Trace-element geochemistry of molybdenite from porphyry Cu deposits of the Birgilda-Tomino ore cluster (South Urals, Russia)

ABSTRACT Mineralogical, electron microprobe analysis and laser ablation-inductively coupled plasma-mass spectrometry data from molybdenite within two porphyry copper deposits (Kalinovskoe and Birgilda) of the Birgilda-Tomino ore cluster (South Urals) are presented.† The results provide evidence that molybdenites from these two sites have similar trace-element chemistry. Most trace elements (Si, Fe, Co, Cu, Zn, Ag, Sb, Te, Pb, Bi, Au, As and Se) form mineral inclusions within molybdenite. The Re contents in molybdenite vary from 8.7 ppm to 1.13 wt.%. The Re distribution within single molybdenite flakes is always extremely heterogeneous. It is argued that a temperature decrease favours the formation of Re-rich molybdenite. The high Re content of molybdenite observed points to a mantle-derived source.


Introduction
PORPHYRY copper deposits are the major source of Re as a by-product (Dill, 2010) and molybdenite is the only economically significant carrier of this element. Rhenium is currently ranked as a critical metal in very short supply in Russia (Trach and Beskin, 2011), making the study of the rhenium distribution in known deposits very relevant. For this reason porphyry copper deposits of the Urals have recently attracted attention as potential sources of both molybdenum and rhenium. General features of rhenium distribution in Uralian porphyry copper deposits were discussed by Grabezhev (2013) while the rhenium behaviour of individual deposits and within single grains of molybdenite has been described recently (e.g. Grabezhev and Shagalov, 2010;Grabezhev and Gmyra, 2014;Grabezhev and Hiller, 2015;Grabezhev and Voudouris, 2015;Plotinskaya et al., 2014aPlotinskaya et al., , 2015. Among the numerous porphyry deposits and occurrences known in the Urals (Plotinskaya et al., 2017a,b) the area of the Birgilda-Tomino ore cluster is one of the most interesting due to a remarkable variability of styles of mineralization (Plotinskaya et al., 2014b) and it is economically promising because of the large Tomino porphyry copper deposit. The rhenium distribution in molybdenite from the Tomino deposit was described by Grabezhev and Hiller (2015).
The present study has provided new mineralogical, electron microprobe analysis (EMPA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) data from molybdenite from two porphyry copper deposits of the Birgilda-Tomino ore cluster, Kalinovskoe and Birgilda. The main goal of this paper is to describe, at the scale of single molybdenite flakes, the distribution of rhenium and other trace elements as well as to discuss the controls of this distribution.

Geological background
The general geology and tectonic setting of the Birgilda-Tomino ore cluster were described in detail by Puzhakov (1999), Grabezhev et al. (1998) and Plotinskaya et al. (2014bPlotinskaya et al. ( , 2017a. The ore cluster is located within the East-Uralian Volcanic Terrane (the shaded area in the inset of Fig. 1a) which is interpreted as a series of fragments of intra-oceanic arcs of Silurian to Devonian age (Yazeva and Bochkarev, 1995;Samygin and Burtman, 2009;Puchkov, 2017). The northeastern part of the area (Fig. 1a) comprises the Early to Middle Ordovician Sargazy Formation with a maximum thickness of 1500 m. It is composed of aphyric basalt and andesitic basalt supplemented by minor porphyric basalt and basaltic volcanoclastic rocks, as well as rhyolite and rhyolite tuffs metamorphosed to greenschist facies (Puzhakov, 1999). This formation hosts all known porphyry copper deposits in this area. In the central part of the area, the Sargazy basalts are overlain by Middle Ordovician to Lower Silurian limestones and marbles of the Biksizak Formation that host the Biksizak base-metal carbonate replacement deposit. The Sargazy basalts and the Biksizak Formation are overlain in turn by volcanics of the Bereznyakovskoe Formation which hosts epithermal Au-Ag deposits and occurrences, including the Bereznyakovskoe ore field. The Bereznyakovskoe Formation comprises andesitic dacite volcanoclastic rocks up to 1000 m thick and minor andesitic dacite lavas with rare limestone interlayers (Grabezhev et al., 1998;Puzhakov, 1999).

