METALLOGENIC APPROACH OF THE OROGENIC GOLD MINERALIZATION PRESENT AT LIBANO, TOLIMA. By Juan Sebastian Duran Torres Thesis dissertation for obtain the degree of: Geoscientist PhD. Yamirka Rojas Agramonte Director MSc. Juan Carlos Molano Mendoza Co-Director UNIVERSIDAD DE LOS ANDES FACULTAD DE CIENCIAS DEPARTAMENTO DE GEOCIENCIAS Bogota, May 2018 ____________________________ PhD. Yamirka Rojas Agramonte ____________________________ MSc. Juan Carlos Molano Mendoza ____________________________ Juan Sebastian Duran Torres To my family… CONTENTS 1. INTRODUCTION 1 1.1 Orogenic Gold Deposits ………………………………… 2 1.2 Intrusion-related Gold Deposits ………………………………… 4 1.3 Fluid Inclusion studies ………………………………… 5 2. REGIONAL GEOLOGY AND TECTONIC SETTING 6 2.1 Tectonic Framework ………………………………… 6 2.2 Regional Geology ………………………………… 8 3. GEOLOGY OF THE MINING AREA 11 4. METODOLOGY 16 4.1 Field work ………………………………… 16 4.2 Laboratory work ………………………………… 17 4.3 Petrography ………………………………… 17 4.4 Scanning electron microscope ………………………………… 18 4.5 Fluid inclusion studies ………………………………… 18 4.6 Raman analysis ………………………………… 18 5. RESULTS 19 5.1 Petrography 5.1.1 Host Rocks ………………………………… ………………………………… 19 19 5.1.1.1 Quartz-chlorite-sericite schists ……..…….. 19 5.1.1.2 Graphitic schists ……..…….. 21 5.1.2 Porphyritic intrusives …………………………… 23 5.1.2.1 DH-16 …………………………… 23 5.1.2.2 DH-15 …………………………… 24 …………………………… 25 5.1.3.1 Samples from the first level………….……….. 25 5.1.3.2 Samples from the fifth level……………… 28 5.1.3.3 Samples from the ninth level ………….… 31 5.1.3.4 Samples from the tenth level……..……… 39 5.1.3 Quartz veins 5.1.4 Igneous dykes …………………………… 41 5.1.4.1 Sample 10-ALT …………………… 41 5.1.4.1 Sample DA-1 …………………… 41 5.2 Mineral paragenesis ………………………………… 44 5.3 Mineral chemistry ………………………………… 46 5.4 Microthermometry ………………………………… 51 5.5 Raman Spectroscopy ………………………………… 60 6. DISCUSSION 6.1 Mineralizing styles and vein textures 62 …………………………….. 62 6.2 Hydrothermal alteration ……………………………63 6.3 Paragenetic sequence .………………………….. 65 6.4 Mineralizing fluids …………………………… 66 6.5 Source of fluids and relationship to magmatism ……..…..…….…. 69 6.6 Comparative table between deposit types ……….………… 70 7. CONCLUSIONS 72 8. RECOMMENDATIONS 73 9. AKWNOWLEDGMENTS 73 10. REFERENCES 74 ANNEXES 77 RESUMEN La mineralización que ocurre en el área de Libano (Tolima) se caracterizó como un sistema ramal vetiforme de tipo oro orogénico, mesozonal, hospedado en esquistos grafitosos y verdes pertenecientes al Complejo Cajamarca. En el depósito, la alteración hidrotermal se presenta en zonas proximales adyacentes a las vetas de cuarzo, principalmente con sericita, calcita y cantidades menores de dolomita, clorita, micas blancas, turmalina y rutilo. Las vetas presentan rumbo preferencial noreste e inclinaciones al noroeste entre 40° y 70°, son concordantes con la foliación del hospedante, y presentan espesores variables entre los 0.8 y 3 metros, alcanzando hasta 6 metros localmente. Mineralógicamente están constituidas por pirita, esfalerita, esfalerita de cadmio, galena, calcopirita, pirrotina, y en menor proporción arsenopirita, argento-tenantita, pirargirita, polibasita, plata nativa y electrum con relaciones variables de Au/Ag, asociados con cuarzo, calcita, dolomita, scheelita y ferberita. Se distinguieron 4 eventos de mineralización definidos por las relaciones de corte y texturas entre las vetas y los minerales, en donde el grado del oro disminuye a medida que aumenta la cantidad de plata en el sistema. Las vetas son de tipo “crack & seal”, presentan una textura bandeada y se interpreta que fueron formadas durante múltiples eventos de fracturación, mezcla y flujo de fluidos. Además, las vetas presentan texturas masivas, brechosas, y drusiformes. Localmente se pueden observar en las vetas “dilational jogs”, zonas de “ore-shoots”, pinchamientos y engrosamientos. El área está controlada por el “Sistema de Fallas La Chucula” como arreglo conjugado tipo Riedel con rumbo N330°W, interpretado como satélite a la falla de Palestina de primer orden. Las fases volátiles que caracterizan el fluido mineralizante son H2O – CO2 + CH4 + N2, con salinidades entre el rango de 1.71-7.86 wt. % NaCleq, temperaturas de homogenización entre 250° y 320 °C, una densidad de 0.8 g/cc y tendencias de evolución de fluidos principalmente de tipo mezcla isotermal. Palabras clave: Oro orogénico, venas tipo crack-seal, CO2, scheelita, esquistos grafitosos. ABSTRACT The mineralization that occurs in the area of Libano (Tolima) was characterized as a vetiform branch system of orogenic gold type, mesozonal, hosted in graphitic schists and greenschists belonging to the Cajamarca Complex. In the deposit, hydrothermal alteration occurs in proximal areas adjacent to the quartz veins, mainly with sericite, calcite and minor amounts of chlorite, white micas, tourmaline and rutile. The veins have a northeast preferential strike and northwest dip between 40 ° and 70 °. Moreover, they are concordant with the foliation of the host rock, and have mainly variable thickness between 0.8 and 3 meters, reaching up to 6 meters locally. Mineralogically, the veins are constituted by pyrite, sphalerite, cadmium sphalerite, galena, chalcopyrite, pyrrhotite, and in a lesser proportions arsenopyrite, argento-tennantite, pirargyrite, polybasite, native silver and electrum with variable Au / Ag ratios, associated with quartz, calcite, dolomite, scheelite and ferberite. Four mineralization events were distinguished, defined by cut off relationships and textures between veins and minerals, where the degree of gold decreases as the amount of silver in the system increases. The veins are of “crack & seal" type, have a banded texture and were formed during multiple fracturing, and fluid flow mixing events. Moreover, veins display massive, brecciated, and drusiform textures. Locally "dilational jogs", areas of "oreshoots", pinch and swell structures occur in the veins. The area is controlled by the “La Chucula” Fault System as a Riedel-type conjugate arrangement with N330° W strike, interpreted as satellite to the Palestine fault of first order. The volatile phases that characterize the mineralizing fluid are H2O - CO2 + CH4 + N2, with salinities between the range of 1.71-7.86 wt. % NaCleq, homogenization temperatures between 250 ° and 320 ° C, a density of 0.8 g / cc and fluid evolution tendencies mainly of isothermal mixture type. Key words: Orogenic gold, crack-seal veins, CO2, graphitic schists. 1. INTRODUCTION Near the town of Libano, which is located on the eastern flank of the central cordillera in the department of Tolima, diverse gold and silver mineralizations have been reported associated to hydrothermal quartz veins. Such veins comprise varying amounts of sulfides, carbonates and scheelite. In turn, veins were find cutting off metamorphic rocks in greenschist facies belonging to the Cajamarca Complex. These characteristics are similar to deposits described as "orogenic gold" type (Groves et al., 1998) or intrusion-related gold systems (Hart et al., 2005). According to Leal-Mejía (2011) these mineral deposits correspond to the mining district of Santa Isabel-Libano, and are classified as gold mineralizations intrinsic to igneous intrusive bodies. Castillo (2016), on the other hand, relates them to orogenic or mesothermal gold deposits due to their structural and mineral characteristics. So, similarity between characteristics of these deposit types makes them difficult to classify. Although Colombia is recognized as a gold producing country per excellence (Leal-Mejia, 2011), there have not been many studies about gold deposits hosted in metamorphic terranes belonging to Colombian territory. These studies are necessary and fundamental for the development of exploration criteria in active mining regions such, as the Libano mining area. Therefore, the present study intends to characterize the mineral deposit that occurs in the underground mine called “Mina el Gran Porvenir del Libano”. Defining different mineralization events based on mineral paragenesis and fluid inclusion families found in the quartz veins. Also with the structural characteristics controlling mineralization, petrography, mineral chemistry, Raman spectroscopy, as well as identifying mineralization styles and alteration mineral assemblages in host rocks. Based on the above, this study opens the possibility to give clues about the formation processes of this gold deposit and the evolution of the ore forming fluid. The present study will also provide valuable information to the metallogenic map of Colombia, developed by the Geologic Survey of Colombia, which is actually in process. 1 The mine is located 5 kilometers to the north of the Libano town and it can be reach over the road that links the Libano and Convenio municipality in approximately one and half hour. The topography of the area is characterized by a steep topographic gradient mountain relief with high to medium slopes, as consequence of pluvio-erosion. Heights vary in the area from 1500 to 1800 meters above sea level (see Figure 1). Figure 1. Location map of the mining area. 1.1 Orogenic gold deposits Orogenic gold deposits are characterized by having an important structural control because they were formed by tectonic events, during compresional to transpressional deformation processes occurred at convergent plate boundaries, along shear zones (Eilu, 1999). In orogenic gold deposits, the host rocks correspond mainly to metamorphic rocks in greenschist facies. In addition, they present diverse quantities of sulfides, such as pyrite, pyrrhotite, arsenopyrite, sphalerite, chalcopyrite, galena and carbonates, white micas (muscovite, fuschite), scheelite, tourmaline and high concentrations of gold and silver (Groves et al., 1998). Also, fineness of gold in this deposit ranges between 780-1000 (Morrison et al., 1990). 2 Hydrothermal alteration processes that took place correspond to sericitization and carbonatization (Goldfarb, 2010), with mineral assemblages of alteration such as chlorite, sericite, calcite, tourmaline, dolomite, hematite and rutile in proximal zones (Eilu, 1999). Mineralizing fluids have a low salinity range between 2- 10 wt% NaCleq, high CO2 content commonly observed in liquid phase in the system H2O CO2 ± CH4, and homogenization temperatures between 200 and 400°C (Wilkinson ., 2001). Most gold-bearing veins in metamorphic belts occur as fault-fill shears (i.e. crack & seal structures) or fractures. Such veins are laminated or banded; locally contain breccia fragments and elongate ore-shoots in some places (Goldfarb et al., 2005). Emplacement of these deposits occurs in forearc and arc settings (Figure 3), to variable depths that range between 2 and 20 kilometers. Thus, depending on formation depth of the deposit, Groves et al., 1998 classified them as hypozonal, mesozonal and epizonal orogenic deposits (see Figure 2). Also, these deposits are spatially and temporally related to transcortical faults and granitic magmatism could be associated (Groves et al, 1998). Figure 2. Epigenetic gold deposits in metamorphic terranes (After Goldfarb et al., 2005; Groves et al., 2003; Groves et al., 1998). 