Morphological, thermoelectrical, geochemical and isotopic anatomy of auriferous pyrite from the Bagrote valley placer deposits, North Pakistan: Implications for ore genesis and gold exploration

Accepted Manuscript Morphological, thermoelectrical, geochemical and isotopic anatomy of auriferous pyrite from the Bagrote Valley placer deposits, North Pakistan: implications for ore genesis and gold exploration Masroor Alam, Sheng-Rong Li, M. Santosh, Attaullah Shah, Mao-Wen Yuan, Hawas Khan, Javed Akhtar, Yong-Jie Zeng PII: DOI: Article Number: Reference:

S0169-1368(18)30702-9 https://doi.org/10.1016/j.oregeorev.2019.103008 103008 OREGEO 103008

To appear in:

Ore Geology Reviews

Received Date: Revised Date: Accepted Date:

17 August 2018 2 July 2019 8 July 2019

Please cite this article as: M. Alam, S-R. Li, M. Santosh, A. Shah, M-W. Yuan, H. Khan, J. Akhtar, Y-J. Zeng, Morphological, thermoelectrical, geochemical and isotopic anatomy of auriferous pyrite from the Bagrote Valley placer deposits, North Pakistan: implications for ore genesis and gold exploration, Ore Geology Reviews (2019), doi: https://doi.org/10.1016/j.oregeorev.2019.103008

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Morphological, thermoelectrical, geochemical and isotopic anatomy of auriferous pyrite from the Bagrote Valley placer deposits, North Pakistan: implications for ore genesis and gold exploration

Masroor Alama,b Sheng-Rong Lib,c*, M. Santoshc,d, Attaullah Shaha, Mao-Wen Yuanb,c , Hawas Khana, Javed Akhtara, Yong-Jie Zengb,c

a

Karakoram International University, Gilgit 15100, Pakistan

b

State Key Laboratory of Geological Processes and Mineral Resources, China University of

Geosciences, Beijing 100083, China

c

School of Earth Science and Resources, China University of Geosciences, Beijing 100083,

China

d

Department of Earth Sciences, University of Adelaide, SA 5005, Australia

*Corresponding author address: State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Beijing 100083, China. E-mail address: [email protected] (S.-R. Li).

Abstract The Bagrote valley in North Pakistan, belonging to the Kohistan island arc, is well-known for regional placer gold mining. However, no economically feasible in situ hydrothermal gold deposits have been discovered in this region due to rugged terrain and remote nature of its location in the western Himalaya. The streams draining the Main Karakoram Thrust (MKT)/Shyoke suture zone carry placer gold in sediments as well as old river terraces, although the primary source remains unknown. In this paper, we employ a multiparametric approach including, X-ray Diffraction (XRD) analysis, thermoelectricity, major and trace element geochemistry and isotopic characteristics of pyrite associated with placer gold with a view to identify the nature of the unknown deposits and ore forming fluids on the catchment of the Bagrote valley. Pyrite in the Bagrote valley placers is euhedral to subhedral indicating the proximal gold sources. The high rate of occurrence of N-type thermoelectric coefficients (89%) with low P-type (11%) and crystallization temperature (290°C - 380 °C) combined with chemical features indicate that the pyrite was derived from porphyry or epithermal type of magmatic hydrothermal gold deposits from the hinterlands of the Bagrote valley. The X-Ray elemental maps show that Fe, As, Mo and Ni are homogenously distributed from core to rim suggesting stable crystallization condition without any alteration by later fluids. The calculated chemical formula of pyrite of our samples is [Au0.0006Fe] S2.004], plots of Au-As and Au-Fe shows that gold occurs in pyrite as micro to nano inclusion as Au0. The δ34 SV-CDT values of pyrite range from – 0.6‰ to 0.9‰ with an average of -0.02‰, indicating the derivation of sulfur from a

homogeneous magmatic source. The Pb isotope data indicates that the Pb was sourced from orogenic-type source, with minor contribution of lower crust. The narrow variations in 206

Pb/204Pb and 208Pb/204Pb values suggest a single lead source. The low, medium and high

Mo/Ni ratios reflect a mixed provenance for the auriferous pyrite. The average value of γ (71.8%), of pyrite computed from thermoelectric parameters (XnP), suggests that the dominant part of the primary source that contributes to the placers might have already been eroded. However, the proximal source and with high content of gold in the pyrite grains (up to 1160 ppm) suggest the possibility of significant economic mineralisation below the present erosion level of the deposits in the hinterlands of Bagrote Valley.

Key words: Detrital Pyrite; thermoelectric coefficient; S-Pb isotopes; trace elements; North Pakistan 1. Introduction Pyrite, as one of the most common constituents of ore bearing mineral assemblages, and as an important gold bearing mineral, has been employed as a potential tracer for ore genesis (Murowchick & Barnes, 1987; Maddox et al., 1998; Abraitis et al., 2004; Prolledesma et. al., 2010; Yan et. al., 2014; Gao et. al., 2017). The mineral accounts for 85% of the major gold-bearing minerals in gold deposits (Gao et al., 2000; Palenov et. al., 2015). The characteristics of pyrite including morphology (Abraitis et al., 2004; Kolgin et. al., 2010), chemical composition (Li et al., 1994, 1996; Abraitis et al., 2004; Reich et al., 2005; Cook et al., 2009a; Yan et al., 2012, 2013), thermoelectricity (Li et al., 1994, 1996, 2013; Abraitis et al., 2004; Cao et al., 2008; Chen et al., 2010, Wang et. al., 2016) and stable isotopes (Yan et al.,2014; Zhang et al., 2014; Gao et. al., 2017; Li and Santosh, 2017; Li et. et al., 2018) have been employed to understand the genesis of gold

deposits. Moreover, it can serve as a geochemical tracer in a wide variety of ore systems, such as porphyry Cu deposits (e.g. Reich et al., 2013), volcanic-massive sulfide deposits (Belousov et al., 2016), Carlin-type gold deposits (e.g. Barker et al., 2009; Muntean et al., 2011), orogenic gold deposits (e.g. Hazarika et al., 2017; Augstin and Gaboury, 2018), etc. The preservation of pyrite on the surface of earth is a factor of hydrospheric, atmospheric, and pedospheric conditions and mechanical stability (Rickard, 2012), and pyrite can be formed in various Earth surface environments, as it exhibits extensive stability over pH=2-10. Pyrite shows stability even in more oxic environments, above the boundary between oxic and anoxic (or suboxic) systems, which is usually taken to be where {SO4-2} ={S(-II) (Rickard, 2012). Another factor conductive to

the pyrite preservation is its resistive behaviour to mechanical abrasion. The cleavage of pyrite, along {100} is poor and imperfect; thus, it shows conchoidal fracture when breaks (Tauson et al., 2015).

Combined with a hardness of 6.5, we assume that pyrite can be transported for long distances before deposition. For example, the pyrites in the Southland placers of New Zealand, are formed in a diagenetic environment and can survive erosion and transportation in streams and be reburied in

younger sediments (Youngson et al., 2006). According to Craw et al. (2003), pyrite can be transported for tens of kilometers in fluvial systems. The abundance of pyrite in pre-2.4Ga sedimentary deposits indicate that it may remain stable during burial diagenesis unless attacked by influx of oxidizing fluids, and even high-grade metamorphic conditions are not enough to destroy the evidence of the origin and history of pyrite grains, as, for example, evidenced from the retention of crystal shape, mineral inclusions, early fabrics, or chemical zoning (Craig and Vokes, 1998).

The study of detrital pyrite may include morphology and grain size, nature of inclusions, texture, chemical composition (Da Costa et al., 2017), isotopic composition, and a wide range of

analytical techniques can be used. Mineral-geochemical and conventional petrographic methods employing petrographic reflected light microscope, scanning electron microscope (SEM), and electron probe micro analyzer (EPMA) are combined to various mass spectrometric methods that facilitated bulk or in situ analysis of the geochemical and isotopic composition of pyrite. The thermoelectric characteristics of the detrital pyrite can make important constrains about the temperature of pyrite formation and the erosion or denudation rate of the source deposits contributing placer gold. Recently multiple techniques have been developed to better understand the origin of pyrite (detrital, authigenic) and the environmental conditions under which it formed in sedimentary rocks, which helped to understand not only the geological past, but to also the mechanisms of formation of ore deposits associated with it (Da Costa et al., 2017). Also, in the areas such as north Pakistan/Western Himalaya, which is poorly explored and characterized by very rugged, glaciated and inaccessible terrane, i.e. Karakoram, Hindukush and greater Himalayan ranges, is absolutely lack of information on the ore genesis of the gold deposits found in this area of the globe. Thus, we think that the detrital pyrite which is ubiquitous and abundant sulfide in the placer deposits of the Bagrote valley can be effectively used for a unique set of analysis (see section 3) to get maximum information on the gold deposits found in these inaccessible, poorly explored rugged terrains of the north Pakistan. North Pakistan is characterized by a wide network of rivers and streams flowing from the high glaciated hinterlands of the northwest Himalaya. Gold washing from the rivers beds is carried out since long by using primitive techniques and by locals. Some mining companies conducted large