The Kalinovskoe deposit
The Kalinovskoe porphyry copper deposit (Fig. 1b) together with the neighbouring Tomino deposit and several smaller occurrences make up the Tomino porphyry copper ore field. Porphyry-style mineralization is confined to a large stock, ∼2 km in diameter, composed of quartz diorite, amphibole plagioclase diorite and porphyritic varieties, which belong to the Birgilda-Tomino Igneous Complex. The mineralization occurs both in diorites and in hosting Ordovician basalts. In the central zones of the diorite stocks, phyllic alteration accompanies chalcopyrite ± bornite ± molybdenite mineralization, while in the peripheral zone, propylitic alteration dominates with pyrite-chalcopyrite mineralization and occasional magnetite and hematite. The latest-stage mineralization, which occurs in the periphery of the Kalinovskoe deposit, includes various Bi-sulfosalts (bismuthinite-aikinite series, matildite), native gold, galena, sphalerite, tetrahedrite (Plotinskaya et al., 2014b) with bornite, chalcopyrite and rare Au-Ag, Ag, Pb, Bi, and Hg tellurides. The oxidation zone is up to 40 m thick and contains malachite, azurite and chalcocite. The total reserves (Russian A + B + C categories) of the Tomino and Kalinovskoe deposits make up 331 Mt at 0.46 wt.% Cu and 0.1 g/t Au (Volchkov et al., 2015). Grabezhev (2013) reported Cu/Mo ratios from 100 to 300, but Mo occasionally rises to 3-80 ppm which decreases the Cu/Mo ratios to 25-50.

The Birgilda deposit
The Birgilda deposit (Fig. 1c) was the first porphyrystyle mineralization discovered in the area S282 FIG. 1. Geological maps of the Birgilda-Tomino ore cluster: (a) the Kalinovskoe deposit, modified after Grabezhev et al. (2000); (b) modified after Chelyabinskgeolsiomka JSC and Puzhakov (1999); (c) The Birgilda deposit, simplified after Narykova et al. (2015). The inset in (a) shows the East-Uralian volcanic terrane highlighted in grey and the yellow star indicates the position of the Birgilda-Tomino ore cluster.

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TRACE-ELEMENT GEOCHEMISTRY OF MOLYBDENITE FROM PORPHYRY Cu DEPOSITS (Romashova, 1984). The mineralization is associated with two stocks of diorite and diorite porphyry known as South and North Birgilda, respectively; each ∼1 km in size. The diorites are altered pervasively to quartz-sericite (phyllic) and mixed chlorite-sericite, while propylitic (chlorite ± epidote) alteration dominates in the host basalts. Pyrite, chalcopyrite and molybdenite are the main ore minerals. Both the mineralization and the alteration are similar to those at Kalinovskoe. The Birgilda deposit was reported by Pravda (2015) to contain 152.2 kt of Cu at 0.51 wt.% Cu. Grabezhev and Belgorodskii (1992) noted a Cu/Mo ratio of 150.

Molybdenite assemblages and sampling
Molybdenite occurs in both study areas as μmto mm-scale nests, usually in white to grey quartz veinlets or, sometimes, disseminated in the host rocks. It occurs mainly within the diorite intrusions where it is accompanied by quartz + sericite ± chlorite alteration, but it is also observed in the host basalt. Molybdenite is always associated with chalcopyrite, chlorite, sometimes with pyrite, white mica, and, occasionally, with epidote and carbonate.
Molybdenite-bearing samples were collected from exploration drill cores. Samples were selected for EMPA and LA-ICP-MS analysis to represent both the central and the peripheral zones of the deposits studied (Fig. 1b,c) as well as from diorite and basalt host rocks. A detailed description of both samples is given in Table 1 and images in Figs 2 and 3. The two most molybdenite-rich samples (K-3/112.7 and Bir-1101/237) were selected for Re-Os dating.