3 1.2 Intrusion-related gold systems Intrusion-related gold systems (IRGS) are best developed in intrusions emplaced in the region behind an accretionary orogen (Groves et al., 2003, figure 3), involving that ore formation is synchronous with granitoid crystallization (Goldfarb et al., 2005). Zonation of ore mineral assemblages outward from the central, mineralizing intrusive body is common, and there is an increase in structural control on more distal mineralized veins from the pluton (Hart, 2007). Opposite to orogenic gold deposits, the intrusion related gold systems are characterized by a wide range of gold grades (generally low) and mineralization styles. The most distinctive characteristic of this deposit types are sheeted array of parallel quartz veins with low sulfide content (Hart et al., 2005). Mineral assemblages are mainly pyrrhotite, pyrite, loellingite, arsenopyrite, and scheelite, with gold intergrowth with bismuth or tellurium and locally molybdenum or scheelite. Commonly there is a lack of copper minerals (Goldfarb et al., 2005). In addition, there is no relation of gold with the presence of wolfram in scheelite (Hart, 2007). Fluid inclusions of IRGS consist of low salinity to high salinity fluids (2 – 40 wt% NaCleq), based in the presence of the one high salinity fluid brine recognized in the majority of IRGS deposits (Mernagh et al., 2007), variable amounts of CO2 and homogenization temperatures between 160 to 380° C. However, fluids that formed Ag-Pb-Zn veins lack of significant CO2 (Hart, 2007). Magmatism and the associated mineralization is completely post-orogenic, and the mineralizing fluids are the cooling result of the igneous bodies instead of fluids coming from the dehydration generated by a metamorphic event (Hart et al., 2005). Figure 3. Different deposit types according to different tectonic settings. (After Groves et al., 2003). 4 1.3 Fluid inclusion studies Fluid inclusions trapped within crystals in hydrothermal veins are recognized as an important tool for describing the nature of mineralizing fluids and processes by which mineral deposits were formed (Wilkinson, 2001). Often, fluid inclusions are present in minerals as different phases such as liquid (L), liquid and gas (L+V), and liquid, gas and solid (L+V+S). Also, fluid inclusions are classified according to the timing of formation of the inclusion relative to that of the host mineral (Samson, et al. 2003). So, fluid inclusions are classified as: -Primary: Inclusions formed during the growth of the host crystal. Hence, they represent the original fluid from which the host crystal formed. -Secondary: Inclusions formed within fracture planes after crystal growth is complete. - Pseudosecondary: They are formed within fractures at the same growing time of the host crystal. Primary and pseudosecondary inclusions are important because they are representative of the ore forming fluid (Wilkinson, 2001). So, measuring different temperatures in microthermometric experiments of cooling and heating inclusions gives important information such as temperature of formation, density, pressure, salinity and volatile content of the mineralizing fluid (Hollister, 1981). Following temperatures must be measured and introduced in different fluid inclusions software that contains empirical equations of state that estimate those fluid characteristics: - Eutectic temperature (Te): When the fluid inclusion is frozen, it corresponds to the temperature at which the inclusion starts to melt. This temperature is useful to determine of the fluid composition (i.e. fluid volatile system). - Final fusion of ice temperature (Tffh): It corresponds to final fusion temperature of ice and it is useful to determine salinity in fluid systems with medium to low content of carbon dioxide (CO2) and methane (CH4). - Final fusion of clathrates (Tffc): Clathrates are gas hydrates trapped into ice cubic structures during cooling experiments (Samson et al. 2003) that play an important role in defining salinity in CO2 - CH4 gas saturated systems (i.e. orogenic or mesothermal deposits). 5 - Homogenization temperature (Th): This temperature is interpreted as trapping temperature of the inclusion. This happen when all phases inside inclusion homogenize into same phase (liquid or vapor) in heating experiments. 2 TECTONIC FRAMEWORK AND REGIONAL GEOLOGY 2.1 TECTONIC FRAMEWORK The Colombian Andes are arranged in three north-south trending mountain ranges denominated as Eastern, Central and Western Cordilleras (Blanco-Quintero et al., 2014). The study area is included into the Central cordillera tectonic domain, which comprise the Cajamarca Complex and other accreted terranes of oceanic and continental affinity called Arquía and Quebradagrande complexes. The Central Cordillera is a tectonic domain composed of a pre-Mesozoic basement corresponding to a low-pressure metamorphic belt (i.e. Cajamarca Complex), which is intruded by Mesozoic and Cenozoic plutons related to the subduction of oceanic lithosphere (Taboada , 2000). Also, the Central Cordillera is limited by the Otu-Pericos (at east) and Cauca-Almaguer (at west) strike-slip faults (BlancoQuintero et al., 2015). Moreover, on the western side of the Central Cordillera, San Jeronimo and SilviaPijao faults define the Romeral fault system that separate terranes of oceanic and continental affinity. Those are strike-slip fault characterized by transpressive movements and their distribution follow an echelon pattern parallel to the Garrapatas Fault (Figure 4), that is possibly related to the accretion of segments of oceanic crust to the west of the cordillera (Taboada, 2000). Study area is influenced by Palestina Fault which is more than 350 kilometers long on the strike, and between 50 to 600 meters wide. Strike movement of this fault follows a regional structural tendency to the north-northeast, and cut off a variety of rocks in the central cordillera (Rodriguez, 2007). According to Feininger (1970) this fault formed as response to a single unchanging regional stress system, and his reactivation produce subordinate structures such as Chapetón-Pericos, Ibagué, El Bagre, Nus and Otú faults. 6 On the other hand, Leal-Mejia (2011) relates the Palestina Fault to an early middle Paleozoic suture between Cajamarca and the early Paleozoic continental margin of northwestern South America. Moreover, the nature and origin of regional-scale faulting is important for metallogeny of gold deposits because those structures allow the emplacement of fertile magmas and the circulation of deep-seated hydrothermal fluids. Thus, subordinate and major faults as the mentioned above are important for the emplacement of dykes and hydrothermal fluids, which lead to precipitation of ore forming minerals (Leal-Mejia, 2011). Figure 4. Fault and suture systems of Colombia. EC: Eastern Cordillera, CC: Central Cordillera, WC: Western Cordillera. (Modified from Leal-Mejia (2011); after (Cediel et al., 2003)) 7 2.2 REGIONAL GEOLOGY The studied mine is located in a tectonically complex area that includes different geological units belonging to the Cajamarca Complex. Also, intrusive and extrusive igneous rocks such as Andesites and the “El Hatillo” stock are present surrounding the mine. Other metamorphic and sedimentary rocks crop out at few kilometers of the studied area (Figure 5). Those units are the Tierradentro amphibolites, Santa Teresa and Honda sedimentary groups. Figure 5. Regional geologic map (Modified from 207-Honda and 226-Libano geological maps produced by the Servicio Geologico Colombiano, 1:10000 scale). CAJAMARCA COMPLEX The Cajamarca complex comprise the core of the Central Cordillera (Maya and Gonzales, 1995), it comes out largely to the west of the department of Tolima and consists mainly of green schists and black schists in greenschist to amphibolite facies. Micaceous schists, amphibole schists, quartzites and amphibolites are also found in lesser amounts. All rocks mentioned above are products of the regional metamorphism from medium to low grade. 8 According to Blanco-Quintero (2014) metabasites and pelitic schists show a strong penetrative foliation, locally related to mylonitization which suggest intense dynamic-thermal metamorphism. The protoliths of these rocks was probably a marine volcano-sedimentary pile formed by lava flows and sediments enriched in organic material (Nuñez, 2001). An age between Proterozoic and Cretaceous has been proposed for this complex, but specific age has not yet been determined. A Permo-Triassic age was proposed for the last important thermal event of the Complex (Restrepo, et al., 1978; Spikings (2015) after Cochrane (2014)) propose an age of 236 ± 0.6 Ma through U / Pb dating and 221.8 ± 1 Ma by Ar / Ar, and BlancoQuintero et al., (2014) reported late Jurassic metamorphism ages between 147 and 158 Ma through Ar/Ar dating methods. TIERRADENTRO AMPHIBOLITES This complex was described by Barrero and Vesga (1976) as quartz-feldespatic stripped gneisses with local variations to amphibolites, product of regional metamorphism that extends on a NE direction on the eastern flank of the Central Cordillera. Associated with this unit there are also marbles, quartzites and granulites. These rocks have been dated as Proterozoic using the whole-rock K-Ar method (1350 ± 270 Ma, after Kroonenberg, 1982; Álvarez, 1981). On the other hand, the complex is found in fault contact with rocks of the Cajamarca Complex to the west, and Santa Teresa Group along with the Ibague batholith to the east. EL HATILLO STOCK This pluton is found intruding the Cajamarca Complex and is overlapped by sediments of the Honda Group. It is an equigranular body of dioritic composition with local variations to hornblende gabbro (Rodríguez, 2007). K/Ar radiometric dating gives an age of 53 ± 1.8 Ma corresponding to Paleocene-Eocene. The quartz diorite is commonly found with narrow aureoles of hornfels at the contact with rocks of the Cajamarca Complex as consequence of contact metamorphism. Also, some auriferous mineralized veins are found associated with this intrusive body (Nuñez, 2001). 9 HONDA GROUP The Honda Group outcrops from south to north within the Tolima department, along the southern end of the Middle Magdalena Valley. In this area, correspond to grey and red sandstones and mudstones in the lower part of the group, including conglomerates and sandstones. Also, in the upper part there are red mudstones and fine grained sandstones. The thickness of this sedimentary group ranges between 120 and 1200 meters. Based on Ar/Ar dating, Guerrero (1993) gives ages of 11.0 to 13.5 Ma. SANTA TERESA GROUP According to INGEOMINAS (1976) this sedimentary group is composed of mudstones, sandstones and conglomerates with presence of metamorphic boulders. For this unit was proposed a Paleozoic age by Gonzáles et al., 1995. QUATERNARY ROCKS These are mainly volcanic deposits that consist of lavas and pyroclastic deposits. The lavas are Andesites with pyroxene and augite (INGEOMINAS, 1976). Those deposits probably are product of highly explosive events from the Cerro Bravo, Cerro Machin, Nevado del Ruiz and Nevado del Tolima volcanoes (Rodríguez, 2007). 