusion of Stage I. (f) Anatase (TiO2) in V1-subtype inclusion of Stage I. (g-h) Calcite daughter S1 inclusions of Stage I. (i) CO2-spectrum of vapor phase of V1-subtype of Stage II. (j) Chalcopyrite in V1 inclusion of Stage II. (k) CO2 of vapour phase and chalcopyrite daughter mineral in S2 inclusion in quartz of the Stage III. (l) Molybdenite in S2 inclusion in quartz of the Stage III.
Figure 8. Fluid inclusion LA-ICPMS signal of analysed elements. (a) S2-type (inclusion #6L) and (b) V1-type (inclusion 3-5.L) inclusions in Stage I. (c) S2-type (inclusion #33D) and (d) V1-type (inclusion #2D) inclusions in Stage II. (e) S2-type (inclusion #9D) and (f) V2-type (inclusion #26D) in Stage III. Background indicates the signal of the host-quartz. See Table 3 for the detail of fluid inclusion metal content.

Figure 9. Element concentration of S and V FIs (b) from the three mineralising stages obtained from LA-ICPMS analyses. Data below the detection limits are not shown in the diagram.

Figure 10. Temperature-Pressure conditions indicated by fluid inclusions of the successive mineralising stages of the Haftcheshmeh Cu-Mo porphyry deposit. Depth assuming lithostatic and hydrostatic conditions are reported. The critical curve of the H₂O-NaCl system (modified by Driesner and Heinrich (2007)) and the V-L curve for the H₂O-NaCl-CO₂ system with 4 mol % CO₂ and 6 wt % NaCl (Gehrig et al., 1986) are reported. L =liquid, V =vapour, H =halite.
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<figure><img src="image_3.png" /></figure>

<figure><img src="image_4.png" /></figure>

<figure><img src="image_5.png" /></figure>

<figure><img src="image_6.png" /></figure>

<figure><img src="image_7.png" /></figure>
<figure><img src="image_8.png" /><figcaption>a</figcaption></figure>

<figure><img src="image_9.png" /><figcaption>b</figcaption></figure>

<figure><img src="image_10.png" /><figcaption>c</figcaption></figure>

<figure><img src="image_11.png" /><figcaption>d</figcaption></figure>

<figure><img src="image_12.png" /><figcaption>e</figcaption></figure>

<figure><img src="image_13.png" /><figcaption>f</figcaption></figure>
<figure><img src="image_14.png" /></figure>

g

1 mm

<figure><img src="image_15.png" /></figure>

h

1 mm

<figure><img src="image_16.png" /></figure>

i

<figure><img src="image_17.png" /></figure>

j

1 mm

<figure><img src="image_18.png" /></figure>

k

1 mm

<figure><img src="image_19.png" /></figure>

l

1 mm
<figure><img src="image_20.png" /><figcaption>a</figcaption></figure>

<figure><img src="image_21.png" /><figcaption>b</figcaption></figure>

<figure><img src="image_22.png" /><figcaption>c</figcaption></figure>

<figure><img src="image_23.png" /><figcaption>d</figcaption></figure>
<figure><img src="image_24.png" /></figure>

a

<figure><img src="image_25.png" /></figure>

b

<figure><img src="image_26.png" /></figure>

c

<figure><img src="image_27.png" /></figure>

d

<figure><img src="image_28.png" /></figure>

e

<figure><img src="image_29.png" /></figure>

f
<figure><img src="image_30.png" /></figure>

<figure><img src="image_31.png" /></figure>

<figure><img src="image_32.png" /></figure>
<figure><img src="image_33.png" /></figure>