scale mining in the Indus river and its tributaries draining Kohistan Island arc and Karakorum Block of North Pakistan (Alam et al., 2018). Previous studies on placer deposits of these rivers mainly focused on the mineralogy of stream sediments. (Ivanac et al., 1956; Ahmad et al., 1975; Tahirkheili, 1974). Various international organizations have conducted a number of mineral exploration activities in northern Pakistan over the last a couple of decades. In the North Pakistan, Austromineral of Vienna (1976,1978) carried out exploration activities and prepared geological maps and also performed local mapping of mineral prospects, trenching, as well as geochemical prospecting. The Gold Exploration and Mineral Analysis Project (GEMAP) was the most extensive and large-scale exploration activity carried out under the Australian Aid for International Development (1992 & 1995). GEMAP focused on Gold and associated minerals in the Gilgit Baltistan, Pakistan, with more than 1430 drainage samples, covering an area of 80,000 km2 (Clavarino et al., 1994). The programme includes collection of a large number of panned concentrate and stream sediments samples from about 4260 sites in North Pakistan predominantly focusing on Au, and six prospect areas were identified for further exploration, and our study area (Bagrote valley) is one of these. The high amount of placer gold occurrence in the rivers and the streams of North Pakistan attracted greater interest to explore the source deposits, and their nature and processes involved for the mineralisation. Ali (2011) and Alam et. al, (2018) studied the morphology and chemistry of placer gold grains and concentration of heavy minerals from different anomalous sites to describe the proximity to bed rock source (<10km) and the possible types of source mineralization in the hinterlands (Ali, et al., 2014). In many areas of north Pakistan, the hydrothermally altered sulfide shear zones indicate the possibility of the occurrences of source rocks for gold (Miandad et al., 2014; Sheikh et al., 2014; Rahman et al., 2015).

In the Bagrote valley, gold mineralisation occurs in hydrothermally altered quartz bearing sulfide shear zones of variable thickness (< 1 m to > 10 m) and length (< 10 m to > 100 m) in the Chirah and Bulchi area (fig.1c) which contain Au ranges from <0.05-0.161 ppm with an average value of 0.083 ppm, but it is considered to be not economically feasible to contribute such an amount of placer gold, as in the same valley, 2.70g Au was obtained by panning a weight of 893.86 kg sediments (Shah & Khan, 2004) and also the river is not draining these veins and gold placers are also found upstream from the location of the known mineralisation, therefore, other unknown gold deposits must found on the catchment of the valleys responsible to contribute the placer deposits, also as mentioned above, there is absolutely lack of information about the ore genesis of the deposits found on the hinterlands contributing palcer gold In this contribution, based on local and regional geological and tectonic framework and a multiparametric approach on pyrite including XRD analysis, thermoelectricity, major and trace element geochemistry, EPMA X-ray elemental maps and isotopic characteristics, we attempt to constrain the nature of deposits, mechanism of gold enrichment in pyrite, source of ore forming fluids and metals, source lithology and denudation or erosion rate of the deposits in the hinterlands contributing placer gold in the Bagrote valley in the Kohistan island arc of North Pakistan. 2.

Geology and metallogeny of North Pakistan Geologically, North Pakistan is composed of three major blocks within the tectonic

framework of the Himalaya. These terranes, from north to south, consist of: (1) the Karakoram Block, (2) the Kohistan–Ladakh Arc (KLA), and (3) the Indian Plate rocks. These terrains in the north Pakistan are separated by the Main Karakoram Thrust (MKT)/Shyok Suture Zone and Main Mantle Thrust (MMT)/Indus Suture Zone (Fig.1b) (Fraser et al., 2001; Zanchi and Gaetani, 2011,

Searle et al., 2016). Along the Indus suture zone, the Indian Plate is subducted under the Asian Plate, (Fig.1a) but the timing of collision between the two plates is still debated (Tahirkheli, 1979; Bignold and Treloar, 2003; Ziabrev et al., 2004; Chatterjee et al., 2013). The geology of the north Pakistan cab be described by the following tectonic terrains.

2.1 Karakoram Block The Karakoram Block forms the southern margin of Asian Plate and is located to the west of southern Tibet, separated from the southern Tibet by the Karakorum Fault (Fig. 1a). From north to south, the Karakoram Block is composed of three segments (Fig.1b): the Northern Karakoram terrane also called northern sedimentary belt (NSB) (Zanchi and Gaetani, 1994), the Cretaceous– Miocene Karakoram axial batholith (locally called Hunza plutonic unit (HPU) (Debon et al., 1987; Parrish & Tirrul, 1989) and the Karakoram Metamorphic Complex (Fig.1b), which is a NWtrending metamorphic belt with Precambrian basement related to the collision of Kohistan Ladakh island arc with the Karakorum Block and the Indian Plate (Fraser et al., 2001). North Karakoram is mainly composed of Permian to Early Cretaceous sedimentary rocks, representing deposition at a passive margin associated with the opening of the Tethys Ocean (Gaetani et al., 1993). The northern sedimentary belt is dominantly consist of the Permian massive lime stone, Triassic massive lime stone/dolomite, Carboniferous black slates and cretaceous sandstone (Fig. 1b) (Kazmi and Jan, 1997). The southern Karakorum metamorphic complex is mainly composed of interlayered kyaniteor sillimanite-grade pelites with garnet + clinopyroxene amphibolites, impure dolomitic marbles

containing diopside, phlogopite, quartz and corundum (ruby), and amphibolites hosting plagioclase, hornblende, biotite and garnet. (Searle et al., 1989; Rolland et al., 2001). 2.2 The Main Karakoram Thrust (MKT) The Main Karakoram Thrust or Shyoke Suture Zone (MKT/SSZ) of North Pakistan is an important Cretaceous-Tertiary suture separating the cretaceous Kohistan island arc from Asian continent (Karakorum Block to the north) (Fig.1b). In previous literature, the Shyok Suture Zone/MKT indicates either the subduction site of Tethyan Ocean or represents an Early Cretaceous intra-continental marginal basin along the southern margin of Asia (Coward et al., 1986; Robertson & Collins, 2002) and forms the southern boundary of the Karakorum Block (Searle et al., 1989; Seong et al., 2008). The SSZ/MKT is generally composed of ophiolites, tectonic mélanges, olistostromes, slates, sandstones, conglomerates, limestone, red shales serpentinites, blocks of volcanic greenstone and mafic-ultramafic fragments in a matrix of chloritized slates (Kazmi and Jan, 1997). 2.3 Kohistan Island Arc According to Shah et al. (2011), rocks of the Kohistan arc were formed in response to intraoceanic subduction (Fig.1b) and are dominantly represented by volcanic and sedimentary suites within the Andean-type plate margin and carrying a number of granitic intrusions (Petterson, 2010). The Kohistan island arc contains volcano sedimentary units which include the Chalt Volcanics, Shamran Volcanics and Yasin Group sediments (Fig.1b). Petterson, (2010) reported that the Yasin Group sediments override the Chalt Volcanics Group which are composed of boninites, basaltic andesites, and tholeiitic meta basalts (Petterson and Windley, 1991; Khan et al., 1998; Petterson and Treloar, 2004). The Kohistan batholith is mainly formed of plutons, dykes, plugs, and sheets of gabbros, diorites, hornblendites, granodiorites, quartz diorites, tonalities,

adamellites, granites, aplites, trondhjemites and pegmatites (Kazmi and Jan, 1997), whereas the Shamaran/Teru Volcanic Group, with a thickness of 3 km comprises undeformed and metamorphosed volcanic rocks (Searle et al., 1999; Petterson 2010) (Fig.1b). 2.4 Indus Suture Zone/MMT The Indus Suture Zone also called as Main Mantel Thrust (MMT), which marks the southern boundary of the Kohistan Arc, and is developed as a consequent of the oceanic lithosphere subduction (closure of the Tethyan ocean) beneath the Kohistan island arc (Rowley, 1996; Anczkiewicz et al., 1998). It is formed of tectonic mélanges containing plutonic, volcanic and sedimentary rocks of oceanic crust, island arc and mid-oceanic origin (Kazmi and Jan, 1997).

2.4 Indian Plate rocks Around 50Ma ago, the Kohistan-Ladakh arc was obducted on to the Indian Plate along the Main Mantel Thrust/MMT (Tahirkheli and Jan, 1979), which is the western extension of the Indus–Tsangpo Suture Zone (Fig.1a). Towards south of the Kohistan Ladakh arc, the Proterozoic Indian Plate crust consumed to form the Nanga Parbat–Haramosh Massif (Treloar and Rex, 1990). The crust of the Indian Plate underwent fast exhumation associated with synchronous metamorphism and anatexis during the period of 12 Ma to 0.7Ma in North Pakistan (Zeitler, 1985; Crowley et al., 2009). The dominant lithologies in the north Pakistan are schist, Cambrian granitic rocks, gneiss of the late Cambrian and early Proterozoic age (Treloar et al., 1989b). 2.5 Geology of the Bagrote valley The Bagrote valley (Fig. 1c) is a hanging U-shaped valley which mainly shares rocks of the Cretaceous Chalt Volcanics (CV), and Gilgit metamorphic complex lie on downstream area.