10 3. GEOLOGY OF THE MINING AREA The “Gran Porvenir del Libano” mine is divided in ten levels, where mineralized quartz-calcite veins occur as branch lodes with banded, brecciated and massive textures (Figure 6). These veins are cutting graphitic and chloritic schists (Figure 7a) in greenschist facies belonging to the Cajamarca Complex. Figure 6. Vein textures observed in the field. Almost three different quartz veins concordant with the host rock foliation (45 to 70° inclination to NW) are recognized within the conjugated system. The first one is a branch vein of massive quartz, locally brecciated (Figure 7b) containing euhedral (cubic) pyrite, galena, locally scheelite and carbonates. This vein is up to 3 meters wide and dips 42 ° to NW. The second vein is found cutting the massive vein (Figure 6) and is of the “crack and seal” type with banded-laminated textures. 11 It is called “veta techo” by locals, and is the principal continuous vein structure along the deposit with dips ranging between 40-70° to NW and an average thickness of 1.5 meters, locally up to 6 meters in ore-shoots. Gangue minerals in this vein are quartz and late calcite accompanied by auriferous sulfides including pyrite, pyrrhotite, galena, sphalerite and chalcopyrite, which are concentrated between bands of graphite (Figure 8a). Third vein is another branch that also has banded texture, similar mineralogy to the previous one, and visible grains of gold that could be observed near the contact with the host rock (Figure 8b). Additionally, supergene enrichment of chalcopyrite occurs in some parts of the mine, where malachite was observed. Figure 7.a) Contact between chlorite schists (up) and graphite schists (bottom). b) Massive brecciated vein. 12 Figure 8. a).Crack and seal type quartz-carbonate vein with proximal alteration zone. Abbreviations: Py = Pyrite, Sph = Sphalerite, Gal = Galena, Cpy = Chalcopyrite, Po = Pyrrhotite, El = Electrum. b). Quartz vein showing visible electrum near the graphite bands. Scheelite-ferberite-dolomite mineral associations are accompanied by minor amount of sulfides as “lenses” between graphite bands in the lower part of the banded principal vein (Figure 9a) Also, drusiform quartz is found in the center of the scheelite horizon filling cracks or spaces between scheelite and dolomite (Figure 9b). Figure 9. a) Scheelite and dolomite within graphite bands at the base of banded vein. b) Drusiform quartz at the center of the lens filling spaces between scheelite and dolomite 13 Native silver veinlets and silver sulfosalts accompanied by quartz were observed cutting banded veins forming breccia textures in sulphides (Figure 11a). On the other hand, hydrothermal alteration occurs in proximal areas adjacent to the quartz veins mainly with sericite, carbonates, chlorite and white micas (Figure 8a) leading to an alteration known as carbonation and sericitización, however alteration haloes are narrow (<10 cm) and localized. Mineralization is controlled by “La Chucula” conjugate riedel fault system (Jimmy Torres, personal communication 2017) , but in site only sinistral strike-slip faults were observed with 330° NW strike and near vertical dip (Figure 10). Locally, dilational jogs (Figure 11 c) and pinch & swell structures are produced due to the shear tectonic regime in the zone. Moreover, dykes and silos are present within (Figure 11c), under and over the veins (Figure 9) locally containing fragments of mineralization. Those dykes display a pervasive sericitic alteration and carbonation, and change in color from center to borders could be observed in some of them (Figure 11 b). Figure 10. Strike-slip fault from “La Chucula” conjugate fault system. 14 Figure 11. a) Silver and silver sulfosalts cutting sulphides within quartz veinlets. b) Igneous intrusive dyke with color change from center to borders within banded vein c) Dilational jog produced due to shear tectonic regime. 15 4. METODOLOGY 4.1 Field Work Fieldwork was carried out on November 2017 and January 2018 in the Gran Porvenir S.A mine, from which the corresponding permission was obtained to access the tunnels. The underground mine has ten levels with north and south mining fronts. Samples of mineralization, host rocks, and dykes found in the host rocks and the mineralized veins were taken (Table 1) as well as structural measurements. SAMPLE ROCK TYPE LEVEL ELEVATION(m) P1 Quartz massive vein One north 1621 VO-1 Mineralization One south 1630 P-5 Mineralization Five north 1506 E2 Host Rock Eight north - E3A Host Rock Eight north - 9N Mineralization Nine north 1452 9S Mineralization Nine south 1450 9S-Ag Mineralization Nine south 1448 9R2 Mineralization with Scheelite Nine north 1450 PV2 Mineralization Nine north 1450 PV3 Mineralization Nine north 1450 DA1 Host rock with dyke Nine north 1450 10N Mineralization with Scheelite Ten north 1420-1435 10ALT Mineralization with dyke Ten north 1420-1435 10ALT2 Host rock with dyke Ten north 1420-1425 DH-15 Altered porphyritic rock - Depth : 305,9 m DH-16 Altered porphyritic rock - Depth : 47,5 m Table 1. Table of collected samples. Samples from the first level, between first and second level, fifth level, nine level and tenth level are listed above (Table 1). Additionally, five samples (PV-1, PV-2, PV-3, PV-4 and PV-5) of mineralization were borrowed from Professor Julian A. Lopez I. from Colombian Geological Service (SGC in Spanish), as complement to The Metallogenic Map of Colombia. The collection of samples was based on the properties of rock and mineralization content, with the purpose of covering most 16 of the characteristics of the mineralogy and the relationships between ore minerals, host rocks and alteration phases. 4.2 Laboratory work Samples were cut at the sample preparation laboratory of Geoscience department at Universidad de los Andes into thirteen polished thin sections (Table 2). Those samples were chosen taking into account the mineral association representativity and the relationships between gangue and ore phases. Other samples were cut with the purpose of observing macroscopic features of the mineralization. SAMPLE P1 VO-1 P-5 E2 E3A 9N 9S 9S-Ag 9R2 PV2 DA-1 10ALT DH-15 DH-16 POLISHED SECTION P1 VO-1 5A E2 E3A 9N 9S 9S-Ag 9R2 PV2 DA-1 10-ALT DH-15 DH-16 ROCK TYPE Quartz massive vein Mineralization Mineralization Host rock Host rock Mineralization Mineralization Mineralization Mineralization with Scheelite Mineralization Host rock with alteration Mineralization with alteration Altered porphyry Altered porphyry LEVEL 1 1 5N 8N 8N 9N 9S 9S 9N 9N 9N 10N - Table 2. Polished thin sections prepared. 4.3 Petrography Optical microscopy studies of 13 polished thin sections (30 μm) in transmitted light were done in order to determine textural relationships between translucent and opaque minerals (Table 2). Transmitted light was also used to discriminate different fluid inclusion families and their characteristics. Otherwise, studies in reflected light were done to describe ore minerals phases, their relationships, and mineral paragenesis. 17 4.4 Scanning electron microscopy (SEM) Semi-quantitative chemical composition analyses (EDS) of different gangue and ore minerals were realized in twelve carbon-coated polished thin sections belonging to the mineralized quartz veins. These analyses were carried out using the scanning electron microscope JEOL, model JSM 6490 LV at the microscopy center in Universidad de los Andes with a 20kV acceleration voltage and 0.5 to 300.000 X magnification. 4.5 Fluid Inclusion Studies Once the families of fluid inclusions were identified in the Petrography phase of the work, quantitative analysis of fluid properties such as density, composition, pressure and temperature of entrapment were carried out in the Laboratorio de Microfluidespectral-Caracterización Litológica at Universidad Nacional de Colombia, using a Zeiss Axio Microscope, and a heating plate Linkam 600. This process is done by cooling and heating pieces at 4°C per minute of crystals or chips of selected double polished thin sections. Next step consist on determining eutectic, final fusion salt, final fusion ice, and homogenization temperatures of the fluid inclusions. Then, the results are processed in fluid inclusion analysis software such as FLUIDS or CLATHRATES depending on the inclusions type (Baker, 2001). 4.6 Ramman Ramman spectrum analysis was carried out in order to probe the presence of volatile species in fluid inclusions, and elucidate the semi-quantitative composition of them. This work was done in the Laboratorio de MicrofluidespectralCaracterización Litológica (Microscopía y Microtermometría) at Universidad Nacional de Colombia with a SHAWN Ramman with a diameter of laser of 732 nm and Laboratorio de Química Inorgánica at Universidad de los Andes with an Olympus Ramman microscope with a diameter of laser of 732 nm. Then, obtained Ramman spectrum of different minerals was compared with RUFF International database using Crystal Sleuth software. 18 5. RESULTS 5.1 Petrography 5.1.1 Host Rocks 5.1.1.1. Quartz-chlorite-sericite schists (E2, E2A) These samples comprise foliated granolepidoblastic metamorphic rock (S1), with microfolds also called crenulation folds (Figure 12 e, f), which define a superimposed foliation (S2). Is composed primary of quartz (33%), chlorite (27%), white micas (15%), albite (7%), sericite (6%) and epidote (3%). Carbonate (10%) veinlets are cutting main metamorphic foliation (S1) and the secondary microfolding foliation (S2) (Figure 12 a, b). Main mineral associations are: quartz and chlorite-white micas- epidote (Figure 12. c, e). These associations are separated by bands of quartz with different sizes (Figure 12d). Moreover, quartz shows deeply contact sutured (grain boundary migration), mosaic, and wavy/shadowy extinction textures (Figure 12d). Also, massive aggregates of quartz are present within the foliation (S1). Alteration phases are present as sericite, calcite (Figure 12 c, d, e) and quartzcarbonate veinlets with euhedral to subhedral grains. However, metamorphic and hydrothermal chlorite cannot be distinguished. Based on mineral association, proposed protolith for this rock corresponds to a pelite. Moreover, quartz textures and microfolding in the rock would correspond to a high deformation tectonic event, as the development of crenulations are accompanied by an intense mineral segregation ; with quartz concentrated at hinge on the microfolds and micas in the flanks (Figure 12e ,Yardley, 1997). Finally, metamorphic facies of this rock would correspond to greenschist facies from medium to high temperatures. 19 Figure 12 a) XPL Calcite veinlets cutting metamorphic foliation. b) PPL calcite veinlets cutting metamorphic flotation S1 and S2. c) XPL White micas intergrown with chlorite accompanied by quartz and calcite d) XPL Foliated quartz bands of different sizes showing recrystallization textures accompanied by chlorite, white micas and calcite e) XPL Mineral association of quartz, white micas, chlorite, clinozoisite and alteration calcite. f) Metamorphic foliation S1 cut by crenulation foliation S2. 