Re-Os dating of molybdenite
Molybdenite-bearing samples were crushed and grains intergrown with molybdenite were handpicked using a needle under a binocular microscope. Molybdenite-rich separates (∼25 to 30 mg) were transferred into Carius tubes resting in dry ice, followed by the addition of a mixed 188  Os/ 185 Re spike as recommended by Markey et al. (2003) and digested in 'inverted aqua regia'. The sealed tubes were placed in an oven at 220°C and allowed to react for 48 h. Osmium was separated by solvent extraction, with a final purification of Os by microdistillation.
Rhenium was separated from a portion of the residual liquid using anion exchange chromatography. Isotopic measurements were made by means of a Thermo-Ionization Mass-Spectrometer (TIMS) Triton™ instrument using the Faraday collectors for both Re and Os. Measured Os isotope ratios were first corrected for contributions from natural Os (based on preliminary isotope dilution calculations), then corrected for mass fractionation based on the 190 Os/ 188 Os ratio of the spike. 187 Os was determined from the 187 Os/ 188 Os ratio of the mixture and corrected for minor contributions from total common Os (blank plus sample). Most of the error in both the Re and Os concentrations is from the uncertainties of the spike calibrations and the mass spectrometric measurements, an error magnification factor, uncertainties on blank corrections and, for the age determination, uncertainty in the decay constant for 187 Re. The weighing error of the sample does not contribute to the uncertainty in the ages because of a mixed-double 188  Os/ 185 Re spike used (Markey et al., 2003). Analytical blanks are insignificant for the age calculations, given the Re and 187 Os concentrations of the samples studied and the sample size used in the analyses. Blank values were 1 pg/g for Re and 4 pg/g for Os with 187 Os/ 188 Os of 0.15. The uncertainty for each individual age determination does not exceed 0.5%, including the 0.3% uncertainty in the decay constant of 187 Re.

EMPA study
The chemical compositions of ore and gangue minerals were determined using a Zeiss EVO 15LS scanning electron microscope with an Oxford Instruments X-Max EDX detector (Natural History Museum, London) using the following beam conditions: beam diameter 1-2 µm, accelerating voltage 20 kV, beam current 3 nA, and a counting time of 20 s. The 1σ analytical error was 0.06-0.08 for Mn and Cr and did not exceed 0.2 wt.% for all other elements. The detection limit was accepted as 1σ.
The molybdenite composition was determined using a Cameca SX-100 electron microprobe with five WDX spectrometers (Natural History Museum, London, UK). X-ray mapping using ReLα, ReMα, MoLα, SKα, CaKα, SiKα, FeKα, and ZnKα was carried out first, and points for single spot analysis were then selected from the resulting X-ray map data.
For the Kalinovskoe deposit the operating conditions were: beam diameter 1-2 µm,

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accelerating voltage 20 kV, beam current 20 nA, and analytical lines ReLα, MoLα, ZnLα and SKα. Counting time was: 60 s for S, 120 s for Zn, 240 s for Mo, and 240 s for Re. The peak overlaps were corrected for 0.002% Mo/S and 0.04% S/Mo. The detection limits were (wt.%): 0.06 for S, 0.03 for Re and Zn and 0.02 for Mo. Standard deviation was (wt.%): 0.33 for S, 0.03 for Re, 0.02 for Zn and 0.40 wt. for Mo.
For the Birgilda deposit the conditions were: beam diameter 1-2 µm, accelerating voltage 20 kV, beam current 40 nA, and analytical lines SiKα, Diorite cut by a small plagiogranite dyke, both with intense quartz-sericite-chlorite alteration; both are cut by a white-grey quartz veinlet with molybdenite in selvages (Fig. 3a).

LA-ICP-MS study
The trace-element data for molybdenite were acquired using the LA-ICP-MS system at IGEM RAS (Moscow  (2007) and calibrated with respect to concentration of elements against standards at UQAC (Sylvester et al., 2005) for Fe, Ag, Re, Au; MASS-1 polymetal sulfide (USGS) for the remaining elements and 33 S was used as the internal standard based on molybdenite stoichiometry. GSE, a synthetic basalt glass with 25 wt.% Si, was used for Si calibration and verification of the other results with Mo as the internal standard. LA-ICP-MS analyses of external standards and molybdenite samples were conducted at the same conditions using a 40 to 60 µm diameter spot size, a laser frequency of 15 Hz, 5-7 mJ input power and 5 µm/s ablation speed for profiles. Acquisition time in spot mode was 30 s for the background and 30 s for the mineral analysis. The washout time was 30 s between measuring individual laser spots. All standards were run before and after each set of 15 unknowns as well as before and after each set of 40 and 60 µm spot sizes. LA-ICP-MS data were processed using the Iolite data-reduction software, v. 2.5 (Paton et al., 2011).