Haramosh gneiss and northern part of Kohistan batholith also extends to the hinterlands of the Bagrote valley but the Bagrote River is mainly draining the Chalt Volcanics (Fig.1c). The MKT passes along the hinterlands of the valley from NE to SW separating the Kohistan island arc from Karakorum Block. The Chalt Volcanics (CV) is mainly composed of pillowed and unpillowed boninites, basalt to andesite lavas with minor rhyolites, thin ignimbrites, primary and reworked volcanoclastic units and minor intrusive rocks (Petterson et al.,1991b; Petterson & Treloar, 2004). Chalt Volcanics (CV) (Fig. 1c) are mainly calcalkaline (Petterson and Windley, 1991) and show a range in Mg contents from high- Mg (9–15 wt.%) basalts and andesites to Low-Mg basalts, andesites and minor rhyolites (Bignold et al.,2006) which are enriched in low field strength elements (e.g. Rb, Ba, Sr, K and LREE (e.g. Ce) relative to high field strength elements and HREE (e.g. Zr, Ti, Y). All the rocks of Chalt Volcanics regardless of their composition display a subduction related signature, most notably, a negative Nb anomaly which is compatible with an island arc tectonic setting and the northward subduction of Tethys produced Chalt Volcanics. (Petterson et al., 1991b). These rocks covered much of the hinterlands of the Bagrot valley (Fig. 1c) where the terraces of glacio-fluvial and fluvial sediments containing placer gold are found on both sides of the river. In the Bagrote valley, the rocks of the CV are mainly greenish-gray on fresh surface and yellowish brown on weathered surface. The gray to green colored steeply dipping volcanic sheets, mainly basalt or basaltic-andesite in character, with intercalations of meta-rhyolite, meta-tuffs, and meta-graywacke are exposed on the hinterlands of Bagrote valley. Petrographically, the rocks of the CV are fine-grained, foliated and display both porphyritic and non-porphyritic character (Miandad et al., 2014).

In the east and western side of the Bagrote valley, the gabbroic-diorites of to the Kohistan batholiths are exposed having intrusive contact with the rocks of the Chalt Volcanics (Fig. 1c). These rocks, on the fresh surface, generally show gray to dark-gray color and display yellowishbrown color on the weather surface as a result of leaching of sulfides. Plagioclase, hornblende, biotite and epidote can be clearly recognized in hand specimen with disseminated pyrite grains. The leaching of pyrites and staining of yellowish-brown color on the weathered surface is very common. Relatively dark colored gabbroic-diorites show high content of hornblende and micaceous minerals (mainly biotite). In the host rocks along these veins, the leaching of sulfides and intrusion of quartz veins and alteration (epidotization) are common (Miandad et al., 2014). 2.6 Gold Metallogeny in North Pakistan According to Searle et al. (2016), in island arc environments, mineralization is mainly found as VMS-type deposits, and Cu-Zn-Pb ± Au-Ag deposits. The Kohistan arc contains some signatures of massive sulfide mineralization but none of these has been proven to be economically feasible, and erosion may also have destroyed the bigger deposits. In particular, the Himalayan arc systems have witnessed regional Barrovian metamorphism and extreme structural shortening, which enhanced the uplift and erosion of higher levels of the arc system. (Searle at al., 2016). Very few know areas of mineralization in the north Pakistan were reported in hydrothermally altered quartz bearing sulfide shear zones in the Kohistan island arc which are found in the Ghizer area (Sheikh et al., 2014), Nomal and Juglote area (Kausar, 1991) Skardu area (Rehman et al., 2015) and in the Bagrote valley (Miandad et al., 2014) etc. 3. Sampling and analytical techniques

Sampling for this study was carried out on the sediments (sand, gravel, cobble and boulder), deposited adjacent to the bends and meanders along the course of the Bagrote river in Kohistan island arc, Gilgit Baltistan Pakistan. Pyrite along with heavy minerals were collected by panning of sediments from 12 locations of the alluvial deposits (Fig.1c). Pyrite grains were separated by hand-picking under a binocular microscope, and their morphology was examined. The specifications of the samples are shown in Table 1. 3.1 Powder XRD analysis XRD analysis was carried out on 3 representative samples. One sample was selected from downstream area and another selected from comparatively upstream and the third sample was selected from the top upstream area of the valley. Pyrite grains were powdered by and grinding in an agate mil. Powder XRD analysis was carried out by XRD apparatus hosted in China university of geoscience Beijing. XRD peaks were analysed by Xpert High Score Plus software to determine crystal habit. 3.2 Thermoelectricity analysis Thermoelectricity coefficients of 1189 pyrite grains of different shapes and morphologies, selected from 12 samples of different localities were analysed. The size of each was larger than 0.17mm. Initially the pyrite grains were cleaned ultrasonically in alcohol and then separated by handpicking to a purity of greater than 99% under binocular microscope. Thermoelectricity of pyrite was analysed by the BHTE-06 thermoelectricity coefficient apparatus (manufactured by Beijing University of Aeronautics and Astronautics) at Mineral Typomorphism Laboratory in China University of Geosciences (Beijing China). The temperature of the freezing end and hot end

were set to 21 °C and 68 ± 3°C (Niu et al., 2015) respectively and the analytical results are shown in Table 2. 3.3 EPMA Analysis and EPMA X-Ray elemental maps The chemistry (major and minor element composition) of the pyrite was determined at the Chinese Academy of Geological Sciences, by a JXA-8230 electron microprobe. Operating parameters were set to produce 20 kV accelerating voltage, a beam current of 20 nA, and the beam diameter of 5 µm. Standard substances refer to GB/T 15074-2008 general rules for EPMA analysis. EPMA data for analyzed pyrite grains are listed in Table 3. Since there was no zonation observed in BSE images of pyrite grains, therefore, only one spot was analysed in each grain of different morphologies selected from 12 samples. EPMA X-Ray elemental maps of selected elements (As, Co, Ni, Mo, Fe, Te, Au and Ag) were obtained at the Chinese Academy of Geological Sciences using a Camaca SX100 electron microprobe equipped with a 4 WDS detector with operating conditions set to 20 kV acceleration, 80 nA beam current and 250-300ms dwell time per spot. The elements As, Co, Ni, Mo, Fe, Te, Au and Ag were analyzed by employing wavelength dispersive spectroscopy (WDS). The size of elemental map is up to 256×256 pixels, with 1-2 μm steps (distance between analysis spots, or spatial definition). 3.4 Sulfur and lead Isotope analysis 6 samples of pyrite were analysed for sulfur and lead isotope from different location from downstream to upstream. The sulfur isotopic composition of pyrite was analysed on a Delta v plus stable isotope mass spectrometer hosted in China academy of geological sciences Beijing

following the procedure proposed by (Glesemann et al.,1994). The results are expressed in δ34SVCDT with an analytical precision of ± 0.2‰, relative to the standard of Vienna Canon Diablo Troilite

(V-CDT) sulfide with δ34S= 0.0‰ by definition. The analytical results of the sulfur isotope are shown in Table 6. The Pb isotopic composition was measured by a Neptune II Multi Collector-Inductively Coupled Plasma Mass Spectrometer (MC-ICP-MS) at China Academy of geological sciences Beijing, China following the procedures described in Zhao et al. (2007). The analytical results are shown in the Table 6. 4. Results 4.1 Morphology of pyrite Different morphologies of pyrite grains are found in the alluvial deposits of the Bagrote valley. Euhedral morphologies (Figs. 2e, 2f) are dominant and secondary euhedral to subhedral pyrite is also present (Figs.2g). Rounded pyrite is also found occasionally which looks similar to the compact rounded pyrite in Witwatersrand gold bearing conglomerates reported by Fleet, (1998) (Fig.2i). All pyrite types contain different mineral inclusion like epidote, titanite, silicate minerals and chalcopyrite, hematite etc. (Figs. 2a, 2b, 2c, 2d), although, cubic pyrite contains rare inclusion of other minerals (Fig.2a). The euhedral pyrite commonly has a striated cubic structure and is smaller in size (Fig.2e) as compared to anhedral (Fig.2h) and subhedral to euhedral types (Figs.2g), although some larger size grains were also found. Some small sized cubes without striations are also observed. The grain size of the pyrite in these alluvial deposit ranges to 50um to 5mm.The large and smaller sized

pyrite grains may have been transported with gravely and silt fraction load respectively (Kolgin et al., 2010). The rounded shapes (Figs.2iand truncated structures (Fig.2e) of the pyrite grains show slightly long distance of transport, but they are very rarein the placer deposit of the Bagrote valley.. 4.2 Crystal habit The shapes of the crystals of minerals are governed by chemical compositions, inner structure, and geological environment, and they can be used to trace back the occurrence history, growth and crystal transformation (Shao, 1988). A cubic crystal {100} indicates low sulfur concentration in the mineralizing fluid and also indicative of low or high temperature environment, whereas a pentagonal dodecahedron {210} reflects high sulfur concentration and forms under moderate temperature (Li et al., 2013). When the vertical face or crystal grow faster than the horizontal one, it results development of {210} or {210+100}, whereas the octahedron 111 forms between the crystallization environment of cube {100} and the pentagonal dodecahedron {210} and always develop the combined forms of {111}, {210} or {100}. Slow cooling, abundant material sources, high supersaturation, and high fugacity of sulfur result in more complex crystal forms (Murowchick et al., 1987; Hu, 2001; Chen et al., 1989; Li et al., 1994; Li et al., 2013).