20 5.1.1.2. Graphitic schists (E3A) This sample shows metamorphic lepidoblastic foliation (Figure 13a). Microfolding or crenulation foliation (S2) is observed superimposing metamorphic foliation (S1) (Figure 13 c, f). Additionally, another foliation (S3) recognized as transposition foliation is cutting the previous ones. This foliation could be recognized because of orientation of some graphite-white micas bands affecting sulphides mineralization (Figures 13 c, f). Some foldings within foliation are asymmetric with chevron structure (Figure 13 e). Graphitic schists are composed of sutured contact quartz (45%), graphite (30 %), white micas (17%) intergrowth with chlorite (3%), and calcite (5%). Mineralization of pyrite, chalcopyrite and sphalerite is observed within microfolds (S2) following the main foliation of the rock (S1) (Figure 13 d, f). Nonetheless, foliation S3 is cutting off pyrite folds (Figures 13 c, d, and f). Principal mineral associations are: quartz and graphite - white micas. Same as E2 sample, quartz show deeply sutured contacts, mosaic, bulging, and grain boundary migration textures (Figure 13 a, c). Also, some wavy and shadowy extinction quartz was observed. Alteration phases are present as minor amounts of sericite and calcite. Folded and intra-foliation pyrite are accompanied by overgrown chalcopyrite on the borders (Figure 13 b, f). Furthermore, chalcopyrite, sphalerite and hematite are present disseminated as anhedral crystals within the foliation (Figure 13 b). Finally, based on mineral association, protolith of this rock would correspond to a metapelitic rock enriched in organic material. 21 Figure 13. a) XPL Intra-foliation pyrite accompanied by white micas and quartz with recrystallization textures. b) Reflected light microphotograph (RLM) of intrafoliation pyrite (Py) accompanied by chalcopyrite (Cpy) and sphalerite (Sph) c) XPL Crenulation foliation (S2) cutted by foliation S3 d) RML intrafoliation folded pyrite affected by foliation S3 e) PPL Chevron-like folds of graphite + white micas and quartz. f) RML intrafoliation folded pyrite accompanied by chalcopyrite following S1 and S2 foliations cutted by S3 foliation. 22 5.1.2 Igneous Porphyry Dikes 5.1.2.1. DH-16: This sample corresponds to a drill core within the Cajamarca Complex near the veins. The section shows a porphyritic texture with euhedral to subhedral phenocrysts of medium to fine grained plagioclase and hornblende partially replaced by sericite and calcite ( Figure 14 a,b,c) , surrounded by a microcrystalline matrix of albite and sericite. Additionally pyrite and sphalerite (< 1%) are present as disseminated grains with subhedral to anhedral morphologies (Figure 14 d). This section consists of 58% matrix and alteration phases, and 42% phenocrysts. Those phenocrysts are plagioclase with partial loosing of polysynthetic twinning (Figure 14 a) (55%), hornblende (35%), fine grained quartz (5%) and orthoclase (5%) recognizable by its baveno characteristic twin. So, this porphyry rock is classified as an Andesite according to the Streckeisen (1976) classification for extrusive rocks. The hydrothermal alteration in this rock, as in DH-15, is strongly pervasive of the carbonatization-sericite type, accompanied by minor amounts of sulphides. Presence of pyrite in this porphyritic rock could be explained by the sulphidization of mafic phenocrysts such as hornblende. Figure 14. a) XPL Hornblende (Hbl) and plagioclase (Pl) ghosts. b) PPL image of a). c) XPL Hornblende after intense sericitization and carbonatization. d) Disseminated anhedral pyrite (Py). 23 5.1.2.2. DH-15: This sample occurred as a drill core within the Cajamarca Complex near the hydrothermal veins. Phenocrysts in this sample are completely replaced by calcite and sericite, with minor amounts of white micas, and iron oxides (Figure 15). This is due an intense pervasive alteration that is known as carbonatization. Original texture of the rock has disappeared and only “ghosts” of phenocrysts can be distinguished. Subhedral quartz is present as a minor phase and calcite veinlets are cutting the rock (Figure 15 c, d). Also, opaque minerals such as disseminated euhedral to subhedral grains of pyrite are present (Figure 15 e, f). Figure 15. a) XPL Subhedral quartz aggregates and pervasive carbonatization and sericitization of the rock. b) PPL of a). c) XPL Calcite veinlet, sericite and iron oxides as alteration phases in the rock. d) PPL of c) e) XPL Sericite and white micas accompanied by disseminated subhedral pyrite. f) PPL image of e). 24 5.1.3 Quartz Veins 5.1.3. 1. Sample from the first level P1: This sample is a translucent pyramidal quartz that was collected from a banded quartz-scheelite-sulphides vein (Figure 4) with euhedral cubic pyrite and galena filling open spaces (Figure 16 a). Almost twenty families of secondary fluid inclusions with similar characteristics are observed in this section. They can be distinguished as secondary because are following fracture planes on quartz and are superimposing between them. However, all inclusions are biphasic of the liquid-gas type and its morphologies are ovoid, tear-like, and polygonal. Those inclusions has “double ring” in the bubble as consequence of highly amounts of CO2 in the parental fluid. In addition, water bubbles are very small in comparison with CO2 bubble and sometimes are moving as response of the Brownian movement. Moreover, one family of primary fluid inclusions is recognized by its size and rectangular shape, following a tridimensional array (Figure 16 b). This family has the same characteristic of double ring equal as the previous described. Additionally, the proportion between fluid and gas phase maintains constant along this family. So a homogeneous entrapment could occur when these inclusions were formed. Figure 16. a) Photograph of sample P1. Pyramidal quartz could be seen in the bottom right, also galena is filling spaces within quartz crystals. b) PPL Primary fluid inclusion family with double ring. 25 VO1: This sample was collected in another family of hydrothermal quartz veins known as “El Oasis” which share similar characteristics with “El Porvenir” veins. Both families of veins are separated a distance of ca. 800 m. This section consists of quartz with different grain sizes and dynamic recrystallization textures such as grain boundary migration and bulging. Quartz is accompanied by bands of graphite and sericite-white micas, sometimes showing stylolitic seams (Figure 17 a). Furthermore, mineralization of sulfides is confined within graphite bands with sericitic alteration at both sides (Figure 17 b). Alteration in this sample is of the sericitic type with minor amounts of rutile within graphite (Figure 17 a, b). Almost two generations of pyrite are distinguished. The first one is coarse-grained, subhedral and highly fractured, with interstitial galena-electrum and sphalerite (Figure 17 d, e). The second one is euhedral, without fractures and is present within or near graphite bands. Sphalerite is subhedral and shows an orange red color in transmitted light. It has emulsion texture of chalcopyrite and contains oriented galena inclusions (Figure 17 c, d). However, sometimes those are intergrown. It is also affecting pyrite borders (amoeba texture) and is present as anhedral crystals within graphite bands. Galena is related to gold (electrum), because both are intergrown within pyrite fractures (Figure 17 e). Also fine grained subhedral crystals are contained within graphite bands and in contacts with them. Pyrrothite is present as minor inclusions within coarse grained pyrite. Moreover, secondary fluid inclusions were found within quartz near graphite bands, those inclusions are biphasic liquid-gas with double ring following fracture planes (Figure 17 f). Proportion between gas phase and fluid phase are not constant within the different families, so a heterogeneous entrapment could have occurred when the inclusions were formed. 26 Figura 17. a) XPL Stylolitic seam of graphite with sericite. Also, quartz show dynamic recrystallization textures. b) XPL Brecciated and fractured pyrite accompanied by sericitic alteration. c) PPL Orange sphalerite (Sph) with oriented inclusions of galena (Gn) and chalcopyrite (Cpy) exsolutions. d) Reflected light image (RLI) of galena filling fractures of pyrite and as oriented inclusions in sphalerite. e) RLI of pale yellow electrum (El) intergrowth with galena filling pyrite fractures. f) PPL Biphasic fluid inclusions following planes. 27 5.1.3.2. Fifth level samples - 5A: This sample was collected in a rich gold zone according to the mining geologist Jimmy Torres (personal communication, 2017). This section shows quartz with dynamic recrystallization textures such as grain boundary migration, bulging, wavy extinction and deformation lamellae (Figure 18 a).Also, another type of quartz is found with comb texture growing over pyrite (Figure 18 b). Moreover, continuous graphite bands with sericite “stylolitic seams” are accompanying mineralization (Figure 18 a, b, e), and euhedral crystals of calcite are overgrowing these graphite bands (Figure 18 b). However, quartz grain size decreases near the band of graphite, also showing a major recrystallization between graphite and calcite. Rutile is present as alteration phase within graphite bands (Figure 18 c, Figure 19 d). Ore minerals are disseminated as individual or intergrown crystals. Almost two generations of pyrite can be observed; the first one is coarse grained, subhedral, massive habit and with fractures filled with galena (Figure 18 f). The second one (Figure 18 d and Figure 19 a, b, d) has medium grain size (ca. 200 μm) and fractures filled with electrum (ca. 100 – 20 μm). Electrum shows high reflectance and a pale yellow-white color, and this could be caused by the relationship gold: silver. However, another type of electrum with strong yellow color but minor grain size is included within pyrite (Figure 19 b). In the borders, this pyrite has overgrowing electrum, sphalerite and galena (Figure 19 d). Sphalerite is present as anhedral massive crystals of brown to orange color and contains pyrite cubic inclusions; it also has emulsion textures of chalcopyrite and overgrowths of electrum in the borders (Figure 18 e, f). Another sphalerite with strong red color and without emulsion textures was identified (Figure 19 c). Last one sphalerite has bigger grain size than the first one. Galena shows typical polishing “pits”, is subhedral and is found interstitially, overgrowing sphalerite and pyrite and accompanying electrum (Figure 18 f and Figure 19 d). Additionally, galena and sphalerite are found as anhedral crystals within graphite bands. Electrum is found within pyrite and in contact with graphite-sericite stylolitic seams. As could be seen in figure 19 a, b, d, and figure 18 c, d. Two types of electrum were identified; type 1 (within pyrite, fine grained) and 2 (free or in crystal-graphite borders), the second one sometimes present as large size crystals (100-200 μm). 