Fluid-inclusion study
Microthermometric measurements of fluid inclusions were carried out on doubly polished thin sections using a LINKAM THM-600 heatingfreezing stage at the Institute of Experimental Mineralogy Russian Academy of Sciences, Chernogolovka. The temperature of phase transitions was measured over the range -196 to +600°C with an accuracy of ±0.2°C between -20°C and +20°C and no less than ±1.0°C outside of this interval. The salt composition of the fluids was determined from the eutectic temperature (T e ) according to Crawford (1981); the salinity was estimated from the temperature of ice melting (T m ) using the NaCl-H 2 O phase diagram (Bodnar and Vityk, 1994). The measurements were carried out for groups of inclusions with similar relationships of phases to avoid errors related to the disintegration of vacuoles after fluid heterogenization (Roedder, 1984). Pressure was calculated using the method proposed by Kaluzhny (1982) for coexisting fluid inclusions of CO 2 and water-salt composition using diagrams from Thiery et al. (1994) and the FLINKOR software (Brown, 1989).

Re-Os ages of molybdenite
For the Kalinovskoe and the Birgilda deposits, the molybdenite samples yielded Re-Os ages of 431.9 ± 1.9 and 432.0 ± 1.7 Ma respectively ( Table 2). The uncertainty of the individual age determination for both samples is in the order of 0.4%.

Kalinovskoe deposit
The EMPA study revealed Re contents above the detection limit in three of the four samples from the Kalinovskoe deposit (Table 3 and Supplementary Material -Appendix 1). From those, the totals of only 41 analyses out of 100 were >98 wt.% because the molybdenite flakes were either too small or too S288 thin. Significant negative correlation was noted between the Re and Mo contents in analyses with a total >99 wt.% (r = -0.56, n = 22) confirming substitution of Mo by Re. X-ray mapping using the ReLα line combined with point analyses revealed an uneven rhenium distribution in all of the molybdenite flakes and, moreover, different distribution patterns in different samples. In sample K-8/100.6 ( Fig. 4a,b) a deformed molybdenite flake has an elevated Re content in the central part (0.06 to 0.08 wt.%) and marginal zones (up to 0.17 wt.%) while the Re content of the remaining part of the flake is below the detection limit. In sample K-1050/157.5 (Fig. 4c,d), Re-rich molybdenite (up to 0.95 wt.% Re) overgrows Re-poor molybdenite (up to 0.1 wt.% Re). In sample K-3/112.7 (Fig. 4e,f ) in a large aggregate of molybdenite flakes, high Re contents (∼0.2 to 0.95 wt.%) form linear zones (up to dozens of μm wide) on the margins of the flakes, or, occasionally spots. K-2210/73.4 is the only sample where the Re contents are below the detection limit.   nnumber of intervals within LA-ISP-MS profiles selected for calculation; Geom. mean = geometrical mean; dl = detection limit; the values below dl were treated as half dl in the statistical analysis; statistical parameters were not calculated for those datasets where more than half of the values were below dl; n.a. = not analysed.
In addition Grabezhev and Hiller (2015) reported Re contents as high as 0.05 to 0.07 wt.% in four of 130 point analyses of the subset of this sample.
Molybdenite grains large enough to be analysed by LA-ICP-MS were observed only in samples K-3/ 112.7 and K-2210/73.4. In both samples, molybdenite shows highly variable trace-element concentrations (Table 4 and Supplementary Material -Appendix 2). Both samples show very high Fe contents (up to 34,900 ppm) and Cu (up to 7900 ppm), while sample K-3/112.7 also has a high Si content (up to 12,400 ppm), probably due to intergrowths with chalcopyrite and silicates. Both samples have up to several hundred ppm of Zn, Se and tens of ppm of As, Pb, Bi and Ag (Table 4). The contents of Co, Ni, Sn, Sb, Te and Au are below the detection limit in sample K-2210/73.4 but reach several ppm to tens of ppm in sample K-3/112.7. The opposite is true for W which is up to 4 ppm in sample K-2210/73.4 and mainly below the detection limit in sample K-3/112.7. The maximum Re content in sample K-3/112.7 is 4540 ppm which is in good agreement with the EMPA data (Fig. 4h,i). In sample K-2210/73.4 Re varies from 9 to 1144 ppm with a geometric mean of 75 ppm, in general agreement with the data of Tessalina and Plotinskaya (2017) who measured 81.5 ppm of Re within the same sample.
Pearson's correlation coefficients were calculated for the whole dataset of trace elements except for Ni and Sn as these elements are below detection limit in more than a half of all analyses (Table 5). There is a significant positive correlation between Fe, Co, Cu, Zn, Ag, Sb, Te, Au, Pb and Bi. In addition, in sample K-3/112 there is a strong positive correlation between Si and Fe, Co and Zn (0.85, 0.78 and 0.88, respectively, at minimum significant 0.5 for n = 16). Arsenic and W, in contrast, have negative correlations with most trace elements but a positive correlation with each other (0.59). Re has negative correlations with W and As and no correlation with other elements. Se doesn't have either positive or negative correlations with any trace elements.