Analyzing the XRD peaks (Fig.3) by Xpert High Score Plus software and combined with observing pyrite grains under binocular microscope it was noticed that grains have complex crystal habit including {-1 1 1}, {1 0 0}, {2 0 0}, {-1 0 2}, {-2 1 1}, {0 -2 2}, {-1-1 3}, {2 -2 2}, {0 -2 3}, {-1 -2 3} and some of their combinations were also identified. Pyritohedrons are commonly found following diploid and cube. In combinations forms {100+210}, (210+111) are commonly identified in binocular microscope although some complex combination forms are difficult to identify.

4.3 Thermoelectricity Pyrite, as a semiconducting mineral with a band gap of 0.95 eV, commonly exhibits both N-type (electron conduction) and P-type (hole conduction) semiconductivity (Pridmore & Shuey, 1976; Schieck et al., 1990; Li et al., 1994, 1996; Abraitis et al., 2004). Under varying temperature conditions, the non-equilibrium carriers in a semiconductor diffuse from the zones of hightemperature to the zones of low temperature, as a result, a thermal electromotive force (E) is generated. This thermoelectric phenomenon, known as the Seebeck effect, is strongly influenced by the chemical composition of the semiconductor. The thermoelectric coefficient (α) of a semiconductor like pyrite can be defined as (Shao et al.,1990):

α = ±E/tH − tC [ ±μv°C]

where tH represents the hot-end temperature and tC denotes the cold end temperature. The negative and positive sign of E is correlated with the negative and positive characteristics of the carriers with a certain conduction type (Shao et al., 1990). The values of the thermoelectric coefficient (α) and the conduction type of pyrite are influenced by isomorphous impurities in the composition of pyrite, defects in crystal structure, density, and external excitation conditions (e.g., temperature and pressure gradients). Because these factors are influenced by conditions at the depth of ore formation, it follows that pyrite thermoelectricity can be used as an indicator of the depth of the ore-forming processes (Abraitis et al., 2004; Shen et al., 2013; Zhang, 2010). The measured thermoelectric coefficients of pyrite of the placer deposits of the Bagrote valley ranges from -317 µV/℃ to 303 µV/℃ and the occurrence rate of P-type is 11%, displaying weak peaks while N-type occurrence rate is 89% showing high peaks at -150 to -50 µV/℃ (Fig. 4a). The

parameters of analysis of 1189 pyrite grains from placer deposits of Bagrote valley placer gold deposits are listed in Table 2. 4.3.1 Temperature calculation using thermoelectric coefficient During ore formation, pyrite thermoelectricity and conduction types changes depending on different temperatures. At high temperatures, the conduction type is mostly N-type, at moderate temperature, more-or-less equal proportions of P and N-types while at low temperature P-type dominates (Chen et al., 1989, Wang et. al., 2016). This supports the observation that N-type pyrites tend to be prevalent at deeper levels while P-type pyrites tend to be formed at shallower levels. Therefore, it appears that crystallization temperature is relevant to pyrite thermoelectricity. The relationships between thermoelectricity and temperature have been defined by equations derived from experimental data as (Zhang, 2010; Xue et al., 2014; Wang et. al., 2016): T (°C) = (704.51-α)/1.818 (N-type), T (°C) = 3(122.22+α)/5.0 (P-type). Our data of pyrite thermoelectric coefficient values were incorporated in the above equations and the crystallization temperatures of pyrites in the Bagrote valley placers are estimated to be between 78°C and 387.5°C. The N type pyrites were formed in the temperature range of 319.1– 387.5 °C and P-type pyrites formed in the range of 78–186.4 °C (Table 2). The histogram of pyrite thermoelectric coefficient–temperatures from the Bagrote valley placers (Fig.4b) shows that the formation temperatures range from 80 °C and 395 °C and are mainly concentrated between 290 °C and 380 °C, suggesting medium to high temperatures for pyrite formation in the deposits found in the hinterlands of the Bagrote valley.

4.3.2 Thermoelectric parameter of pyrite The pyrite thermoelectric parameter (XnP) can be calculated based on the thermoelectric coefficient (Yang and Zhang, 1991; Yang and Meng, 1991; Shen et al., 2013; Xue et al., 2014; Wang et al., 2016), thus: XnP=(2fⅠ+fⅡ) -(fⅣ+2fⅤ),

Here, f denotes the levels of thermoelectric coefficients of pyrite in the measured samples: fⅠ is number of the values of thermoelectric coefficient (α)> 400 μV/°C, f Ⅱ is thermoelectric coefficient (α) in the range 200 – 400 μV/°C, fⅣ is α in the range 0 – -200 μV/°C, while fⅤ denotes the value of α < −200 μV/°C. The values of XnP of pyrites in the Bagrote valley placer deposits vary from −105 to -82 (Table 2), the XnP values have been employed to estimate the erosional or exhumation level (γ) of gold deposits as γ = 50 – XnP/4 (Yang and Meng, 1991; Xue et al., 2014, Wang et al., 2016). The XnP values and corresponding γ values from pyrites (Table 2) suggest that the deposits found on the hinterland of Bagrote valley have been significantly been eroded. For example, XnP values of pyrites vary from −105 to −82 with a mean of −90.7 (Table 2) suggesting that the orebody on the catchment of the valley likely represents the lower part of the deposits (Wang et al., 2016). More ever, values of γ of pyrite computed from thermoelectric parameters (γ = 50 – XnP/4) vary from 66.3% to 73.5%, with a mean of 71.8%, suggesting that the dominant part of the source deposits contributing placers have already been eroded (Wang et al., 2016). According to Searle et al., (2016), erosion may also have destroyed bigger deposits in the Karakorum block and Kohistan island arc of north Pakistan. However, the morphology (Fig.2) (euhedral to subhedral)

of pyrite indicating proximal distance to source and combined with high content of gold in EPMA analysis (up to 1160 ppm) (Table 3) suggests significant economic mineralization may like occur beneath the present level of erosion of the deposits found on the hinterlands. 4.4 Major and trace element compositions of pyrite Co, Mo and As are the abundant trace elements found in the auriferous pyrite of the Bagrote stream placers with range from 0.07wt% to 1.804wt%, 0.059wt% to 0.064% and 0.008wt% to 0.4175% respectively. Mo and Co are above detection limit in all analysed grains but As is below detection limit in 3 grains out of 19 analysed grains. Ni is above detection limit in 9 grains ranging from 0.001 to 0.47wt%. Other trace elements like Zn, Pb, Cd are below detection limit in most of the grains (Table 3). The content of major elements Fe and S in Pyrite ranges from 43.625 to 46.62 with a mean of 46.048 and from 52.376 to 53.373 with an average of 53.027l respectively. The analysed Fe and S contents of pyrite when compared with the standard value (Fe=46.55wt%, S=53.45wt %), show that most of the grains have low content of Fe and S as compared to their standard value. Only three grains show higher Fe content and two grains show higher S content than the standard value (Table 4). According to Wang et al. (2016), the S/Fe molar ratios of pyrite in gold deposits are complicated due to presence of different trace elements such as Ni and Co, which isomorphously substitute Fe, and As, Se, and Te, which in turn can isomorphously replace S. These isomorphous substitutions of trace elements can lead to the distribution of gold in the crystal lattice of pyrite and enhance the Au-bearing capacity of pyrite. A molar S/Fe ratio of <2 is attributed to sulfur loss, >2 to iron loss (Doyle and Mirza, 1996). The computed S/Fe molar ratios of the different pyrite grains are about 2, ranging from 1.95 to 2.07 (Table 4). The S/Fe ratios of 14 out of the 19 analysed

pyrite grains are higher than 2 (Fe loss), indicating that most of the pyrite grains are sulfur-rich. Chen et al. (1989) studied 36 deposits in Jiaodong Peninsula, China and concluded that epithermal or sedimentary pyrite are visibly lack of Fe. 4.4.1 Element distribution in pyrite On the basis of EPMA data, a representative pyrite grain was selected for elemental mapping to evaluate trace element distribution and zoning. Eight elements, i.e. Au, As, Ag, Ni, Co, Mo, Fe and Te, were analyzed (Fig.5) some of these show discrete quantitative distribution characteristics and others show homogenous distribution. The Te, As and Co are concentrated on the lower rim without any relation to Au (Fig.5). The other elements including gold has a smooth distribution on the domain of the pyrite grain. It appears that there is no major change in crystallization condition and material source because the Fe content has an even and homogeneous distribution form core to rim of the analysed grain (Yuan et al., 2017). The Ni, Ag, Mo and Au shows homogenous distribution pattern. In contrast the distribution of Co is uneven on the domain of the analysed grain as the colors show that it is relatively enriched on the lower rim. The EPMA analysis of this grain shows 1160ppm Au on the core of the grain (Fig.5). 4.5 Isotopic composition of pyrite 4.5.1 Sulfur isotopic composition of pyrite The sulfur isotopic composition of 6 pyrite samples is shown in Table 6. The δ34 SV-CDT values of pyrite from Bagrote valley placer deposits range from – 0.6 to 0.9 with a mean of -0.02, showing a fairly narrow range of composition. The sulfur isotopic composition of our pyrite samples partially overlaps with that of volcanic SO2 and arc basalt and andesite and is also within the range

of granitic rocks and meteorite (Fig.8). The δ34S data of pyrite from placer gold deposits of Bagrote valley are mainly concentrated between -1‰ and +1‰, (Fig. 9) comparable to the meteorite sulfur isotopic composition. The sulfur isotopic composition is also in the range of porphyry epithermal type of deposits but distinct from structurally controlled alteration rock type deposits (Fig.8) (Hoefs et al.,1975; Li and Santosh, 2014 & Gao et al., 2017). 4.5.2 Lead isotopic characteristics of pyrite The values of the ratios of

206

Pb/204Pb,

207

Pb/204Pb and

208

Pb/204Pb for pyrite from placer

deposits of Bagrote valley shows narrow ranges from 18.3775 to 18.4337 with an average of 18.395, from 15.5803 to 15.6032 with an average of 15.587 and from 38.4451 to 38.5469 with a mean of 38.476 respectively. The Pb isotopic variation is fairly narrow in the samples of pyrite from the Bagrote valley placer deposits (Table 6). 5.