28 Figure 18. a) XPL Quartz showing dynamic recrystallization textures accompanied by subhedral cubic pyrite within graphite bands. b) XPL Quartz showing comb texture over pyrite. Also calcite is overgrowing quartz and pyrite. c) RLI Subhedral cubic pyrite filled with electrum (El) , also free electrum in contact with graphite (Gr) –sericite (Ser)- rutile (Rt) bands. d) RLI Electrum (El) in borders and within fractures of pyrite, accompanied by sphalerite and galena. e) PPL Orange sphalerite with emulsion texture of chalcopyrite. f) RLI Interstitial galena filling fractures of massive pyrite overgrowth by emulsion-like sphalerite. 29 On the other hand, biphasic secondary fluid inclusions were found near host rock following planes perpendicular to orientation of quartz veins. They show “double ring” structure and proportions between gas and liquid seem to be constant (Figure 19 e). Other family of fluid secondary biphasic fluid inclusions was found near one free electrum grain of 200 μm (Figure 19 f). This family doesn’t present constant relation of volume gas, which suggests heterogeneous entrapment. Inclusions of both families has tear, ovoid and elongated morphologies and sizes range between 5 and 8 μm. Figure 19. a) RLI Electrum (El) on pyrite borders. b) RLI Electrum dot within pyrite, also radial fractures are observed around this electrum grain. c) PPL Iron sphalerite (Sph) including pyrite and overgrowing quartz. d) Rutile (Rt) + Graphite (Gr) + Sericite (Ser) band accompanied by electrum, galena and cubic pyrite. e) PPL Biphasic fluid inclusions following planes. f) PPL Biphasic fluid inclusions following planes near free anhedral electrum crystal. 30 5.1.3.3. Ninth level samples 9S This section shows quartz with recrystallization textures such as grain boundary migration, bulging and deformation lamellae. Also, quartz presents wavy extinction (Figure 20 a, b). Dolomite and calcite are present as an introduction mineral and brecciate pyrite and quartz (Figure 20 d). Alteration mineral assemblages are characterized by white micas, sericite, tourmaline and rutile within altered wallrock (graphite) bands (Figure 20 a, c and d). Ore minerals are conformed by pyrite, chalcopyrite, sphalerite, galena, pirargyrite and electrum. Euhedral to subhedral pyrite is found with breccia textures and fractures (Figure 20 c, d), those fractures are filled with chalcopyrite or galena (Figure 20 c, d, e). This pyrite is also accompanied by alteration mineral phases and contains sphalerite and galena as unoriented inclusions. Sphalerite is anhedral, has a red color and is found within pyrite crystals. Another fine-grained anhedral sphalerite is present surrounding chalcopyrite. Moreover, subhedral to anhedral galena is intergrowth with electrum or chalcopyrite. Galena could be seen as unoriented inclusions within pyrite or filling fractures. Chalcopyrite is coarse grained (1-5 mm), is euhedral to subhedral, and is accompanied by calcite overgrowing quartz crystals (Figure 20 b). Pirargyrite displays a grey color and red internal reflections, is found within calcite near chalcopyrite or within chalcopyrite itself (Figure 20 f). Two different electrums were distinguished. First one is found within pyrite as yellow anhedral inclusions (15 um) (Figure 20 d), and the other one displays pale yellow color and is intergrowth with galena (Figure 20 e). 31 Figure 20. a) XPL Dynamic recrystallization textures on quartz and sericitic alteration accompanying mineralization of pyrite (Py) and Sphalerite (Sph). b) XPL Calcite (Cal) after chalcopyrite (Cpy) filling spaces between quartz crystals. c) Reflected light microphotography (RLM) of brecciated pyrite with chalcopyrite and galena within fractures. d) RLM Strong yellow electrum (El) and galena as inclusions within Pyrite. Also, sericite (Ser) + graphite (Gr) are present as alteration phases. e) RLM Pyrrothite and electrum intergrowth with galena as inclusions within pyrite. f) RLM Brecciated pyrite due to chalcopyrite. Also, pirargyrite (Pyrg) is present within and outside chalcopyrite. 32 9S-Ag In this sample two different quartz were identified. The first one, is coarse grained and fractured. The second one is fine grained, displays intense recrystallization textures (GMB, bulging) and deformation lamellae (Figure 21 a). Alteration mineral phases are white micas- sericite within graphite bands. Moreover, ore minerals in this section are pyrite, sphalerite, galena, chalcopyrite, and silversulfosalts. Pyrite is found as euhedral cubic (10-370 um) aggregates (Figure 21 c) with unoriented galena inclusions sometimes embedded within sphalerite (Figure 21 f) and as massive (8 mm) brecciated crystals with fractures filled with galena, chalcopyrite and silver-sulfosalts (Figure 21 b). Sphalerite is clean and displays a brown pale color (Figure 21 d). It is anhedral and occurs in borders of massive pyrite also having same size and containing galena and silver-sulfosalts inclusions. Galena is subhedral, occurs in borders of euhedral pyrites, sphalerite, and is intergrowth with silver-sulfosalts and chalcopyrite (Figure 21 b, e). Silver-sulfosalts are solid solutions between argento-tetrahedrite and argentotennantite (Figure 21 e), and display grey-greenish color with deep red internal reflections. Those sulfosalts are found filling fractures of brecciated pyrite (Figure 21 b), within pyrite, sphalerite or in contact with them. Also they are accompanied by chalcopyrite-galena and sizes range between few microns up to 1 mm. 33 Figure 21. a) XPL Quartz showing different grain sizes and recrystallization textures around cubic aggregates of pyrite. b) Reflected light microphotography (RLM) of massive pyrite fractured and filled with intergrowths of galena (Gal) and polybasite (Pol). c) Aggregates of euhedral cubic pyrite overgrown by sphalerite and galena. d) RLM of Pale brown sphalerite accompanied by pyrite and quartz. e) RLM Polybasite crystal with exsolutions of argento-tennantite (Ag-tn) after cubic pyrite. f) RLM Aggregates of cubic pyrite embedded within sphalerite (Sph) and galena (Gn). 34 9N Same as the previous samples, quartz displays dynamic recrystallization textures such as GMB, bulging, etc. (Figure 22 a). It is accompanied by introduction calcite and dolomite (Figure 22 b). Alteration mineral assemblages of white-micas, magnesium chlorite, tourmaline and rutile are present within graphite bands (Figure a, c, d). Tourmaline could be distinguished because his pyramidal habit with six faces in c axis. Also, display greenish to brown colors with strong zonation from center to borders. On the other hand, rutile displays high relief, acicular habit and yellow to green color (Figure 22 d). Ore minerals comprise pyrite, chalcopyrite and sphalerite, galena and electrum. Brecciated and fractured subhedral pyrite is found with skeletal textures due to dolomite and calcite introduction (Figure 22 b, e) and with intergrowth textures with chalcopyrite. It also has fractures filled with chalcopyrite (Figure 22 e, f). Chalcopyrite is subhedral and it occurs in borders of pyrite or filling fractures. It also is disseminated within dolomite. Galena occurs as intergrowths with chalcopyrite and as unoriented inclusions within pyrite. Yellow anhedral electrum within pyrite) and pale yellow dots of electrum within chalcopyrite (Figure 22 f) were distinguished. Those electrum grains range in size between 25 um and 63 um. 35 Figure 22. a) XPL Quartz showing dynamic recrystallization textures accompanied by bands of graphite (Gr) + Sericite (Ser) and White micas (Mca). b) XPL Skeletal pyrite due to introduction of dolomite (Do). c) PPL Alteration mineral assemblage: White micas (Mca) + sericite (Ser) + graphite (Gr) + tourmaline (Tur). d) PPL Alteration rutile (Rt) accompanied by graphite (Gr) e) Reflected light microphotography (RLM) of pyrite with galena (Gn) inclusions and chalcopyrite (Cpy) filling fractures. f) RLM Chalcopyrite overgrowing pyrite with pale yellow electrum inclusion (El). 36 9R This sample was taken from the vein that is showed in the figure 9 and shows brecciated and fractured scheelite (Figure 9a, b and Figure 24 a, e) with wavy extinction. It is accompanied by overgrowing dolomite, calcite and quartz with dynamic recrystallization textures (GMB, bulging, etc.) Also veinlets of clean quartz are cutting the scheelite and contain fragments of scheelite and dolomite (Figure 24 b). Some calcite twins seem to be deformed. The mineral assemblages of alteration are characterized by: graphite bands with sericite, white micas and magnesium chlorites (Figure 24 c). In this sample ore minerals are pyrite, sphalerite, galena and chalcopyrite. Two types of pyrite were recognized. The first one (Py 1) is fractured, subhedral with oriented inclusions of galena and grows around dolomite, calcite and scheelite (Figure 24 d). The second one is found filling fractures of scheelite accompanied by galena, dissease sphalerite and calcite (Figure 23 a, Figure 24 e). Sphalerite has strong red to orange color and display exsolution texture of chalcopyrite (Figure 23 b, Figure 24 f). Also, it has an overgrowing rim of calcite (Figure 24 c) while other clean sphalerite is filling spaces between carbonates (Figure d). Galena is subhedral to euhedral and is overgrowing pyrite, sphalerite, dolomite, scheelite and quartz (Figure 24 d) and it is also filling spaces and fractures. Figure 23. a) XPL Scheelite (Sch) fracture filled with pyrite and calcite (Cal). b) PPL Red to orange dissease sphalerite (Sph). 37 Figure 24. a) XPL Brecciated scheelite accompanied by calcite (Cal), quartz (Qtz) and late galena (Gn) b) XPL Quartz veinlet cutting scheelite (Sch) and dolomite (Do) c) XPL Sphalerite (Sph) with calcite rim, accompanied by quartz with recrystallization textures and sericitic alteration. d) Reflected light microphotograph (RLM) of pyrite (Py), sphalerite (Sph) and late galena (Gn) overgrowing calcite (Cal). e) RLM Pyrite, sphalerite and galena filling fractures within scheelite (Sch). f) RLM Sphalerite with exsolutions of chalcopyrite (Cpy) and galena inclusions (Gn). 38 5.1.3.4. Tenth level samples 10N This sample display sutured contact quartz with recrystallization textures (Grain boundary migration, bulging, etc.) and wavy extinction. On borders of quartz crystals recrystallization is intense and the size of crystals decreases by a factor of 50 (1.25 mm to 25 um). Quartz is accompanied by brecciated scheelite and ferberite (Figure 25 a). Calcite is an introduction mineral that remobilizes sulfides (Figure 25 b), wolphramates, and is also filling spaces between quartz crystals (Figure 25 a, b). Ferberite was distinguished because of his brown color in reflected light, low relief compared to scheelite, cleavage planes and red internal reflections (Figure d, e). Ore minerals are pyrite, pyrrothite, arsenopyrite, sphalerite, galena and chalcopyrite. Pyrite is present as subhedral cubic aggregates with embayments of sphalerite and galena, also pyrrothite and arsenopyrite (Figure 25 c) are present in borders or included. Sizes of pyrite range between 125 um and 1000 um. Sphalerite is strong red to orange and shows exsolution textures with chalcopyrite growing in cleavage planes (Figure 25 d, e, f). Its range size is between 125 um and 1.25 mm and has a subhedral morphology. Moreover, sphalerite is reddish at center and in cleavage planes that contains dots of chalcopyrite, it color turns to orange (Figure 23 b and Figure 25 f). This happen because chalcopyrite in those cleavage planes is incorporating iron in his mineral structure. Galena is crystallized within cleavage planes of other minerals, and as oriented inclusions in pyrite or sphalerite. Chalcopyrite is present as small anhedral crystals (5 um) within calcite or filling fractures on pyrite (Figure 25 d). 