<figure><img src="image_34.png" /></figure>

L-type

10 µm

<figure><img src="image_35.png" /></figure>

<figure><img src="image_36.png" /></figure>

V2-subtype

10 µm

<figure><img src="image_37.png" /></figure>

<figure><img src="image_38.png" /></figure>

S1-subtype

10 µm

<figure><img src="image_39.png" /></figure>

<figure><img src="image_40.png" /></figure>

V1-subtype

10 µm

<figure><img src="image_41.png" /></figure>

<figure><img src="image_42.png" /></figure>

L-type

10 µm

<figure><img src="image_43.png" /></figure>

<figure><img src="image_44.png" /></figure>

V1-subtype

10 µm
<figure><img src="image_45.png" /></figure>

V1-subtype

<figure><img src="image_46.png" /></figure>

10 µm

<figure><img src="image_47.png" /></figure>

S1-subtype

<figure><img src="image_48.png" /></figure>

10 µm

<figure><img src="image_49.png" /></figure>

V1-subtype

<figure><img src="image_50.png" /></figure>

10 µm

<figure><img src="image_51.png" /></figure>

V1-subtype

<figure><img src="image_52.png" /></figure>

10 µm

<figure><img src="image_53.png" /></figure>

S2-subtype

<figure><img src="image_54.png" /></figure>

10 µm

<figure><img src="image_55.png" /></figure>

S2-subtype

<figure><img src="image_56.png" /></figure>

10 µm
<figure><img src="image_57.png" /></figure>

<figure><img src="image_58.png" /></figure>

<figure><img src="image_59.png" /></figure>

<figure><img src="image_60.png" /></figure>

<figure><img src="image_61.png" /></figure>

<figure><img src="image_62.png" /></figure>
<figure><img src="image_63.png" /></figure>

<figure><img src="image_64.png" /></figure>
<figure><img src="image_65.png" /></figure>
<table><caption>Table 1. Paragenitic sequence of quartz vein-veinlets and alteration minerals based on petrography and crosscutting relationships.</caption><thead><tr><th>Stage</th><th>Sample type</th><th>Vein minerals</th><th>Dominant FI types</th><th>Vein thickness</th></tr></thead><tbody><tr><td>I</td><td>Barren quartz vein-veinlets</td><td>Qtz+Kfs+Anh+Bt+Hb+Py+Ccp</td><td>S, V1</td><td>0.5 to &gt;5 cm</td></tr><tr><td>II</td><td>Qtz-molybdenite and quartz-chalcopyrite-bornite-magnetite-hematite</td><td>Qtz+Mo+Ccp+Bn+Py+Mt+Hem+Bt+Kfs</td><td>S, V1, V2</td><td>Several mm to &gt;5 cm</td></tr><tr><td>III</td><td>Quartz polymetallic vein-veinlets</td><td>Qtz+Py+Ccp+Sp+Gn+Mo+Ser+Chl</td><td>S, V2, L</td><td>0.5-6 cm</td></tr></tbody></table>

Mineral abbreviations: Anh=anhydrite, Bt=biotite, Bn=bornite, Chl=chlorite, Ccp=chalcopyrite, Chl=chlorite, Gn=galena, Hem=hematite, Hb=hornblende, Kfs=K-feldspar, Mt=magnetite, Mo=molybdenite, Py=pyrite, Qtz/quartz, Sp=sphalerite, Ser=sericite.
<caption>Table 2. Summary of microthermometric data of the different types of FIs found in Stage I (a), Stage II (b) and Stage III (c) of the Haftcheshmeh Cu-Mo porphyry deposit.</caption>