Discussion

5.1 Deposit types inferred in the hinterlands Since the catchment of the valleys contains undiscovered gold deposits, we compared our data of major and trace elements geochemistry of pyrite with that of different genetic types of gold deposits to find clues on unknown types of gold deposits in the catchment area of the valley. The chemical composition of the pyrite from Bagrote valley placers is represented by Curve 5 in figure 6a, which follow curve 2 of magmatic hydrothermal gold deposits. where curve 5 (Bagrote valley placers) is compared with curve 2 (magmatic hydrothermal). Curve 5 (Bagrote Valley) has high Co and slightly low Cu, Pb, Zn. The Co content is increased in pyrite as consequence of Ni release during the evolution of magma. Ni is removed from the fluid to the

solid phase rapidly than Co in the process of magmatic differentiation, and hence the concentration of Co relatively increased in residual magmatic fluids. The element content of pyrite from Bagrote valley shows that the pyrite is derived from magmatic hydrothermal gold deposits from the hinterlands of the valley. Figure 6b displays the δFe/δS-As characteristics of the pyrite from Bagrote valley. The plots of δFe/ δS-As fall mainly in the domain of the magmatic hydrothermal gold deposits and Carlin type deposits but the geology of the catchment area (Fig.1c) is not consistent with the formation of Carlin type deposits. Therefore, we consider the presence of undiscovered magmatic hydrothermal type gold mineralisation in the hinterlands. The (Fe+S)-As characteristics of pyrite from the Bagrote valley placers deposit is shown in the Figure 6c. Most of the (Fe+S)-As plots are in the area of the magmatic hydrothermal gold deposits. This further supports the idea that the studied pyrite grains are derived from magmatic hydrothermal gold deposits from the catchment area of the Bagrote valley. The Co-Ni-As ternary diagram of the pyrite (Fig.6d) also shows that all the plots fall on the field of magmatic hydrothermal and epithermal gold deposits. The thermoelectricity and temperature estimates (290-380°C) further categorize the deposit types in the hinterland of the valley. It is generally recognized that magmatic hydrothermal deposits exhibit a wide range of temperature, with epithermal deposits formed below 300°C while porphyry deposits formed higher than 300°C and up to 700°C (Foster, 1991; Hedenquist & Lowenstern, 1994; Richards, 1995; Poulsen, 1996). Our calculated temperature from thermoelectric data of pyrite is mainly concentrated from 290°C to 380°C (Table 2 & Fig.3a) and in consistent with porphyry epithermal type of mineralisation. The sulfur isotope values of our pyrite samples (Table 6 Fig.8) are also in the range of porphyry and epithermal type of deposits (Gao et al.,2017). In previous studies based on the placer gold grains chemistry and their mineral

inclusions from the same valley by Ali (2011) and Alam et al. (2018) described that the hinterlands of the valley host porphyry epithermal type of deposits and the porphyritic character of the rocks belonging to Chalt Volcanics (CV) (Miandad et al., 2014), which cover the dominant drainage of the valley also favors the presence of porphyry deposits on the hinterlands of the Bagrote valley. Porphyry and some epithermal gold deposits are formed from the hydrothermal fluids produced from cooling calc-alkaline, water rich magma emplaced in volcano plutonic arcs above subduction zone (Richard, 2009). Porphyry Au deposits have recently been reported by some authors and these deposits are seen to be related to high-K calc-alkaline to shoshonitic magma from arc collisional environments including collision with continents, microcontinent fragments, or mature island arcs. Our study area (Figs. 1a, 1b) shows arc continent collision environment i.e. the collision of Kohistan island arc with India along MMT (61Ma) and with Asia along MKT (50Ma) (Khan et al. 2009) (Figs.1a,1b). Other examples from different regions include: the SW Pacific Neogene porphyry deposits, which followed collision or subduction reversal, described by Solomon, (1990); In NW Iran, the Sari Gunay Epithermal gold deposits (Late Miocene) followed Paleogene–early Neogene Neo-Tethyan collision reported by Richards et al. (2006) ; the Çöpler epithermal gold deposit (Eocene) located in eastern Turkey, which postdate Cretaceous– Paleocene Neo-Tethyan collision based on the work of Keskin et al. ( 2008); and porphyry Cu-Au deposits (mid-Miocene) in Tibet, followed Late collision between Asia and India (Hou et al., 2005) (Fig 1a) and Duobaoshan ore field north China is also characterized by similar island arc-related collision and subduction setting which contains a number of porphyry and epithermal gold deposits (Ren et al.,1997; Richards, 2011; Wu et al., 2011; Seltmann et al., 2014; Zeng et al., 2014). Based on the above arguments, we conclude that the hinterlands of Bagrote valley might contain porphyry epithermal type deposits.

With very few exceptions, orogenic gold deposits also formed in subduction-related tectonic settings in accretionary to collisional orogenic belts from Archean to Tertiary times (Grooves et al., 2018), and orogenic Au intimately relates to subduction and associated metamorphic processes forms via devolatilization in the crust and in sub-crustal regions within the temperature range of 220 to 450°C (Goldfarb and Grooves, 2015). The tectonic setting of our study area (Fig.1), crystallization temperature of pyrite (290-380°C) suggesting the prevalence of orogenic gold deposits on the hinterlands, but other evidences like S isotope values and trace element content is not in consistent with the formation of orogenic gold deposits. For example, δ34S data for most of the orogenic gold deposits found worldwide is typically δ34 SV-CDT  = 0 to 9‰ (Groves et al., 1998; McCuaig and Kerrich, 1998; Kerrich et al., 2000; Goldfarb et al., 2001), while the δ34SVCDT

of pyrite in our study ranges from – 0.6 to 0.9, and according to Goldfarb and Grooves (2015),

isotope data for genesis of orogenic gold are equivocal and may vary with time. Geochemical enrichments of orogenic gold deposits have most consistent anomalies and characterized by elevated Ag, As, Au, B, Bi, Sb, Te and W (Kerrich, 1983; Phillips and Groves, 1983; Groves et al., 1998; Goldfarb et al., 2005), but in contrast, the concentration of these trace elements specifically W, Bi, Ag, Sb and Te in our studied pyrite grains is very low (Table 3). Therefore, we suggest porphyry epithermal type mineralisation found on the hinterlands of Bagrote valley. However, after discovery of hidden deposit on the hinterlands of north western Himalaya north Pakistan, fluid inclusion data and meteorite values from ore forming stages will further make clear the doubts about the type of source deposits in a continent-arc setting contributing placer deposits in the valleys downstream.

5.2 Mineralisation and source lithology Many researchers have used the Co/Ni ratios as an empirical indicator for the depositional environment (Bralia et al., 1979; Roberts 1982; Raymond, 1996; Craig et al., 1998; Clark et al., 2004). The Co/Ni ratio lesser than 1 is generally known to represent pyrite of syn-sedimentary origin. In contrast, highly varying Co/Ni ratios, usually greater than 1, are considered to be consequent of hydrothermal processes (Bralia et al., 1979; Large et al., 2009). The Co/Ni ratio in the Bagrote valley placer deposits is generally greater than 1, and in some grains, far greater with an average of 31.1 (Table 5), suggesting that hydrothermal fluids are closely related to mineralisation. The pyrite chemistry can also provide clues about the lithology from which it was eroded. In other words, the geology of the hinterland can be reflected in the chemistry of the pyrite that was eroded from the hinterlands. Ultramafic and, to a lesser extent, mafic rocks are strongly enriched in Ni (Li et al., 2016). In contrast, highly differentiated magmatic rocks, such as granites, are enriched in the incompatible metal Mo (Koglin et al.,2010). As a result, the Mo/Ni ratio may be good indicator to constrain the relative proportion of mafic to ultramafic over felsic rocks in the source areas (hinterland). The values of the Mo/Ni ratios in the pyrite from the Bagrote locality placer deposits range from 1.32 to 59 with an average of 14.80. The Chalt Volcanic Group followed by the Kohistan Batholith constitutes the dominant hinterland of the Bagrote valley. A mixed provenance of mafic to intermediate and felsic Chalt Volcanics and Kohistan Batholith (Fig.1c) postulated from the geology of the Bagrote valley, is well reflected in pyrite chemistry, i.e. medium mean value of Mo/Ni ratios (Table 5).