39 Figure 25. a) XPL Brecciated scheelite (Sch) accompanied by calcite (Cal) b) XPL Pyrite (Py) subhedral crystals embedded within introduction calcite. Also quartz (Qtz) shows recrystallization textures. c) Reflected light microphotograph (RLM) of arsenopyrite (Apy) filling empty spaces within pyrite. d) RLM Reddish brown ferberite (Fb) overgrown by dissease sphalerite (Sph) and pyrite (Py). e) RLM Ferberite (Fb) overgrown by galena (Gn), accompanied by anhedral pyrite and dissease sphalerite. f) PPL Red sphalerite accompanied by pyrite. Also another brown sphalerite with minor grain size is present at left. 40 5.1.4 Igneous dykes 5.1.4.1. 10 ALT This sample displays the contact between intrusive igneous dyke shown in figure 11 b, and the mineralized vein. In the contact zone, quartz is broken and the intrusive body is filling fractures on the quartz (Figure 26 a, b). In addition, quartz within the vein appear with sutured contact and shows deformation lamellae and recrystallization textures such as the mentioned before. Alteration mineral assemblages in the quartz vein are composed of graphite bands with tourmaline, rutile, sericite and white micas intergrown with calcite (Figure 26 c, d, and e). On the other hand, igneous dyke is completely altered and replaced by carbonates and sericite (Figure 26 a, b) with some disseminated pyrite and hematite (Figure 26 f). Ore minerals in this section are scarce and are disseminated cubic pyrite with galena inclusions (50 um) within graphite bands. 5.1.4.2 DA-1: This sample shows the contact between one intrusive dyke and graphitic schist (host rock of mineralization). In the contact zone there is possible to see high deformation on graphite and white micas of the schist (Figure a, b, c) in addition to recrystallization of quartz. Also some quartz aggregates with microcrystalline border, sutured contact and wavy extinction are present within the dyke (Figure 27 d). In those quartz aggregates, disseminated pyrite and chalcopyrite occurs (Figure 27 e) with carbonate rims. Also skeletal pyrite with inclusions of pyrrothite, chalcopyrite and galena inclusions is dragged into the graphitic schist (Figure 27c, f). 41 Figure 26. a) XPL Euhedral quartz crystals fractured due to completely altered intrusive igneous dike b) PPL Graphite (Gr) bands with sericite (Ser) and white micas (Mca). c) XPL Sericitic alteration accompanied by disseminated pyrite. d) PPL image of c). e) XPL Graphite bands with sericitic alteration (Mac+ Ser) overgrowth by calcite (Cal) f) Reflected light microphotograph (RLM) of disseminated euhedral pyrite. 42 Figure 27. a) XPL Recrystallized quartz within the contact of dyke and host rock. b) XPL Contact between intrusive altered dyke and host rock. c) XPL Graphitic schist with graphite bands (Gr) + white micas (Mca) and sericite (Ser). Also subhedral cubic pyrite is present inside the graphite bands. d) XPL Pervasive carbonatization and sericitization of the igneous dyke with quartz aggregates. e) Reflected light microphograph (RLM) of quartz aggregates with pyrite (Py) and Chalcopyrite (Cpy) inside the altered dyke. f) RLM Dragged skeletal pyrite with pyrrothite (Po) and chalcopyrite (Cpy) inclusions into graphitic schist. 43 5.2 Mineral paragenesis Based on mineral textures and cross-cutting relationships between minerals and mineralized veins, four mineralization events were recognized. The paragenesis of the mineralized veins is divided in massive quartz vein and crack & seal veins. So, mineralization event number 1 corresponds to crystallization of cubic pyrite, scheelite and carbonates accompanied by milky quartz (Figure 7b). The second, third and fourth mineralization events occur within banded or laminated quartz veins (Figure 8, 9, 11) and are described below. The second mineralization event corresponds to quartz, scheelite, ferberite, dolomite (Do 1), calcite, pyrite (Py 2) and dissease sphalerite (Sph 1). The third mineralization event starts with introduction of quartz (3), brecciation and fracturing of scheelite, ferberite, dolomite and calcite. Also, pyrite (Py 2) is subhedral, massive, and sometimes displays cubic habits (Figure 20 c) or filling scheelite fractures (Figure 24 e). As seen in figure 18 f, this pyrite is accompanied by another cubic subhedral pyrite (Py 3) related to two different electrums. The first one is within pyrite 2 or 3 (Electrum 1, Figure 19 b and Figure 20 d) and the other one is present in fractures or borders of pyrite 2 or 3 (Electrum 2, Figure 18 c, d and Figure 19 a). Sphalerite (Sph 2) overgrows pyrite (Py 2, 3) and often present emulsion textures of chalcopyrite (Cpy 1, Figure 17 c and Figure 18 f). Galena (Gn 1) is overgrowing previous minerals in the sequence and is filling spaces and fractures within them (Figure 24 d and Figure 25 d). Pyrrothite is included or overgrowing pyrite 2, and arsenopyrite is filling spaces of pyrite 2. The introduction of calcite and dolomite (Do 2) produce brecciation, fracturing, and remobilization of sulphides, producing skeletal textures in some pyrites (Py 2) (Figure 22 b). Those carbonates are accompanied by subhedral chalcopyrite (Cpy 2) often with electrum grains inside it (El 3). Pirargyrite is present within chalcopyrite 2 or carbonates (Figure 20 f). The fourth mineralization event is characterized by the presence of silver sulfosalts such as Polybasite (Pol), Argento-tennantite (AgTn) intergrown with chalcopyrite (Cpy 3) and galena (Gn 2) with late deposition of native silver (Figure 11 a). Aggregates of cubic pyrite (Py 5), brown pale sphalerite without exsolution or dissease texture (Sph 3, Figure 21 d) and galena overgrowing or filling fractures are accompanying these silver minerals. 44 The quartz of second, third, and fourth event present dynamic recrystallization textures such as grain boundary migration and bulging. Finally, the fifth event corresponds to supergenic local enrichment of copper minerals producing malachite and oxidation of some areas inside the mine due to interaction with meteoric waters. Figure 28. Paragenetic sequence of mineralized veins. Each event is separated based on mineralogy and brecciation/fracturing events (Toothed lines represent brecciation or fracturing events). 45 5.3 Mineral Chemistry Energy dispersive X-ray spectroscopy (EDS) analysis was performed for the different minerals that occur in the deposit. Thus, structural chemical formulas of minerals were computed and different families of ore minerals were identified. ELECTRUM Electrum show different gold-silver contents (Figure 29) based on EDS analysis. Three types of gold were recognized based the composition of individual grains. The first Type 1 electrum is included as dots and subhedral blebs within pyrite showing fineness ranging between 730 and 750. Also in SEM images display radial fractures within pyrite (Figure 30 a). The second of them includes free electrum, Type 1 (within pyrite - el Oasis vein), in contact with pyrite or graphite (Figure 18 c, d, Figure 19 a, d, and Figure 30 b) associated with galena and fineness ranges between 530 and 570. The third one, are Type 2 electrum grains related to chalcopyrite within fractures (Figure 22 f) and fineness of this grains range between 417 and 466. Also one electrum grain associated with galena shows the same gold-silver proportions. Figure 29. Chemical composition of electrum particles analyzed by EDS in atoms per formula unit (apfu). 46 Figure 30. a) SEM image of electrum grain displaying radial fractures within pyrite. b) Electrum accompanied by graphite and rutile (light grey). SPHALERITE EDS analysis of sphalerite show high contents of iron and zero cadmium content in host rock sphalerite. Three populations of sphalerite are confirmed analysis optical based (Figure on this 31) and observations. High Cadmium (up to 3.1 wt %) and low contents of iron are present sphalerite in pale brown without exsolutions of chalcopyrite. Figure 31. Chemical composition of sphalerite particles analyzed by EDS in atoms per formula unit (apfu)calculated based on 1 sulfur atom. Lower contents of cadmium and high contents of iron are present in dark red sphalerite or with exsolution (emulsion-like) textures. Finally, as the host rock, dissease sphalerite does not have cadmium. 47 SULFIDES Structural chemical formula of pyrite, pyrrhotite, arsenopyrite, galena and chalcopyrite was calculated showing little or none variation in these minerals along the deposit. Rock Type Host Rock (E2) Quartz veins Mineral Cpy Sph Py Apy Py Po Cpy Sph -av Gn Iron 0.982 0.13 1.02 1 0.97 0.43 0.99 0.084 0 Zinc/Cadmium Copper 0 0.77 / 0 0 0 0 0 0 0.833 / 0.0183 0 0.94 0 0 0 0 0 0.94 0 0 Lead 0 0 0 0 0 0 0 0 1.085 Arsenic 0 0 0 0.981 0 0 0 0 0 Sulfur 2 1 2 1 2 1 2 1 1 Table 3. Structural chemical formula of sulphides. (Abbreviations: Cpy = Chalcopyrite, Sph-av = Average-Sphalerite, Py = Pyrite, Apy =Arsenopyrite, Po = Pyrrhotite, Gn = Galena) Figure 32 a. is a SEM image of arsenopyrite filling cavities within pyrite. Also intrafoliation pyrite SEM image (Figure 32 b) confirmed that pyrite and chalcopyrite were formed within foliation of graphite bands. Figure 32. a) Arsenopyrite filling cavities within pyrite. b) Intrafoliation pyrite in the graphitic schist, also chalcopyrite is present. 48 SILVER SULFOSALTS Silver sulfosalts in quartz veins were confirmed after petrographic characteristics of these minerals using EDS compositions. Complex structural chemical formulas with silver and other metals denote the presence of pirargyrite and other silver sulfosalts such as argento-tetrahedrite, argento-tennanite and polybasite (Figure 33) (Table 4). Mineral Sulfur Pyrg 3 Pol 11 Pol 11 Ag-Tn 13 Pol 11 Silver Iron 2.71 0 13.72 0.564 13.96 0.30 6.45 1.92 12.55 0.55 Zinc 0 0 0 0 0.61 Copper 0 1.58 1.15 4.1 1.11 Lead 0 0 0 0 0.14 Arsenic 0 0 0 0.94 0.48 Antimony 1.05 1.97 1.8 2.87 1.16 Table 4. Structural chemical formula of sulfosalts. (Abbreviations: Pyrg = Pirargyrite, Pol = Polybasite, Ag-Tn = Argento-tennantite). SEM images of this sulfosalts show mineral intergrowth between them and a lot of heterogeneity between crystals (Figure 33 a). Additionally, those silver related minerals are filling pyrite fractures (Figure 33 b). Figure 33. a) Polybasite crystal with argento-tennantite exsolutions. b) Fractures of pyrite filled with silver sulfosalts. 