a. Stage I

<table><thead><tr><th>FI type</th><th>Number of FI</th><th>Size /µm</th><th>T<sub>m</sub>(CO<sub>2</sub>) /°C</th><th>T<sub>e</sub> /°C</th><th>T<sub>m</sub>(ice) /°C</th><th>T<sub>m</sub>(cla) /°C</th><th>T<sub>h</sub>(CO<sub>2</sub>) /°C</th><th>T<sub>h</sub>(LV-&gt;L) or T<sub>h</sub>(LV-&gt;V) /°C</th><th>T<sub>m</sub>(hal) /°C</th><th>T<sub>m</sub>(syl) /°C</th><th>Salinity /wt% NaCl<sub>eq.</sub></th><th>Density /g.cm<sup>-3</sup></th><th>Pressure /MPa</th></tr></thead><tbody><tr><td>L</td><td>12</td><td></td><td></td><td>-23 to -48</td><td>-4.3 to -9.5</td><td></td><td></td><td>324 to 399</td><td></td><td></td><td>6.8 to 13.4</td><td>0.6 to 0.8</td><td>11 to 27</td></tr><tr><td>V1</td><td>78</td><td>8 to 30</td><td>-56.7 to -56.6</td><td></td><td></td><td>3.2 to 7.3</td><td>11 to 29.2</td><td>410 to 599</td><td></td><td></td><td>5.5 to 12</td><td>0.3 to 0.5</td><td>42 to 92</td></tr><tr><td>V2</td><td>28</td><td>10 to 25</td><td></td><td>-24 to -46</td><td>-2.5 to -7.6</td><td></td><td></td><td>400 to 496</td><td></td><td></td><td>4.1 to 11</td><td>0.2 to 0.6</td><td>27 to 69</td></tr><tr><td>S1</td><td>69</td><td>10 to 30</td><td></td><td></td><td></td><td></td><td></td><td>310 to 466</td><td>398 to 498</td><td>118 to 338</td><td>30.4 to 59.4</td><td>0.9 to 1.3</td><td>35 to 275</td></tr><tr><td>S2</td><td>66</td><td>8 to 30</td><td></td><td></td><td></td><td></td><td></td><td>383 to 569</td><td>302 to 425</td><td>110 to 267</td><td>27.3 to 46.4</td><td>0.4 to 1.0</td><td>12 to 60</td></tr></tbody></table>

b. Stage II

<table><thead><tr><th>FI type</th><th>Number of FI</th><th>Size /µm</th><th>T<sub>m</sub>(CO<sub>2</sub>) /°C</th><th>T<sub>e</sub> /°C</th><th>T<sub>m</sub>(ice) /°C</th><th>T<sub>m</sub>(cla) /°C</th><th>T<sub>h</sub>(CO<sub>2</sub>) /°C</th><th>T<sub>h</sub>(LV-&gt;L) or T<sub>h</sub>(LV-&gt;V) /°C</th><th>T<sub>m</sub>(hal) /°C</th><th>T<sub>m</sub>(syl) /°C</th><th>Salinity /wt% NaCl<sub>eq.</sub></th><th>Density /g.cm<sup>-3</sup></th><th>Pressure /MPa</th></tr></thead><tbody><tr><td>L</td><td>11</td><td>8 to 25</td><td></td><td>-38 to -23</td><td>-4.1 to -6.9</td><td></td><td></td><td>331 to 375</td><td></td><td></td><td>6.5 to 10</td><td>0.7-0.8</td><td>12 to 21</td></tr><tr><td>V1</td><td>87</td><td>8 to 35</td><td>-56.6</td><td></td><td></td><td>2.9-8.9</td><td>11.3-30</td><td>318-500</td><td></td><td></td><td>1.8 to 12.1</td><td>0.3 to 0.5</td><td>21 to 86</td></tr><tr><td>V2</td><td>46</td><td>10 to 30</td><td></td><td>-22 to -40</td><td>-1.2 to -5.8</td><td></td><td></td><td>266 to 464</td><td></td><td></td><td>2 to 8.9</td><td>0.4 to 0.9</td><td>10 to 48</td></tr><tr><td>S1</td><td>41</td><td>8 to 25</td><td></td><td></td><td></td><td></td><td></td><td>282 to 350</td><td>322 to 399</td><td>110 to 317; n=17</td><td>27.2 to 44.8</td><td>0.9 to 1.2</td><td>29 to 108</td></tr><tr><td>S2</td><td>68</td><td>10 to 35</td><td></td><td></td><td></td><td></td><td></td><td>323 to 399</td><td>267 to 365</td><td>116 to 290; n=15</td><td>23.3 to 43.5</td><td>0.3 to 1</td><td>10 to 27</td></tr></tbody></table>