5.3 Au incorporation in Pyrite In sulphide minerals, Au is mostly dispersed as ‘‘invisible’’ gold. In pyrite and arsenopyrite, incorporation of invisible gold can occur either through nano scale inclusions (nanoinclusions), such as native Au, tellurides, and antimonides (Deditius et al., 2011), or in the mineral structure (Wu & Delbove, 1989). In the latter case, various mechanisms control the Au uptake, such as substitution of monovalent gold (Au+) for Fe2+ according to different coupled substitutions (Simon, et al., 1999; Tauson, 1999), or the incorporation of Au3+ or other elements in the 3+ oxidation state (Sb3+, As3+) for Fe2+ as a way to balance valences after the replacement of As and production of (AsS) 3- anions (Cook & Chryssoulis, 1990; Arehart, et al., 1993). According to Reich et al. (2005), Au-As points plotted above the solubility line contain Au as micro to nano sized inclusion as (Au0), whereas the plots falling below the solubility line represent the prevalence of Au in solid solutions as (Au+1) (Reich et al., 2013). In our pyrite samples, the Au-As (Fig.7a) are all plotted above the segmented / dashed-line (solubility line), described by Reich et al. (2005) as the empirical solubility limit of Au is a function of As in pyrite (Reich et al., 2013). This shows that Au is found in the form of inclusions as Au0 in the pyrite from Bagrote valley placer deposits. More ever, the scattered plots in the absence of negative correlation of Fe-Au (Fig.7b) further support this interpretation (Reich et al., 2013). The calculated chemical formula of pyrite of our samples which is [Au0.0006Fe] S2.004 (Table 3), shows that Au is not enriched in pyrite as a result of isomorphism. 5.4 Ore forming fluids and source of metals and sulfur Sulfide minerals are important indicators of hydrothermal mineralization, and to constrain the origin of sulfides, the stable isotopic composition of sulfur offer a useful tool (Seal, 2006; Zhu et

al., 2011). Although, the sulfur isotopic composition is affected by pH value, temperature, ion activity and oxygen fugacity, under reduced hydrothermal conditions (m∑H2S>>m∑SO4), the mean value of δ34S of minerals would correspond to that of the total sulfur in the hydrothermal fluid in a relatively simple mineral assemblage (Sakai,1968; Hoefs et al., 1975; Li et al., 2018). The precipitation of the sulfide minerals usually occurs under low oxygen fugacity conditions; therefore, their sulfur isotope composition can be regarded to reflect those of the mineralizing fluid (Zheng and Chen, 2000; Li S.R. et al. 2013; Li L. et al., 2015; Li and Santosh, 2017). In the Bagrote valley placer deposit, as compared to the other sulfide minerals like chalcopyrite, galena and sphalerite, pyrite is abundant in panned concentrates (above 90%), suggesting that the mineral assemblage of the deposits in the catchment of the Bagrote valley may not carry complex mineral assemblages. Thus, we consider the δ34S composition of pyrite to reflect the total sulfur to discuss the nature of the ore-forming fluid. The origin of sulfide minerals is reflected from Sulfur isotope data (Rollinson, 1993). The sulfur isotopic composition of our pyrite samples partially overlaps with volcanic SO2, island arc basalt and andesite and is also within the range of granitic rocks and meteorite (Fig.8). The pyrite within the Bagrote valley placer deposit has a narrow range of 

34

S compositions (Fig. 8,9),

suggesting these pyrites formed under stable chemical and physical conditions and were derived from a relatively homogeneous source (Ohmoto and Rye, 1979; Ohmoto and Goldhaber, 1997). As shown by  34S values, the majority of the pyrite is relatively depleted in heavy S isotopes, that range from –0.6‰ to 0.9‰ (Table 6). This range is consistent with the S isotope composition of sulfides from magmatic and magmatic-related deposits ranging from –3‰ to 1‰ (Hoefs, 2015),

which suggests that the metals and sulfur in the deposits found on the hinterlands of the Bagrote valley has a magmatic origin and may derived from rocks of Chalt Volcanics. As shown in the Figure 10, the plots of 206Pb/204Pb vs.

208

Pb/204Pb data straddle between the

evolution curve of orogenic and lower crustal sources and is closer to the orogenic evolution curve (Fig.10a). The

206

Pb/204Pb vs.

207

Pb/204Pb plots straddle the evolution cure of orogenic source

(Fig.10b), which indicates that the source of lead and by inference the ore metals originated from orogenic belts with minor contribution of lower crust. The narrow variations in, 208

207

Pb/204Pb,

Pb/204Pb and 206Pb/204Pb suggest a single lead source. The Pb isotopic composition of the Chalt

Volcanics (Petterson et al., 2010), which lies on the drainage area of Bagrote river, partially overlap with that of pyrite derived from the downstream placer deposits (Fig.10) which suggests that the Chalt Volcanics may have provided metals for mineralization. The higher As and Co content reveals the involvement of meteoric water and magmatic water respectively. When meteoric water exceeds in volume in the ore forming fluid, the plots in Co-NiAs diagram will tend to be closer or concentrated at the As end. In contrast, the plots concentrated in Co end indicate dominance of magmatic water in ore forming fluids (Yan et al., 2012; Niu et al., 2016: Yuan et al 2017). The Co-Ni-As diagram (Fig.6d) indicate different amounts of meteoric and magmatic water. In the Co-Ni-As diagram, the plots of the Bagrote valley placer deposit are scattered from Co to As ends but are slightly closer to Co end and are far from Ni end (Fig.6d), which may suggest dominance of magmatic water and later addition of meteoric water in the ore forming fluids. 6. Conclusions

Our multiparametric study on pyrite grains from the placers deposits of the Bagrote valley provide important insights into gold ore genesis and source characteristics. The pyrite grains display euhedral to subhedral morphologies and euhedral pyrite, mostly cubic, occurs as secondary grains. Rounded grains are rare showing short distance of transport from the source deposits. The major and trace element chemistry of pyrite, crystallization temperature derived from thermoelectricity data, and sulfur isotopic composition combined with information from previous studies on placer gold grains suggest that the deposits on the hinterlands of the Bagrote valley might belong to porphyry or epithermal type of deposit. The lead isotope data shows that the source of lead and by inference the source of metals are orogenic, and that the Chalt volcanic group might have supplied the metals for mineralisation. The Co-As-Ni relationship suggests that the ore forming fluids contained both magmatic and meteoric waters. The calculated chemical formula of pyrite of our samples [Au0.0006Fe] S2.004], plots of Au-As and Au-Fe shows that gold occurs in pyrite as micro to nano inclusion as Au0. The range of low high Mo/Ni ratios indicate a mixed provenance. The overlapping Pb isotope data suggest that the Chalt Volcanics as the source of metals. Thermoelectric parameters have important implications to study source deposits contributing placers in other hinterlands, as well as their exhumation and denudation rate in the high glaciated mountains of north Pakistan. The chemistry of detrital pyrite can be successfully applied to obtain insights about the source lithologies hosting gold mineralisation.

ACKNOWLEDGEMENTS We are grateful to Dr. Zhen-Yu Chen and Ms. Yuan Ma for their valuable help to carry out EMPA analysis. Thank full to Ms. Wang Qi for her kind cooperation for conducting isotopic analysis and

to obtain EPMA X-ray elemental maps. Thanks are due also to a team of local gold washers for helping to collect panned concentrate samples. We also thank the colleagues at Mineral picking laboratory in Langfang, China for picking and separating pyrite grains from panned concentrates samples. The financial support from the Ministry of Science and Technology of China for the State Key Research and Development Plan (grant no. 2016YFC0600106) is acknowledged.

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Figure Captions Fig. 1 (a) Location of the studied zone. Modified after Mahéo et al. (2004) and Pêcher et al. (2008). (b) Regional geological map of the study area modified after Searle et al. (1996) and Alam et al. (2018)