49 WOLPHRAMATES Two different wolphramates were recognized based on their structural formulas; scheelite and ferberite. Mineral Scheelite Ferberite Ferberite Scheelite Scheelite Calcium 0.85 0 0 0.971 0.941 Iron 0 0.93 1.019 0.061 0 Wolphram 1.051 1.024 0.994 0.991 1.021 Oxygen 4 4 4 4 4 Table 5. Structural chemical formula of wolphramates. Figure 34. Ferberite (center) filled with galena in cleavage planes, accompanied by pyrite, sphalerite, chalcopyrite and scheelite. ALTERATION MINERALS Structural formula of rutile, tourmaline, and hematite was calculated as follow: Rutile: Ti0.92O2 Hematite: Fe1.98O3 Tourmaline: Na0.507 (Mg 1.49 Al 0.51) (Al 6.034 Fe 1.372) (BO3)3 (Si5.971 O18) (OH, F)4 50 5.4 Microthermometry Measurements of only primary fluid inclusion families were realized in three translucent quartz crystals belonging to different sites of the mine. Sample 9S-Drusa 9N-Drusa P1 Mineral Quartz Quartz Quartz Site in the mine Nine level-south Nine level-north First level Mineral association Sulphides + Qtz Sch + Dol + Qtz Qtz+Py+Gn Table 6. Samples selected for microthermometric measurements. Sample: 9S-Drusa This sample was collected from a sulphide vein within the 9 level that are showed in the figure 11 c, the selected fluid inclusion family is primary, all inclusions present double ring (Liquid H2O + Liquid CO2 + Vapor CO2) and petrographic, microthermometric and fluid characteristics are listed below. Figure 35. Localization and characterization map of FIA 1. This family is hosted by translucent quartz which belongs to crack-seal vein accompanied by sulphides. 51 Inclusion 1 2 3 4 5 6 7 8 9 Morphology Liquid area (um2) Tear 327.96 Ovoid 243.03 Ovoid 86.18 Ovoid 128.86 Ovoid 23.97 Elongated 115.57 Irregular 16.36 Tear 179.75 Ovoid 75.16 Vapor area (um2) 32.38 18.72 14.4 7.38 1.08 3.66 0.71 7.18 3.47 Phases 2L + V 2L + V 2L + V 2L + V 2L + V 2L + V 2L + V 2L + V 2L + V Relation V/V+L 0.090 0.072 0.143 0.054 0.043 0.031 0.041 0.038 0.044 Table 7. Petrographic characteristics of fluid inclusion family 1. Inclusion 1 2 3 4 5 6 7 8 9 T°Eu T°ffh T°fcl -60.8 -60.4 -61.0 -60.7 -61.2 -60.7 -60.4 -60.8 -61.0 -6.1 -5.8 -6.0 -6.6 -7.0 -6.4 -6.3 -6.4 -6.3 8.4 8.6 8.1 8.6 8.4 8.6 8.7 8.4 8.4 T°h CO2 T°h Homogenization (L or V) 26.1 26.1 26.2 26.6 26.7 26.3 26.5 26.2 26.3 315 320 313 318 315 313 317 314 308 Liquid CO2 Liquid CO2 Liquid CO2 Liquid H2O Liquid CO2 Liquid CO2 Liquid H2O Liquid CO2 Liquid CO2 Table 8. Microthermometric measurements of fluid inclusion family 1. Inclusion Density (g/cc) Salinity NaCl %wt 1 2 3 4 5 6 7 8 9 0.847 0.876 0.829 0.888 0.895 0.913 0.906 0.909 0.913 2.74 2.36 3.31 2.36 2.74 2.36 2.17 2.74 2.74 Pressure vapor phase (Mpa) 6.60 6.60 6.61 6.67 6.69 6.63 6.66 6.61 6.63 Table 9. Fluid characteristics for each inclusion within first family. 52 Sample: 9N-Drusa This sample was collected from the vein that is showed in the figure 9. Measured fluid inclusions were formed at same time as host crystal because are elongated in the growth direction of quartz. Moreover, measured crystal was found filling spaces between scheelite in the central part of the vein. Thus, that crystal must have formed after the scheelite and dolomite. Same as the previous sample all inclusions present double ring (Liquid H2O + Liquid CO2 + Vapor CO2) and petrographic, microthermometric and fluid characteristics are listed below. Figure 36. Localization and characterization map of FIA 2. This family is hosted by translucent pyramidal quartz formed within a druse between scheelite and dolomite. 53 Inclusion 1 2 3 4 5 6 Morphology Liquid area (um2) Irregular 173.633 Elongated 350.642 Elongated 157.505 Elongated 200.521 Elongated 130.687 Elongated 351.161 Vapor area (um2) 15.815 32.076 31.634 50.931 8.23 45.509 Phases Relation V/L 2L + V 2L + V 2L + V 2L + V 2L + V 2L + V 0.083 0.085 0.123 0.152 0.059 0.096 Table 10. Petrographic characteristics of fluid inclusion family 1. Inclusion 1 2 3 4 5 6 T°Eu T°ffh T°fcl -59.9 -59.8 -59.9 -60.8 -59.9 -59.8 -4.4 -2.8 -2.5 -2.7 -2.5 -2.9 6.4 6.6 5.6 5.7 6.6 6.6 T°h CO2 T°h Homogenization (L or V) 24.1 24.3 24.2 24.1 24.2 24.1 253.8 253.6 253.8 253.6 253.7 253.8 Liquid H2O Liquid H2O Liquid H2O Liquid H2O Liquid H2O Liquid H2O Table 11. Microthermometric measurements of fluid inclusion family 2. Inclusion 1 2 3 4 5 6 Density Salinity %wt 0.79 0.93 0.69 0.689 0.79 0.92 6.43 6.07 7.86 7.68 6.07 6.07 Pressure (Mpa) 6.30 6.33 6.31 6.30 6.32 6.30 Table 12. Fluid characteristics for each inclusion within second family. 54 Sample: P1 This sample was collected in the first level ore-shoot within the banded texture vein (Figure 6). This vein comprise sulfides (pyrite, galena, sphalerite) and it was a rich gold zone in the past (Torres, Personal communication 2017). Same as the previous samples, all inclusions within the following three families present “double ring” (Liquid H2O + Liquid CO2 + Vapor CO2) and petrographic, microthermometric and fluid characteristics are listed below. Figure 37. Localization and characterization map of FIA 3. This family is hosted by translucent pyramidal quartz formed within a crack-seal vein accompanied by sulphides. 55 Inclusion 1 2 3 4 5 Morphology Liquid area (um2) Ovoid 101.788 Ovoid 299.091 Horn 448.319 Horn 201.000 Horn 244.211 Vapor area (um2) 8.942 31.031 26.046 11.000 13.470 Phases 2L + V 2L + V 2L + V 2L + V 2L + V Relation V/L 0.081 0.094 0.055 0.052 0.052 Table 13. Petrographic characteristics of fluid inclusion family 3. Inclusion 1 2 3 4 5 T°Eu T°ffh T°fcl -61.3 -61.3 -61.2 -61.3 -61.7 -5.5 -5.6 -5.5 -5.7 -7.7 8.2 8.8 6.8 8.3 8.7 T°h CO2 T°h Homogenization (L or V) 27.6 27.5 29.6 29.5 26.6 281.4 281.9 279.9 281.5 281.8 Liquid CO2 Liquid CO2 Liquid H2O Liquid CO2 Liquid CO2 Table 14. Microthermometric measurements of fluid inclusion family 3. Inclusion 1 2 3 4 5 Density Salinity %wt 0.84 0.90 0.91 0.79 0.87 3.11 2.02 5.70 2.93 2.17 Pressure (Mpa) 6.83 6.81 7.15 7.13 6.67 Table 15. This is the fluid characteristics of each inclusion within family 3. Inclusion 1 2 3 4 5 6 Morphology Liquid area (um2) Irregular 69.71 Ovoid 166.4 Triangular 357.96 Ovoid 194.06 Irregular 554.78 Ovoid 39.95 Vapor area (um2) 4 15.5 17.52 13.32 30.92 2.0 Phases Relation V/L 2L + V 2L + V 2L + V 2L + V 2L + V 2L + V 0.054 0.085 0.046 0.064 0.053 0.048 Table 16. Petrographic characteristics of fluid inclusion family 4. 56 Figure 38. Localization and characterization map of FIA 4. This family is hosted by translucent pyramidal quartz formed within a crack-seal vein accompanied by sulphides. Inclusion 1 2 3 4 5 6 T°Eu -61.1 -61.2 -61.2 -61.0 -61.2 -61.3 T°ffh -5.5 -6.6 -5.4 -5.3 -6.2 -6.3 T°fcl 7.5 8.4 8.5 8.3 8.2 8.7 T°h CO2 29.7 31.0 29.2 30.9 27.8 27.2 T°h 282 281.2 280 263 282 296.2 Homogenization (L or V) Liquid CO2 Liquid CO2 Liquid H2O Liquid CO2 Liquid H2O Liquid H2O Table 17. Microthermometric measurements of fluid inclusion family 4. Inclusion 1 2 3 4 5 6 Density Salinity %wt Pressure (Mpa) 0.87 0.88 0.87 0.85 0.86 0.80 4.42 2.73 2.55 2.93 3.11 2.17 7.16 7.38 7.08 7.36 6.86 6.76 Table 18. Fluid characteristics for each inclusion. 57 Figure 39. Localization and characterization map of FIA 5. This family is hosted by translucent pyramidal quartz formed within a crack-seal vein accompanied by sulphides. Inclusion 1 2 3 4 5 Morphology Liquid area (um2) Ovoid 55.5 Ovoid 46.13 Ovoid 67.40 Rectangular 236.58 Ovoid 200.97 Vapor area (um2) 3.10 3.42 4.67 26.31 15.03 Phases Relation V/L 2L + V 2L + V 2L + V 2L + V 2L + V 0.053 0.070 0.065 0.100 0.070 Table 19. Petrographic characteristics of fluid inclusion family 5. 58 Inclusion 1 2 3 4 5 T°Eu T°ffh T°fcl -60.5 -60.5 -60.5 -60.8 -60.6 -6.6 -5.5 -6.5 -5.6 -6.6 8.7 8.5 8.6 9.2 8.6 T°h CO2 28.4 28.1 28.2 28.4 28.2 T°h 300 308 311 299.3 305 Homogenization (L or V) Liquid CO2 Liquid CO2 Liquid H2O Liquid CO2 Liquid CO2 Table 20. Microthermometric measurements of fluid inclusion family 5. Inclusion Density Salinity %wt 1 2 3 4 5 0.87 0.83 0.85 0.80 0.83 2.17 2.55 2.36 1.21 2.36 Pressure (Mpa) 6.95 6.90 6.92 6.95 6.92 Table 21. Fluid characteristics for each inclusion within family 5. Based on the decrease of eutectic temperature in all fluid inclusions; CO2 and methane CH4 could be present as volatile phases in the fluid system. Salinity is low, ranging between 1.21 – 7.86 wt percent NaCl, and the bulk fluid density is around 0.8 g/cc. Moreover, V/L relation is not constant in all fluid inclusion families showing a heterogeneous trapping because of mixing of fluids (Wilkinson, 2001). Homogenization temperatures are consistent between 250 °C and 320 °C. Also, bulk fluid composition ranges of inclusions were calculated and the amounts of substance fractions that compose them are: H2O between 0.66 and 0.92, CO2 between 0.03 and 0.32, and NaCl between 0.0054 and 0.045. This means that the average of fluid inclusions are made up of 82.36 % water and 15.78 % CO2 with minor amounts of dissolved salt (NaCl). 59 5.5 Raman spectroscopy Raman spectroscopy of fluid inclusions of the first and second families was done in order to confirm the presence of volatiles in the system also having into account the decrease of eutectic temperature in all analyzed inclusions. Inclusion – FIA 1 Figure 40. Ramman spectrum of volatile species within one FIA 1 inclusion. Four raman vibrations (cm-1) were identified in the spectrum for the FIA 1 inclusion. The first two peaks correspond to “Fermi doublet”: 1285 - 1388 cm-1,, and confirms the presence of CO2. Next peak of 2330 cm-1 corresponds to Nitrogen, and the last peak (2917 cm-1) corresponds to the main vibration of methane (Frezzotti et al., 2012). Inclusion – FIA 2 Figure 41. Ramman spectrum of volatile species within one FIA 2 inclusion. 60 In this case only three vibrations were recognized. The first two correspond to the Fermi doublet of CO2, and the third vibration corresponds to methane. Also, this raman spectrum has lower resolution than the previous one, which can be explained by the orientation of the inclusion and his depth within the crystal. 61 6. DISCUSSION 6.1 Mineralization styles and vein textures The mineralization that occurs in the “El Gran Porvenir del Libano” mine is emplaced in metamorphic rocks corresponding to greenschist facies, similar to those deposits known as “Orogenic gold deposits” (Groves, 1998; Goldfarb et al., 2005; Eliu, 1999). Mineralized bodies within the deposit display massive, brecciated and banded textures (Figure 42). Banded texture is typical of the crack & seal quartz vein type. Thus, indicating brittle-ductile regimes in a shear zone characterized by hydraulic fracturing during multiple fluid flow events (Goldfarb, et al. 2005). This means that multiple mineralization events could be evidenced in the “lamination” or bedding-parallel arrays of those veins. On the other hand, breccias are typical of brittle conditions and reflect cataclastic deformation of host rocks. Figure 42. Schematic diagram of vein textures interpreted in the field, based on Ore shoot mineralization present in the first level of the mine (Figure 6). 