c. Stage III

<table><thead><tr><th>FI type</th><th>Number of FI</th><th>Size /µm</th><th>T<sub>m</sub>(CO<sub>2</sub>) /°C</th><th>T<sub>e</sub> /°C</th><th>T<sub>m</sub>(ice) /°C</th><th>T<sub>m</sub>(cla) /°C</th><th>T<sub>h</sub>(CO<sub>2</sub>) /°C</th><th>T<sub>h</sub>(LV-&gt;L) or T<sub>h</sub>(LV-&gt;V) /°C</th><th>T<sub>m</sub>(hal) /°C</th><th>T<sub>m</sub>(syl) /°C</th><th>Salinity /wt% NaCl<sub>eq.</sub></th><th>Density /g.cm<sup>-3</sup></th><th>Pressure /MPa</th></tr></thead><tbody><tr><td>L</td><td>18</td><td>8 to 20</td><td></td><td>-22 to -30</td><td>-2.3 to -7.8</td><td></td><td></td><td>200 to 316</td><td></td><td></td><td>3.8 to 11</td><td>0.7 to 0.9</td><td>1 to 10</td></tr><tr><td>V1</td><td>27</td><td>8 to 35</td><td></td><td></td><td></td><td>4.9 to 8.9</td><td>23 to 30</td><td>257 to 384</td><td></td><td></td><td>1.8 to 9.8</td><td>0.2 to 0.6</td><td>19 to 60</td></tr><tr><td>V2</td><td>31</td><td>10 to 35</td><td></td><td>-26 to -48</td><td>-1.1 to -3.2</td><td></td><td></td><td>244 to 317</td><td></td><td></td><td>1.8 to 5.1</td><td>0.6 to 0.8</td><td>10 to 3.2</td></tr><tr><td>S1</td><td>8</td><td>10 to 30</td><td></td><td></td><td></td><td></td><td></td><td>260 to 290</td><td>291 to 360</td><td>97 to 199; n=3</td><td>23.9 to 43.1</td><td>0.3 to 1</td><td>7.7 to 120</td></tr><tr><td>S2</td><td>113</td><td>8 to 35</td><td></td><td></td><td></td><td></td><td></td><td>235 to 396</td><td>145 to 279</td><td>82 to 195; n=16</td><td>17.5-36.4</td><td>0.2-0.9</td><td>3-26</td></tr></tbody></table>
Table 3. Cation content in ppm of V- and S-type fluid inclusions from the three mineralization stages of the Haftcheshmeh porphyry deposit as determined by LA-ICPMS. The uncertainties are given below 20% (bold font), between 20 and 50 % (normal font), between 50 and 80 % (italic font), higher than 80 % (italic grey font) and below detection limit (bdl, grey). The analyses are ordered with increasing salinity (wt.% NaCl<sub>eq</sub>) within each stage. The elements are ordered with decreasing concentration to the right. The column FI # reports the inclusion reference number. a. Stage I, b. Stage II and c. Stage III.