Birgilda deposit
The EMPA study revealed Re contents above the detection limit in most analyses of all four samples from the Birgilda deposit (Table 3 and Supplementary Material -Appendix 1). The totals were >98 wt.% in 107 of 140 analyses due to the small grain size.
X-ray mapping using the ReLα line revealed an uneven distribution of Re in all the molybdenite flakes (Figs 5-7). In all four samples, Re-enriched zones encompass areas from several μm across in sample Bir-42/84 (Fig. 5a,b) to tens of μm wide (samples Bir-1101/237 and Bir-1101/291.2) and up to hundreds of μm long (Figs 6 and 7). These zones are confined to either axial or marginal parts of molybdenite flakes but are always parallel to the  (Table 4 and Supplementary Material -Appendix 2). Similar to molybdenite from the Kalinovskoe deposit, the Fe, Cu and Si contents reach thousands of ppm because of numerous inclusions of silicates and chalcopyrite. The Co, Ni, Sn, Te and Au contents are below the detection limit in most analyses but occasionally reach several ppm. All samples show similar ranges of Zn, As, Se (tens to a few hundreds (d,e) fragments of (c) with the EMPA profiles; ( f ) ReLα X-ray map of (c); (g) LA-ICP-MS spectra for line 5.

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of ppm), Ag, Pb, Bi and W (several ppm to a few tens of ppm Pearson's correlation coefficients were calculated for the entire trace-elements dataset except for Co, Ni, Sn, Te and Au because those elements were below the detection limit in more than a half of the analyses ( Table 6). The highest positive correlations (>0.9) exist between Fe and Cu and between Pb and Bi. The Birgilda deposit is similar to the Kalinovskoe deposit with most trace elements showing positive correlations with each other, i.e. Si, Fe, Cu, Zn, Ag, Sb, As, Se, Pb and Bi. Rhenium has negative correlations with Pb, Sb, Bi, Se and As, while W has negative correlations with Se and As. For the Birgilda deposit, the calculation (Table 6) indicates a positive correlation (0.55) between Re and W. However, on a Re vs. W diagram (Fig. 8a), samples Bir-4905/294.4 and Bir-1101/237 and sample Bir-1101/291.2 clearly form two distinct trends each of which shows a significant negative correlation between Re and W (-0.62 for sample Bir-1101/291.2). This demonstrates that the W and Re behaviour in molybdenite from the Birgilda deposit is similar to that from the Kalinovskoe deposit. Despite the negative correlation between Re and Se for molybdenite from the Birgilda deposit (Fig. 8b), there is a positive Re vs. Se correlation for analyses with Re <2500 ppm (+0.64 at minimum significant 0.44, n = 20) and negative Re vs. Se correlation for analyses with Re >2500 ppm (-0.59 at minimum significant 0.5, n = 16).

Chlorite chemistry and thermometry
Molybdenite is intimately intergrown with chlorite in all the molybdenite-bearing samples studied (Figs 2f,g, 3c (d-f ) fragments of (a) with EMPA profiles.

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alteration halo. The chlorite chemical composition was obtained in order to evaluate its formation temperature (Table 7, Appendix 3 and Fig. 9). All the chlorite grains from both Kalinovskoe and Birgilda deposits belong to the clinochloredaphnite series with minor but variable amounts

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overgrown by molybdenite (Fig. 10a). The quartz is interpreted as preceding the molybdenite formation. At room temperature, two coexisting types of fluid inclusions were identified: (1) VL 1 L 2 -type fluid inclusions have oval or negative crystal shapes and range from 10 to 15 µm in size; they consist of aqueous liquid and vapour bubbles (30-50 vol.%) surrounded by a thin rim of carbonic liquid (Fig. 10b); and (2) V-type inclusions, 10-15 µm in size, consisting of vapour, sometimes with a thin rim of liquid. In the two samples from Birgilda, fluid inclusions were found in anhedral quartz grains that form intimate intergrowths with molybdenite (Fig. 10c) and are cut by carbonate veinlets. The quartz grains are presumed to have formed at the same time as the molybdenite. They contain fluid inclusions of VLtype, which are irregularly shaped, range from 10 to 20 µm in size, and consist of aqueous liquid and a vapour bubble that occupies some 20-30 vol.% of the inclusions (Fig. 10d).
All these inclusions are considered to be primary according to the criteria proposed by Roedder (1984). No daughter minerals or trapped solids were observed.