KO: Kohistan, LA: Ladakh, ISSZ: Indus Sangpo Suture Zone, NSB: Northern

sedimentary belt Fig. 1(c) Geological map of the Bagrote valley showing samples locations, modified from Searle et al. (1996), Miandad et al. (2014) and Alam et al. (2018) Fig. 2 Representative BSE images (a, b, c, d) and cartons images of the pyrite (e, f, g, h, I) showing morphology of the pyrite grains from the Bagrote valley placer deposits. Red circles show the analysed EPMA spots on BSE images. See text for discussion. bdl: below detection limit Fig. 3 Powder XRD curves of pyrite from placer deposits of the Bagrote valley. Fig. 4 Histogram of thermoelectric coefficient (a) and temperature (b) of pyrite from the Bagrote valley Placer deposits, see text for discussion. Fig. 5 EPMA elemental images of the auriferous pyrite grain from the Bagrote valley placer deposits, BSE: Back scattered electron image; Level: Relative content, see text for discussion. Fig. 6 (a) Element content of auriferous pyrite in the placer deposits of Bagrote valley (Fe, S and As are in % and the other elements are in ppm). 1: Epithermal gold deposit, 2: Magmatic hydrothermal gold deposit, 3: Metamorphic hydrothermal gold deposit, 4: Carlin-type gold deposit, 5: Bagrote valley placer deposit (this study) (b) The δFe/δS-As characteristics of the auriferous pyrite from Bagrote Valley. A- Magmatic hydrothermal gold deposits, B- Carlin-type

gold deposits, C -Metamorphic hydrothermal gold deposits. 1: Bagrote valley placer deposit (this study). 2: Epithermal gold deposit. 3: Magmatic hydrothermal gold deposit. 4: Metamorphic hydrothermal gold deposit. 5: Carlin-type gold deposit (c) The (Fe+S)-As characteristics of the placer deposits of Bagrote valley. A- Carlin-type gold deposits, B- Magmatic hydrothermal gold deposits, C- Volcanic hydrothermal gold deposits, D -Metamorphic hydrothermal gold deposits. 1-5 are same as in figure 6b. Figures 6a, 6b, and 6c has been modified after Yan et. al. (2014). (d) Co-Ni-As ternary diagram of the pyrite from Bagrote valley placer deposit. Modified from Yan et al. (2012), Niu et al. (2016) and Yuan et al. (2017), see text for discussion. Fig. 7 (a) Au-As and (b) Fe-Au plots of auriferous pyrite from placer gold deposits of Bagrote valley, modified after Reich et al. (2005). See text for discussion. Fig. 8 Sulfur isotopic compositions of the of the Bagrote valley placers deposits, modified after Hoefs et al. (1975), Li and Santosh, (2014), Gao et al. (2017). See text for discussion. Fig. 9 Histogram showing sulfur isotopic compositions of the of the Bagrote valley placers deposits. Fig. 10 Pb isotope characteristic of pyrite from placer deposits of the Bagrote valley. (a)208Pb/204Pb verses 206Pb/204Pb diagram (b) 207Pb/206Pb verses 206Pb/204Pb diagram. modified from Zartman & Haines (1988). See text for discussion. Fig. 11

Tables captions Table 1 showing specifications of the samples collected for this study from the Bagrote valley

Table 2 Thermoelectricity data of pyrites from the Bagrote valley placer deposits. P (%) is the occurrence rate of P-type pyrite. N (%) is the occurrence rate of N-type pyrite. Xnp is thermoelectric parameter. γ is denudation percentage. Table 3 Representative EPMA results of pyrite in wt% from Bagrote valley placer deposits (bdl: bellow detection limit) Table 4 S/Fe, δFe/δS and Fe+S values of pyrite grains from placer deposits of the Bagrote valley. Table 5 Co/Ni and Mo/Ni ratio of pyrite from Bagrote valley placer deposits Table 6 S-Pb Isotopic composition of pyrite from the Bagrote valley placer deposits and Chalt Volcanic group (CV).

Fig. 1 (a) Location of the studied zone. Modified after Mahéo et al. (2004) and Pêcher et al. (2008). (b) Regional geological map of the study area modified after Searle et al. (1996) and Alam et al. (2018) KF: Karakoram Fault, KO: Kohistan, LA: Ladakh,

Fig. 1(c) Geological map of the Bagrote valley showing samples locations, modified from Searle et al. (1996), Miandad et al. (2014) and Alam et al. (2018)

Fig. 2 Representative BSE images (a, b, c, d) and cartoons (e, f, g, h, I,) of pyrite grains showing morphology from the Bagrote valley placer deposits, red circles show the analysed EPMA spots on BSE images, see text for discussion. bdl: below detection limit

Fig. 3 Powder XRD curve of pyrite from placer deposits of Bagrote valley.

Fig. 4 Histogram of thermoelectric coefficient (a) and temperature (b) of pyrite from Bagrote valley Placer deposits, see text for discussion.

Fig. 5 EPMA elemental images of the auriferous pyrite grain from the Bagrote valley placer deposits, BSE: Back scattered electron image; Level: Relative content, see text for discussion.

Fig. 6 (a) The whole element content of auriferous pyrite in the placer deposits of Bagrote valley (Fe, S and As are in % and the other elements are in ppm). 1: epithermal gold deposit, 2: magmatic hydrothermal gold deposit, 3: metamorphic hydrothermal gold deposit, 4: Carlin-type gold deposit, 5: Bagrote valley placer deposit (this study) (b) The δFe/δS-As characteristics of the auriferous pyrite from Bagrote Valley. A- Magmatic hydrothermal gold deposits, B- Carlin-type gold deposits, C -metamorphic hydrothermal gold deposits. 1: Bagrote valley placer deposit. (this study). 2: epithermal gold deposit. 3: magmatic hydrothermal gold deposit. 4: Metamorphic hydrothermal gold deposit. 5: Carlin-type gold deposit (c) The (Fe+S)-As characteristics of the placer deposits of Bagrote valley. A- Carlin-type gold deposits, B- magmatic hydrothermal gold deposits, C- volcanic hydrothermal gold deposits, D -metamorphic hydrothermal gold deposits. 1-

5 are same as in figure 6b. Figures 6a, 6b, and 6c has been modified after Yan et. al. (2014) (d) Co-Ni-As ternary diagram of the pyrite from Bagrote valley placer deposit. Modified from Yan et al. (2012), Niu et al. (2016) and Yuan et al. (2017), see text for discussion.

Fig. 7 (a) Au-As and (b) Fe-Au plots of auriferous pyrite from placer gold deposits of Bagrote valley, modified after Reich et al. (2005, 2103). See text for discussion.

Fig. 8 Sulfur isotopic compositions of the of Bagrote valley placers deposits. Modified after Hoefs et al. (1975), Li and Santosh, (2014) & Gao et al. (2017). See text for discussion.

Fig. 9 Histogram showing sulfur isotopic compositions of the of Bagrote valley placers deposits.

Fig. 10 Pb isotope characteristic of pyrite from placer deposits of Bagrote valley. (a)

206

Pb/204Pb

verses 208Pb/204Pb diagram (b) 206Pb/204Pb verses 207Pb/204Pb diagram. modified from Zartman & Haines (1988). See text for discussion.

Table 1 showing specifications of the samples collected for this study from the Bagrote valley Sample No

BG-01 BG-02 BG-03 BG-04 BG-05 BG-06 BG-07 BG-08 BG-09 BG-10 BG-11 BG-12

GPS points

35.874550°, 74.480141° 35.877756° 74.480869° 35.888920° 74.483126° 35.906057° 74.492801° 35.928265° 74.501434° 35.967487° 74.523475° 35.972682° 74.524045° 35.979865° 74.529105° 35.987171° 74.532100° 35.999620° 74.539827° 36.019346° 74.549918° 36.035832°, 74.566469°

Location

Sediments panned

pyrite

Quartz

gold

2.4 g

No of grains of Rutile >500

Down stream

20 kg

15 mg

133 grains

Down stream

30 kg

2g

>100

40 mg

51 mg

Down stream

20 Kg

4g

>1000

60 mg

166 mg

Down stream

20 kg

4.7 g

-

15 mg

150 grains

Mid-stream

20 kg

3.8 g

>300

50 mg

280 grains

Mid-Stream

20 Kg

5.5 gm

>80

80 mg

110 grains

Mid-Stream

20 kg

0.9 gm

>200

35 mg

238 grains

Mid-Stream

30 kg

2.6 gm

>400

20 mg

34 mg

Up-stream

20 Kg

2.7 gm

>500

80 mg

152 mg

Up-stream

20 kg

2.6 gm

>200

20 grains

Up-stream

20 kg

2g

>300

> 2000 grains 20 mg

Up-stream

20 Kg

1.1 g

200

70 mg

200 grains

240 grains

Table 1Thermoelectricity data and analysis of pyrites from Bagrote valley placer deposits. P (%) is the occurrence rate of P-type pyrite. N (%) is the occurrence of N-type pyrite. Xnp is thermoelectric parameter. γ is denudation percentage.

Sample No

N-type thermoelectricity, α(μV/°C)

N (%)

Maximum

Minimum

Average

-33.9

-268.7

-122.6

82.8

BG-2

-31.6

-445

-8.1

BG-3

-17.8

-278.4

BG-4

-18

BG-5

Temp. (°C)

P-type thermoelectricity, α(μV/°C)

P (%)

Temp. (°C)

XnP

γ

Maximum

Minimum

Average

322

284.7

1.5

129

17.2

150.7

-82

70.5

91

321.9

257

26

133.6

9

78

-91

72.5

-112.9

86

325.2

263.8

8.8

141.5

14

158.2

-83

70.8

-250

-106.1

89.9

329

245.1

48

142.4

9.1

153.1

-91

72.5

-29.2

-240

-119

84

321.9

303.8

29.2

163.1

16

171.2

-86

71.5

BG-6

-43

-270.4

-127

94

317.5

291.7

27

142.8

6

159

-105

66.3

BG-7

-4.5

-263.3

-118.8

87

322

286.6

54

137.3

13

78.8

-92

73

BG-8

-14.7

-269.4

-107

89

328.4

228.3

21.8

119.4

11

145

-90

72.5

BG-9

-18.1

-229.7

-122

92

320.2

267

116

181.8

8

182.4

-91

72.8

BG-10

-31.6

-263.6

-119.2

93

321.7

288.2

87.3

172.7

7

177

-95

73.5

BG-11

-42.6

-212.8

-99.6

89

332.5

290.3

52.3

188.5

11

186.4

-84

71

BG-12

-28.4

296.2

-124.4

92

319

276.7

20.6

171.9

8

176.5

-98

74.5

BG--1

Table 2 Representative EPMA results of pyrite in wt% from the Bagrote valley placer deposits (bdl: bellow detection limit) Grain No