a. Stage I

<table><thead><tr><th>FI type</th><th>FI #</th><th>Size / µm</th><th>Salinity / wt% NaCl<sub>eq</sub></th><th>K</th><th>Fe</th><th>Mn</th><th>Cu</th><th>Ti</th><th>Zn</th><th>Mg</th><th>Pb</th><th>Rb</th><th>Sr</th><th>Bi</th><th>Mo</th><th>Ba</th><th>Sn</th><th>Sb</th><th>Cs</th></tr></thead><tbody><tr><td>V2</td><td>37D</td><td>22</td><td>7.3</td><td>26900</td><td>12300</td><td>2710</td><td>50</td><td>840</td><td>880</td><td>360</td><td>372</td><td>137</td><td>16</td><td>4</td><td>bdl</td><td>bdl</td><td>bdl</td><td>bdl</td><td>bdl</td></tr><tr><td>V2</td><td>36.4.1D</td><td>20</td><td>8.6</td><td>18000</td><td>45000</td><td>1170</td><td>4300</td><td>1280</td><td>6300</td><td>900</td><td>140</td><td>46</td><td>120</td><td>38</td><td>bdl</td><td>bdl</td><td>100</td><td>bdl</td><td>bdl</td></tr><tr><td>V1</td><td>36.50L</td><td>28</td><td>9.4</td><td>6500</td><td>6900</td><td>480</td><td>3200</td><td>970</td><td>250</td><td>600</td><td>bdl</td><td>60</td><td>70</td><td>bdl</td><td>bdl</td><td>bdl</td><td>bdl</td><td>bdl</td><td>bdl</td></tr><tr><td>V1</td><td>3.2L</td><td>28</td><td>9.8</td><td>17000</td><td>21800</td><td>3290</td><td>2850</td><td>2800</td><td>1590</td><td>1300</td><td>507</td><td>66</td><td>32</td><td>14</td><td>200</td><td>bdl</td><td>bdl</td><td>bdl</td><td>bdl</td></tr><tr><td>V1</td><td>3.5L</td><td>22</td><td>11.3</td><td>51000</td><td>19000</td><td>2190</td><td>5100</td><td>28000</td><td>11900</td><td>7000</td><td>226</td><td>152</td><td>106</td><td>50</td><td>bdl</td><td>170</td><td>bdl</td><td>34</td><td>bdl</td></tr><tr><td>S2</td><td>12L</td><td>26</td><td>32.3</td><td>81000</td><td>41000</td><td>33000</td><td>44000</td><td>4300</td><td>1600</td><td>120</td><td>3900</td><td>1900</td><td>110</td><td>32</td><td>bdl</td><td>bdl</td><td>1500</td><td>bdl</td><td>50</td></tr><tr><td>S2</td><td>55D</td><td>24</td><td>32.8</td><td>83000</td><td>31000</td><td>2900</td><td>1840</td><td>94000</td><td>13300</td><td>16000</td><td>150</td><td>480</td><td>17</td><td>910</td><td>140</td><td>bdl</td><td>680</td><td>320</td><td>bdl</td></tr><tr><td>S2</td><td>6L.D</td><td>24</td><td>34.1</td><td>20800</td><td>34000</td><td>6800</td><td>4100</td><td>7600</td><td>1800</td><td>5200</td><td>443</td><td>50</td><td>45</td><td>bdl</td><td>bdl</td><td>730</td><td>120</td><td>bdl</td><td>17</td></tr><tr><td>S2</td><td>6L</td><td>26</td><td>38.7</td><td>7800</td><td>11900</td><td>2650</td><td>1890</td><td>550</td><td>650</td><td>300</td><td>295</td><td>bdl</td><td>25</td><td>14</td><td>bdl</td><td>bdl</td><td>55</td><td>50</td><td>bdl</td></tr><tr><td>S2</td><td>2L</td><td>28</td><td>47.1</td><td>45100</td><td>48000</td><td>1470</td><td>1890</td><td>11000</td><td>990</td><td>46000</td><td>198</td><td>243</td><td>49</td><td>41</td><td>bdl</td><td>bdl</td><td>92</td><td>bdl</td><td>bdl</td></tr></tbody></table>