Microthermometry of fluid inclusions
The results of a microthermometric study are presented in Table 8 and Fig. 11. Fluid inclusions of the VL 1 L 2 type from Kalinovskoe show low salinities (10.4 to 12 wt.% NaCl equiv.) and eutectic temperatures of -43 to -39°C indicating that divalent chlorides (Mg 2+ and (or) Fe 2+ ) are dominant. The VL 1 L 2 and V types of inclusion both have T m (CO 2 ) from -58.5 to −58.9°C which is lower than for pure CO 2 (-56.6°C ), suggesting a small admixture of CH 4 (Collins, 1979). VL 1 L 2 -type inclusions homogenize to the liquid phase upon heating at 365 to 502°C. Pressure, as calculated for single-phase CO 2 -bearing inclusions from Kalinovskoe, corresponds to 650-802 bar. These data are in agreement with previous results for Kalinovskoe (Groznova et al., 2015).
Fluid inclusions of the VL type from Birgilda show moderate salinities (12.7-18.9 wt.% NaCl equiv.) and eutectic temperatures of -38.5 to -30°C indicating the presence of both NaCl and divalent chlorides. They homogenize to the liquid phase at 195-265°C.
The coexistence among the VL 1 L 2 and V types of fluid inclusion in the Kalinovskoe samples suggests that the fluids had undergone CO 2 effervescence. In this case the estimates of T h can be regarded as real trapping temperatures (Roedder, 1984). For VL-type inclusions from Birgilda the T h estimates may be considered as minimum trapping temperatures. It is worth noting that the T h estimates for sample Bir-1101/237 (230-265, mean 248°C) overlap with the temperature estimates obtained for chlorite (248-259, mean 255°C, Table 7) calculated after Kotelnikov et al. (2012). The T h estimates for sample mean 208°C) are somewhat lower than the temperatures obtained from chlorite geothermometry (249-267, mean 257°C, Table 7). There is no reliable pressure estimate for the Birgilda samples but the pressure was probably similar to that estimated for late-stage mineralization at Kalinovskoe and in the range 190-350 bars (Groznova et al., 2015). Pressure corrections for the homogenization temperatures (Potter, 1977) will, in this case, increase the temperature estimate by 30°C, to 225-351°C. If the pressure is higher and ∼760 bar as suggested for the early Kalinovskoe assemblages, then the correction will reach 70°C (265-271°C). Both intervals overlap with the temperatures calculated from chlorite geothermometry (Kotelnikov et al., 2012).

Re-Os dating of molybdenite
Previous Re-Os dating of three molybdenite samples from the marginal zone at Kalinovskoe Classification of chlorites after Bailey (1988 The two ages presented here and those from the earlier work can be considered to represent a single age population, within the analytical uncertainty, that concurs with the emplacement age of the ore-bearing porphyry diorite stock at Tomino (428 ± 3 Ma) obtained by zircon dating .

Trace elements in molybdenite
The trace-element contents of molybdenite from Kalinovskoe and Birgilda are generally similar (Tables 3, 4). Molybdenite from Kalinovskoe is slightly higher in Ag and Bi but lower in W and it