Se

As

w

Ag

Pb

Cd

Au

S

Fe

Zn

Cr

Cu

Te

Sb

Co

Mo

Ni

Total

BG-Py-1

bdl

0.017

bdl

bdl

bdl

0.007

0.014

53.003

46.254

bdl

0.027

bdl

bdl

0.005

0.121

0.059

0.001

99.508

BG-Py-2

0.011

0.008

bdl

bdl

0.107

0.001

0.005

52.999

46.729

bdl

0.005

0.016

bdl

bdl

0.099

0.06

bdl

100.04

BG-Py-3

bdl

0.062

bdl

bdl

bdl

0.012

bdl

53.085

45.92

bdl

bdl

0.005

0.007

0.009

0.099

0.061

bdl

99.26

BG-Py-4

bdl

0.06

bdl

0.022

0.009

0.01

0.034

53.056

45.94

bdl

0.018

bdl

bdl

bdl

0.117

0.06

0.008

99.334

BG-Py-5

0.009

bdl

bdl

0.003

bdl

0.041

bdl

52.833

45.934

bdl

0.029

0.011

bdl

bdl

0.154

0.061

bdl

99.075

BG-Py-6

bdl

0.071

bdl

bdl

bdl

bdl

bdl

53.203

46.42

bdl

0.035

bdl

0.001

bdl

0.12

0.063

bdl

99.913

BG-Py-7

bdl

0.026

bdl

0.003

bdl

bdl

bdl

53.301

46.238

bdl

bdl

0.045

bdl

bdl

0.11

0.062

bdl

99.785

BG-Py-8

0.009

0.069

bdl

bdl

bdl

0.031

0.053

53.098

46.248

0.009

bdl

0.001

bdl

bdl

0.111

0.061

0.002

99.692

BG-Py-9

bdl

0.417

bdl

bdl

0.049

0.01

0.087

52.821

44.581

bdl

0.013

0.014

bdl

bdl

1.804

0.062

bdl

99.858

BG-Py-10

bdl

0.014

bdl

0.004

bdl

bdl

bdl

53.084

45.969

bdl

0.013

0.008

bdl

bdl

0.355

0.063

0.007

99.517

BG-Py-11

bdl

bdl

bdl

bdl

bdl

bdl

0.053

53.444

46.349

0.002

bdl

bdl

bdl

bdl

0.145

0.064

0.029

100.086

BG-Py-12

0.008

bdl

bdl

bdl

bdl

0.036

0.101

53.149

45.327

bdl

0.013

0.006

0.004

bdl

1.083

0.062

bdl

99.789

BG-Py-13

bdl

0.039

bdl

0.004

bdl

0.016

0.072

53.487

45.988

bdl

bdl

bdl

bdl

bdl

0.11

0.062

0.047

99.825

BG-Py-14

bdl

0.268

bdl

0.001

bdl

bdl

0.034

53.188

45.989

bdl

0.005

0.004

0.01

bdl

0.115

0.062

bdl

99.676

BG-Py-15

bdl

0.112

bdl

bdl

bdl

0.031

bdl

53.541

46.746

0.025

bdl

0.028

0.003

bdl

0.094

0.063

0.009

100.652

BG-Py-16

bdl

0.063

bdl

0.018

bdl

bdl

bdl

53.317

46.25

0.002

bdl

bdl

bdl

0.016

0.133

0.062

0.015

99.876

BG-Py-17

bdl

0.103

bdl

bdl

0.033

bdl

0.116

51.934

46.618

0.013

0.024

0.019

bdl

bdl

0.092

0.061

bdl

99.013

BG-Py-18

0.006

0.025

bdl

0.001

0.045

0.019

bdl

53.43

46.264

bdl

bdl

bdl

0.009

bdl

0.394

0.062

bdl

100.255

BG-Py-20

bdl

0.219

bdl

bdl

bdl

0.022

0.063

52.9

46.221

bdl

0.002

bdl

bdl

bdl

0.07

0.063

0.005

99.565

Mean

0.086

0.098

0.007

0.049

0.02

0.057

53.1

46.10

0.010

0.016

0.014

0.006

0.01

0.29

0.061

0.014

99.72

Table 3 Showing S/Fe, δFe/δS and Fe+S values of pyrite grains from placer deposits of Bagrote valley. Grain No

S

Fe

S/Fe

δFe

δS

δFe/δS

Fe+S%

BG-Py-1

53.003

46.254

2.00

9836.41

9816.37

1.00

99.26

BG-Py-2

52.999

46.729

1.98

9938.45

9815.62

1.01

99.73

BG-Py-3

53.085

45.92

2.02

9764.66

9831.71

0.99

99.01

BG-Py-4

53.056

45.94

2.02

9768.96

9826.29

0.99

99.00

BG-Py-5

52.833

45.934

2.01

9767.67

9784.57

1.00

98.77

BG-Py-6

53.203

46.42

2.01

9872.07

9853.79

1.00

99.62

BG-Py-7

53.301

46.238

2.02

9832.98

9872.12

1.00

99.54

BG-Py-8

53.098

46.248

2.01

9835.12

9834.14

1.00

99.35

BG-Py-9

52.821

44.581

2.07

9477.01

9782.32

0.97

97.40

BG-Py-10

53.084

45.969

2.02

9775.19

9831.52

0.99

99.05

BG-Py-11

53.444

46.349

2.02

9856.82

9898.88

1.00

99.79

BG-Py-12

53.149

45.327

2.05

9637.27

9843.69

0.98

98.48

BG-Py-13

53.487

45.988

2.04

9779.27

9906.92

0.99

99.48

BG-Py-14

53.188

45.989

2.02

9779.48

9850.98

0.99

99.18

BG-Py-15

53.541

46.746

2.00

9942.11

9917.03

1.00

100.29

BG-Py-16

53.317

46.25

2.02

9835.55

9875.12

1.00

99.57

BG-Py-17

51.934

46.618

1.95

9914.61

9616.37

1.03

98.55

BG-Py-18

53.43

46.264

2.02

9838.56

9896.26

0.99

99.69

BG-Py-20

52.9

46.221

2.00

9829.32

9797.10

1.00

99.12

2.01

9804.3

9834.2

1

99.20

Mean

Table 4 Co/Ni and Mo/Ni ratio of pyrite from the Bagrote valley placer deposits Grain no. BG-Py-1 BG-Py-4 BG-Py-8 BG-Py-10 BG-Py-11 BG-Py-13 BG-Py-15 BG-Py-16 BG-Py-20 Mean

Au(wt%) 0.014 0.034 0.053 bdl 0.053 0.072 bdl bdl 0.063 0.048

Co(wt%) 0.121 0.117 0.111 0.355 0.145 0.11 0.094 0.133 0.07 0.14

Mo(wt%) 0.059 0.06 0.061 0.063 0.064 0.062 0.063 0.062 0.063 0.061

Ni(wt%) 0.001 0.008 0.002 0.007 0.029 0.047 0.009 0.015 0.005 0.014

Co/Ni 121.00 14.63 55.50 50.71 5.00 2.34 10.44 8.87 14.00 31.38

Mo/Ni 59.00 7.50 30.50 9.00 2.21 1.32 7.00 4.13 12.60 14.80

Table 5 S-Pb Isotopic composition of pyrite from Bagrote valley placer gold deposits and Chalt Volcanics (CV). S isotope Sample ID BG-2 BG-3 BG-5 BG-6 BG-8 BG-12 Average PL28 PL29 NI15 NI16 NI38 NI39 NI61 IK580 Average

Mineral/Rock

Pb isotope δ34S

V

208Pb/204Pb

207Pb/204Pb

206Pb/204Pb

208Pb/206Pb

207Pb/206Pb

38.458 38.547 38.457 38.498 38.445 38.452 38.476 38.113 38.199 38.340 38.224 38.315 38.187 38.124 38.103 38.201

15.583 15.603 15.581 15.594 15.581 15.582 15.587 15.518 15.536 15.552 15.540 15.569 15.535 15.524 15.520 15.537

18.383 18.433 18.386 18.403 18.378 18.385 18.395 18.187 18.226 18.348 18.243 18.283 18.299 18.168 18.113 18.233

2.09212 2.09114 2.09155 2.09196 2.09195 2.09154 2.092 -

0.84768 0.84646 0.84741 0.84737 0.84779 0.84756 0.847 -

Source

-CDT

Pyrite Pyrite Pyrite Pyrite Pyrite Pyrite Chalt Volcanics Chalt Volcanics Chalt Volcanics Chalt Volcanics Chalt Volcanics Chalt Volcanics Chalt Volcanics Chalt Volcanics Chalt Volcanics

-0.6 -0.5 0.4 0.9 -0.4 0.1 -0.02 --

This study This study This study This study This study This study This study Khan et al.,1997 Khan et al.,1997 Khan et al.,1997 Khan et al.,1997 Khan et al.,1997 Khan et al.,1997 Khan et al.,1997 Khan et al.,1997 -