b. Stage II

<table><thead><tr><th>FI type</th><th>FI #</th><th>Size / µm</th><th>Salinity / wt% NaCl<sub>eq</sub></th><th>K</th><th>Fe</th><th>Mn</th><th>Cu</th><th>Ti</th><th>Zn</th><th>Mg</th><th>Pb</th><th>Rb</th><th>Sr</th><th>Bi</th><th>Mo</th><th>Ba</th><th>Sn</th><th>Sb</th><th>Cs</th></tr></thead><tbody><tr><td>V1</td><td>2D</td><td>26</td><td>5.2</td><td>19700</td><td>27500</td><td>5900</td><td>3050</td><td>bdl</td><td>1320</td><td>152</td><td>410</td><td>53</td><td>43</td><td>bdl</td><td>150</td><td>bdl</td><td>bdl</td><td>bdl</td><td>bdl</td></tr><tr><td>V2</td><td>7.20</td><td>30</td><td>5.7</td><td>12400</td><td>12000</td><td>4500</td><td>16900</td><td>6000</td><td>3600</td><td>1300</td><td>350</td><td>150</td><td>90</td><td>bdl</td><td>17</td><td>70</td><td>100</td><td>bdl</td><td>17</td></tr><tr><td>V1</td><td>35D</td><td>28</td><td>7.6</td><td>34500</td><td>35600</td><td>5680</td><td>2190</td><td>15200</td><td>3950</td><td>12700</td><td>515</td><td>127</td><td>65</td><td>26.3</td><td>87</td><td>250</td><td>bdl</td><td>bdl</td><td>bdl</td></tr><tr><td>V2</td><td>73L.D</td><td>24</td><td>8.7</td><td>95600</td><td>30600</td><td>3610</td><td>1760</td><td>2100</td><td>430</td><td>84</td><td>190</td><td>106</td><td>187</td><td>bdl</td><td>bdl</td><td>540</td><td>bdl</td><td>bdl</td><td>bdl</td></tr><tr><td>V1</td><td>46D</td><td>28</td><td>9.8</td><td>24100</td><td>27300</td><td>7900</td><td>7740</td><td>1800</td><td>1170</td><td>900</td><td>840</td><td>260</td><td>30</td><td>bdl</td><td>180</td><td>79</td><td>bdl</td><td>bdl</td><td>bdl</td></tr><tr><td>S2</td><td>36D</td><td>26</td><td>31.0</td><td>103000</td><td>51000</td><td>11100</td><td>3800</td><td>7000</td><td>6100</td><td>3700</td><td>1650</td><td>360</td><td>124</td><td>4</td><td>bdl</td><td>bdl</td><td>250</td><td>90</td><td>bdl</td></tr><tr><td>S2</td><td>32D</td><td>32</td><td>31.0</td><td>86000</td><td>95000</td><td>17100</td><td>38500</td><td>85000</td><td>13100</td><td>15000</td><td>1500</td><td>270</td><td>143</td><td>281</td><td>390</td><td>105</td><td>170</td><td>97</td><td>8</td></tr><tr><td>S2</td><td>33D</td><td>30</td><td>31.2</td><td>101000</td><td>59000</td><td>15000</td><td>27500</td><td>42000</td><td>9600</td><td>19000</td><td>2420</td><td>420</td><td>1230</td><td>109</td><td>1040</td><td>300</td><td>60</td><td>bdl</td><td>15</td></tr><tr><td>S2</td><td>H4.1</td><td>26</td><td>32.9</td><td>69000</td><td>43000</td><td>bdl</td><td>600</td><td>73000</td><td>17900</td><td>5400</td><td>68</td><td>bdl</td><td>42</td><td>280</td><td>350</td><td>80</td><td>180</td><td>110</td><td>bdl</td></tr><tr><td>S2</td><td>34D</td><td>24</td><td>33.3</td><td>236000</td><td>420000</td><td>89000</td><td>8200</td><td>26000</td><td>18900</td><td>3500</td><td>7900</td><td>1640</td><td>207</td><td>109</td><td>190</td><td>910</td><td>180</td><td>bdl</td><td>226</td></tr><tr><td>S2</td><td>96.50.1</td><td>28</td><td>46.0</td><td>31000</td><td>118000</td><td>21900</td><td>2800</td><td>1900</td><td>9600</td><td>2200</td><td>1330</td><td>30</td><td>220</td><td>5</td><td>bdl</td><td>850</td><td>600</td><td>bdl</td><td>120</td></tr></tbody></table>