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also shows a wider range of Re content than that from Birgilda. Overall, the Re content of both sites is similar to molybdenite from the Tomino deposit, where Grabezhev and Hiller (2015) reported 0.04 to 0.38 wt.% Re by EMPA point analyses and 0.05 to 0.26 wt.% by ICP-MS analyses of molybdenite mineral fractions. This is also similar to calculated Re contents from spectrophotometry analysis of bulk samples which gave values of 440-3140 ppm Re in molybdenite (Grabezhev, 2013). Correlation analysis revealed a group of elements with positive correlations: Si, Fe, Co, Cu, Zn, Ag, Sb, Te, Pb and Bi. For Kalinovskoe this group includes Au, while As and Se are included at Birgilda. Mineralogical data provide evidence that all these elements form mineral inclusions in molybdenite. Numerous discrete regions within the LA-ICP-MS profiles indicating elevated proportions of these elements (Figs 4h,i,k,5g,6c,7c) support this conclusion. The Si-Fe correlation, most evident in sample K-3/112.7 (Fig. 8c), is likely to be the result of multiple intergrowths of molybdenite with chlorite and, to a lesser degree, with epidote (Figs 2b,f,3c,f,h,i,4e). Numerous inclusions of chalcopyrite (Figs 3e, 4j, 5c) resulted in positive Fe-Cu correlations (Fig. 8d). Inclusions of matildite (Fig. 2h), and, perhaps, of other Bi-and Pb-sulfosalts and tellurides led to positive correlations for Pb-Bi, Bi-Ag (Fig. 8e,f ), Bi-Cu and Bi-Te.
Rhenium, which has either no correlation or a negative correlation with the other trace elements (using LA-ICP-MS data) also shows a negative correlation with Mo in the EMPA analyses and is most likely to be incorporated in the molybdenite lattice. Inclusions of rheniite, similar to those described by Voudouris et al. (2009) and too small to be detectable by SEM cannot, however, be ruled out. Other elements including W and Se can be incorporated into the molybdenite structure with Re (see review in Pašava et al., 2016 for detailed references). However, W demonstrates extremely irregular LA-ICP-MS spectra (Figs 4-6) suggesting the presence of inclusions of W-bearing minerals. High Se contents (1000 ppm or more) bound isomorphically to molybdenite were proven by Ciobanu et al. (2013) based on an LA-ICP-MS study. Moreover, Kalinin et al. (2013) reported up to 15 wt.% of Se in molybdenite based on EMPA data. In the Birgilda deposit, positive Re vs. Se correlation for analyses with <2500 ppm Re suggests that some Se may be incorporated in the molybdenite lattice. However, our previous mineralogical study of the Kalinovskoe ore (Plotinskaya et al., 2014b) revealed up to 0.69 wt.% Se in matildite and 0.57 wt.% Se in tetradymite which, in addition to a positive Se-Bi correlation (Table 5), provides evidence that Se is mainly due to mineral inclusions in molybdenite.

Deposit-scale variations of rhenium
The limited number of samples investigated does not allow any conclusions to be drawn on variations of the Re content of molybdenite on a deposit scale. Most samples from Kalinovskoe and Birgilda have high Re contents averaging 1200 to 5700 ppm (Table 4). No correlation with the host rocks is evident; diorite-and basalt-hosted samples have similar molybdenite Re contents. The only exception is sample K-2210/73.4 with Re contents considerably lower than the other samples and averaging 71 ppm. This value is close to two other samples from the same ore body (drill hole K-2210) reported by Tessalina and Plotinskaya (2017) with Re contents of 147 and 228 ppm Re. Perhaps this is a feature of this peripheral ore body, but that requires further investigation.

Rhenium distribution in individual grains of molybdenite
All the samples investigated demonstrate extremely irregular Re distributions in single molybdenite flakes. The Re contents vary by one or two orders of magnitude, e.g. from 302 to 4540 ppm in sample K-3/112.7, or from <10 to >1000 ppm in sample K-2210/73.4 (Table 4). The irregular distribution of Re in molybdenites from deposits of various genetic types has been identified by EMPA (Kovalenker et al., 1974;Voudouris et al., 2009;Maksimyuk and Kulikova, 2013;Rathkopf et al., 2017), by LA-ICP-MS (Ciobanu et al., 2013;Bogdanov and Krumov, 2016;Kovalenker et al., 2018, etc.), and by NanoSIMS (Barra et al., 2017). Aleinikoff et al. (2012) and Ciobanu et al. (2013) also noted variations in W and Se. This suggests that the irregular distribution of rhenium in single grains of molybdenite is a common phenomenon. X-ray mapping using the ReLα line (Figs 4b,d,f,5b,f,6b,7b) showed that most Re-enriched areas form linear zones up to tens of μm wide. Similar linear distribution patterns were revealed in molybdenites from other porphyry Cu-(Mo) deposits of the Urals by X-ray mapping, such as the Verkhneuralskoe Mo-porphyry occurrence Plotinskaya et al., 2014a), the Voznesenskoe Cu-porphyry deposit (Grabezhev and Voudoris, 2014) and the Mikheevskoe Cuporphyry deposit (Grabezhev and Shagalov, 2010;Plotinskaya et al., 2015). Perhaps there are Reenriched layers, or groups of layers, within the molybdenite structure. It has been assumed that such layers could be formed of the 3R-polytypes of molybdenite (e.g. Newberry, 1979;Rekharskii et al., 1983;Filimonova et al., 1984;Melfos et al., 1991;Maksimyuk and Kulikova, 2013). However, the presence of high Re contents in both natural (Voudouris et al., 2009;Ciobanu et al., 2013) and synthetic (Drabek et al., 2010) molybdenites formed of the 2H-polytype suggests other mechanisms of incorporation of Re into the molybdenite structure. For example, Ciobanu et al. (2013) attributed a high Re content to lattice defects in 2H-molybdenite.

Controls of Re incorporation in molybdenite
The controls of Re incorporation in molybdenite have been discussed by Berzina et al. (2005) and in experimental studies by Xiong et al. (2006). It has been established that lower temperatures and a decrease in f O 2 are favourable for the formation of high-Re molybdenite. Both the high-and low-Re molybdenite observed in this study have similar FIG. 12. Mean T (°C) vs. mean wt.% Re from the EPMA analyses (Table 3). Error bars are shown for 1 sd. The temperature was calculated after Kotelnikov et al. (2012) (Table 2). The correlation coefficient is given for the whole dataset excluding sample Bir-42/82.

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assemblages (chalcopyrite, pyrite, chlorite, epidote, muscovite, calcite) which does not allow any estimation of differences in variation of f O 2 . Chlorite, however, can be used to test the temperature influence on the incorporation of Re in molybdenite. The chlorite thermometer of Kotelnikov et al. (2012) was selected because it gives a better agreement with the fluid-inclusion results from the two Birgilda samples. Figure 12 shows mean the Re contents vs. mean calculated temperatures. Samples with higher Re contents (K-1050/157.5, K-3/112.4, Bir-1101/291.2 and Bir-1101/237) were formed at lower temperatures than those with lower Re contents (K-2210/73.4, K-8/ 100.6, and Bir-4905/294.5). Sample Bir-42/84 is the only exception, but the temperature was calculated from only three chlorite analyses and, thus, may be unrepresentative. The remaining seven samples demonstrate a significant negative correlation (-0.81) between temperature and Re content.

Sources of rhenium and other metals
It has been suggested that high Re contents in molybdenite provide evidence for a mantle input (Stein et al., 2001;Sun et al., 2004, etc.). Reviews by Mao et al. (2013) and Pašava et al. (2016), using data from the literature, propose that <10 ppm Re in molybdenite indicates crustal sources, 10-100 ppm indicates a mixed mantle/crustal source and >100 ppm Re in molybdenite indicates molybdenite derived from mantle sources. Therefore, the high Re contents of most molybdenites from Kalinovskoe and Birgilda may indicate a predominantly mantle source for the metals. The Sm-Nd systematics of the diorite porphyry intrusions of the Birgilda-Tomino igneous complex (Grabezhev, 2009) confirms a mantle-derived source of the magma and most of the metals. A lead isotope study (Plotinskaya et al., 2017a) also provided evidence for a mantle-derived lead source. There was, however, the possibility of some input of both magma and metals from a crustal source such as might have been produced in a mature volcanic arc with the input of sediments containing crustal lead from denudation of pre-Cambrian crust into a subduction zone. This could explain the deposit-scale variation of Re content in molybdenite observed at the Kalinovskoe deposit.

Conclusions
The trace-element patterns of molybdenite from the Kalinovskoe and Birgilda porphyry copper deposits of the Urals are broadly similar. Most trace elements (Si, Fe, Co, Cu, Zn, Ag, Sb, Te, Pb, Bi, Au, As and Se) form mineral inclusions within molybdenite. Rhenium is most likely to be incorporated into the molybdenite lattice. The present results demonstrate an extremely irregular distribution of Re within individual molybdenite flakes, with Re-enriched areas forming μm-scale linear zones. A negative relationship is shown between the Re contents of molybdenite and the temperature of formation of the co-existing chlorite.
The high Re contents (up to 1.13 wt.%) in molybdenite indicate a mantle-derived source.