c. Stage III

<table><thead><tr><th>FI type</th><th>FI #</th><th>Size / µm</th><th>Salinity / wt% NaCl<sub>eq</sub></th><th>K</th><th>Fe</th><th>Mn</th><th>Cu</th><th>Ti</th><th>Zn</th><th>Mg</th><th>Pb</th><th>Rb</th><th>Sr</th><th>Bi</th><th>Mo</th><th>Ba</th><th>Sn</th><th>Sb</th><th>Cs</th></tr></thead><tbody><tr><td>V2</td><td>26D</td><td>28</td><td>5.7</td><td>16500</td><td>16000</td><td>1610</td><td>660</td><td>100000</td><td>3800</td><td>bdl</td><td>167</td><td>bdl</td><td>bdl</td><td>27</td><td>520</td><td>bdl</td><td>bdl</td><td>bdl</td><td>bdl</td></tr><tr><td>V1</td><td>12D</td><td>28</td><td>6.3</td><td>23700</td><td>26000</td><td>4100</td><td>2500</td><td>bdl</td><td>1350</td><td>bdl</td><td>82</td><td>126</td><td>37</td><td>bdl</td><td>bdl</td><td>bdl</td><td>bdl</td><td>bdl</td><td>bdl</td></tr></tbody></table>
<table><tr><td>V2</td><td>18D</td><td>28</td><td>6.5</td><td><strong>15100</strong></td><td>22200</td><td><strong>5890</strong></td><td><strong>1970</strong></td><td>3100</td><td>1140</td><td><strong>1360</strong></td><td><strong>550</strong></td><td>63</td><td>23</td><td>5</td><td>bdl</td><td>bdl</td><td>bdl</td><td>bdl</td><td>bdl</td></tr><tr><td>V2</td><td>42D</td><td>30</td><td>6.8</td><td>29000</td><td>18600</td><td>5200</td><td>730</td><td>1400</td><td>1460</td><td>3800</td><td>1090</td><td>130</td><td>47</td><td>bdl</td><td>bdl</td><td>80</td><td>bdl</td><td>bdl</td><td>bdl</td></tr><tr><td>V2</td><td>4D</td><td>28</td><td>7.9</td><td><strong>23700</strong></td><td>30500</td><td><strong>4600</strong></td><td>6200</td><td>190</td><td>3500</td><td>340</td><td>420</td><td>bdl</td><td>bdl</td><td>8</td><td>1200</td><td>bdl</td><td>bdl</td><td>bdl</td><td>bdl</td></tr><tr><td>S2</td><td>43D</td><td>32</td><td>32.9</td><td>202000</td><td>356000</td><td>72000</td><td>28000</td><td>5300</td><td>22500</td><td>2300</td><td>6800</td><td>1260</td><td>470</td><td>40</td><td>bdl</td><td>540</td><td>bdl</td><td>bdl</td><td>60</td></tr><tr><td>S2</td><td>9D</td><td>32</td><td>34.0</td><td><strong>271000</strong></td><td><strong>291000</strong></td><td><strong>69000</strong></td><td><strong>24900</strong></td><td>80000</td><td>18400</td><td>bdl</td><td><strong>4610</strong></td><td>1020</td><td>390</td><td>25</td><td>bdl</td><td>1600</td><td>bdl</td><td>bdl</td><td>273</td></tr><tr><td>S2</td><td>13D</td><td>26</td><td>35.2</td><td>186000</td><td>295000</td><td><strong>34500</strong></td><td><strong>32900</strong></td><td>bdl</td><td>5300</td><td>3000</td><td>4100</td><td>1030</td><td>310</td><td>35</td><td>96</td><td>250</td><td>bdl</td><td>bdl</td><td>18</td></tr><tr><td>S2</td><td>15D</td><td>28</td><td>35.2</td><td>273000</td><td>283000</td><td>86000</td><td>300</td><td>4400</td><td>25200</td><td>bdl</td><td><strong>4420</strong></td><td>1890</td><td>660</td><td>76</td><td>390</td><td>990</td><td>bdl</td><td>bdl</td><td>75</td></tr><tr><td>S2</td><td>24D</td><td>30</td><td>40.3</td><td>82973</td><td><strong>427000</strong></td><td><strong>93000</strong></td><td>1400</td><td>3600</td><td><strong>21700</strong></td><td>20000</td><td><strong>7700</strong></td><td><strong>2270</strong></td><td>66</td><td>37</td><td>300</td><td>680</td><td>bdl</td><td>bdl</td><td>80</td></tr><tr><td>S2</td><td>5D</td><td>28</td><td>40.3</td><td>80000</td><td>420000</td><td>64000</td><td>20400</td><td>2000</td><td>16000</td><td>2240</td><td>7300</td><td>2700</td><td>109</td><td>33</td><td>840</td><td>bdl</td><td>bdl</td><td>bdl</td><td>100</td></tr><tr><td>S2</td><td>41D</td><td>32</td><td>44.4</td><td><strong>132000</strong></td><td>203000</td><td>22500</td><td>14800</td><td>4000</td><td>8500</td><td>2500</td><td><strong>4690</strong></td><td>880</td><td>163</td><td>55</td><td>bdl</td><td>180</td><td>bdl</td><td>bdl</td><td>34</td></tr></table>