62 Structural control on the mineralization occurs in subordinate third order oblique faults (i.e. “Sistema de fallas la Chucula” with NW strike) related to NE trending movement of the first order structure; Palestina fault. According to Goldfarb, et al. (2005) first order structures are needed for carrying great volumes of auriferous fluids. While second to third order structures provide favorable environments for deposition of auriferous veins in areas of jogs, changes in strike or bifurcations of faults. So, it suggests that mineralization in the Libano area could be strongly influenced by Palestina fault and other fault systems of second to third order. 6.2 Hydrothermal alteration Alteration mineral assemblages found in the deposit (Figure 43) are present in the proximal zone within alteration haloes up to 10 centimeters. Present minerals on the intermediate zone stands for alteration of non-adjacent host rocks, dykes and porphyritic intrusive bodies. Alteration mineralogy is similar of those described by Eliu (1999) for orogenic gold-lode deposits in upper greenschist facies (Figure 44). Figure 43. Paragenetic alteration sequence of the mineralization in the Libano area. 63 Figure 44. Schematic paragenetic sequence around orogenic lode-gold deposits in upper greenschist facies. Black represents the common case and green indicates a less common occurrence. (Taken from Eliu, 1999). In this case, the main alteration processes are carbonatization and sericitization of host rocks with calcite, sericite, white micas, tourmaline and rutile as key alteration minerals. These are two of the main alteration processes that took place in the formation of orogenic gold deposits, together with silicification and sulfidation (Goldfarb, 2010). 64 6.3 Paragenetic sequence Four mineralization events with a supergenic enrichment of copper minerals were recognized in the mineralized veins and local zones of the mine. The first event correspond to introduction of great volumes of quartz and cubic pyrite with minor amounts of scheelite and carbonates. The second event starts with introduction of quartz as response of hydraulic fracturing process that builds up crack & seal veins, which could produce brecciation of the first massive vein due to high pressure fluctuations during fluid injection. Then, precipitation of wolphramates is followed by carbonates and non-auriferous sulfides such as pyrite and sphalerite that occur in the second event. This also could be corroborated because scheelite and carbonate pulses are located in the lower part of the veins. Also, since the crystallization of fracture-fill veins occur from outer to center, the mineralization deposited on the outer part is considered to be older than those deposited in central parts. The third event corresponds to the auriferous event, represented by pyrite, sphalerite, galena, arsenopyrite, pyrrothite and chalcopyrite. During this event multiple remobilizations of electrum and auriferous sulphides could have occur because of remobilization effects of calcite and dolomite. Within this event, gold grade is decreasing because of the increasing of silver content into the veins. Thus, three different electrums were recognized by his color, mineral association and EDS compositions. The decrease in gold fineness is anomalous for the orogenic gold deposit type where ranges are between 780 and 1000 (Morrison et al., 1990). So an intrusion related gold system will explain better the variations of gold grades along the deposit. The fourth event is represented by silver sulfosalts (Pirargyrite, Polybasite, AgTennantite) and native silver accompanied by quartz, pyrite, cadmium-rich sphalerite and galena. Those atypical mineral assemblages of silver sulfosalts in orogenic gold deposits could be explained by interaction of metamorphic fluids with surface water influx (Wilkinson (2001). Finally, supergenic enrichment of copper minerals leads to formation of malachite. Moreover, oxidation zones in the mine lead to formation of iron oxides. 65 6.4 Mineralizing fluids According to microthermometric and Raman measurements, the mineralizing fluid system is formed by H2O – CO2 + CH4 + N2 volatile species. Additionally, “double ring” CO2 inclusions, low salinities (ranging from 1.21 – 7.86 % wt NaCl) and homogenization temperatures between 250 °C and 320 °C are consistent with those reported for orogenic gold deposits (Groves, 1998; Goldfarb, 2005; Wilkinson, 2001; Goldfarb, 2010). Temperature °C - Salinity wt% Homogenization temperature (°C) 800 700 600 500 FIA 1 400 FIA 2 300 FIA 3 200 FIA 4 100 FIA 5 0 0 10 20 30 40 50 60 70 80 Salinity (wt% NaCl equivalent) Figure 45. Homogenization temperature °C - salinity diagram illustrating ranges for inclusions from different deposit types (Modified from Wilkinson, 2001). Figure 45 shows that all fluid inclusions studied in this work correspond to orogenic gold deposits (“Lode Au”) or epithermal systems. However, epithermal deposits lack of significant amounts of CO2 as volatile phases within the system (Wilkinson, 2001). Compare to intrusion related gold systems; results show similarity between low salinities and homogenization temperatures ranging from 180 to 360 °C. Nonetheless, mineralized veins in Libano contain silver, zinc and lead, and according to Hart (2007); Ag-Zn-Pb intrusion related veins lack significant amounts of CO2. This is the opposite of what was found in this study (Figure 46). 66 As seen in Figure 46, fluid fraction of CO2 present within fluid inclusions is relatively high, and suggests that the deposit might correspond to an orogenic gold deposit. Figure 46. Fluid fraction diagram to discriminate between porphyry, epithermal and orogenic gold deposits. (Modified after Goldfarb, 2010). Fluid trends displayed in figure 47 present isothermal mixing, also corroborated by the relationship V/L which remains not constant for all fluid inclusion families. Isothermal mixing trend is consistent with the hydraulic fracturing process that makes up the crack and seal veins. Also, mixing of fluids is one of the processes that take place in the deposition of metals and gold within orogenic systems (Wilkinson, 2001; Goldfarb, 2010). Additionally, it is possible to see a “Surface fluid dilution” trend which means interaction with superficial fluids, and would help to explain the presence of complex silver sulfosalts in the paragenesis. 67 Trends of Fluid Evolution Homogenization Temperature °C 425 400 375 350 FIA 1 325 FIA 2 300 FIA 3 275 FIA 4 250 FIA 5 225 200 0 2 4 6 8 10 12 Salinity (wt% NaCl equivalent) Figure 47. Fluid evolution trends of studied fluid inclusion families (Modified from Wilkinson, 2001). Frequency vs Homogenization temperature °C 10 Frequency 8 6 FIA 5 4 FIA 4 2 FIA 3 0 FIA 2 205215225 235 245 255 265 FIA 1 275 285 295 305 315 325 335 345 355 365 Homogenization temperature °C Figure 48. Frequency versus homogenization temperatures of fluid inclusion families measured on “El Gran Porvenir del Libano “veins. 68 Finally, a comparison between homogenization temperatures versus frequency of fluid inclusions families within the veins of “El Gran Porvenir” mine (Figure 48) relative to “Las animas- Santa Isabel mining district” veins (Figure 49) shows that peaks are highly correlated between 250 and 320 °C . It is important to mention that the Santa Isabel mining district is located 25 kilometers away from the “El Gran Porvenir” mine. The mineralizations in Santa Isabel are reported as orogenic related to secondary and third order structures associated to the first order Chapeton-Pericos- Palestina faults (Correa, 2012). Figure 49. Frequency versus homogenization temperatures of fluid inclusion families measured on “Las Animas “– Santa Isabel mining area veins (Taken from Acevedo, 2010). 6.5 Source of fluids and relationship to magmatism Based on petrographic observations of host rocks, intrusive dykes and porphyritic rocks; Metamorphic fluids could play an important role in deposition of gold, sulfides and wolphramates. The presence of intrafoliation pyrite overgrown by chalcopyrite and sphalerite, within folds of the graphitic schists, is a strong argument to propose a metamorphic fluid enriched in base metals and gold, that could have produced the mineralization. On the other hand, some dykes are carrying pieces of the quartz veins with mineralization suggesting postmineralization emplacement of the dykes. Porphyritic rocks also contain minor amounts of sulfides and are completely altered by carbonatization and sericitization processes. However, the influence of deep-seated magmatic fluids in the development of the deposit is not discarded. 69 Comparative table between deposit types and “El Gran Porvenir” deposit. Intrusion related gold system Orogenic Gold Mine “El Gran Porvenir” Tectonic Framework Plutonic suites emplaced during subduction, collision and obduction of outboard terranes. Compressional to transpressional deformation processes in convergent plate boundaries and shear zones Transpressional shear zone. Host rocks Commonly plutons , sedimentary or metasedimentary rocks Deformed metamorphic rocks Gangue minerals Quartz, mica, scheelite, K-feldespar Quartz, calcite, dolomite, scheelite. Alteration minerals Sericite, carbonates, pyrite, Biotite, Kfeldspar, chlorite Calcite, dolomite, ankerite, chlorite, sericite, fuchsite, tourmaline, rutile Au-Bi-Te±W, As, Sb,Ag-Zn-Pb Py, Apy, Po, Mo, BiSulfosalts Distal : Sph, Gn Au-Ag, Zn, Pb, Cu, As, As,Sb ,W, Hg, Bi Metal signatures Ore minerals Vein textures Gold fineness Fluid system Salinity & Th°C Py, Apy, Po, Tth, Stb, Cpy, Gn, Sph, Mo Graphitic schists and chloritic schists in greenschist facies. Quartz, calcite, dolomite, scheelite, ferberite. Sericite+ carbonates, rutile, tourmaline, white micas, chlorite, hematite, pyrite. Au-Ag, Zn, Pb, Cu, As-Sb, W Py, Apy, Po, Cpy, Gn, Sph, Pol, Ag-tn, Pyrg Arrays of sheeted quartz veins Breccias, Laminated crackseal veins, Oblique extension Massive, Breccias, crack & seal veins. Variable 780-1000 460 - 780 H2O – CO2 H2O – CO2 + CH4 + N2 2 – 40 wt. % NaCl 160-380°C 2 – 10 wt. % NaCl equiv. 200 – 400 ° C H2O – CO2 + CH4 + N2 1.21 – 7.86 wt. % NaCl 250 – 320 ° C Table 22. Table comparing between the different characteristics of intrusion related gold systems, orogenic gold deposits, and the “El Gran Porvenir del Libano “deposit. (References taken from: (Groves, 1998; Goldfarb et al, 2005; Goldfarb, 2010; Hart, 2005; Eilu, 1999; Hart, 2007). 70 Metalogenic model approach of the deposit Figure 47. Metalogenic model of the hydrothermal quartz veins occurring in the “El Gran Porvenir del Libano” mine. Black lines within veins correspond to faults. Red lines correspond to intrusive dykes present near or within veins. Based on the above, mineralization of hydrothermal gold-silver veins that occurs in the Libano areas correspond to an orogenic gold deposit formed at mesozonal depths due to vein textures, fluids characteristics, and metal signatures. Therefore, the influence of metamorphic fluids with different events of mixing during multiple fluid flow events leads to formation of banded – crack & seal veins. However, the influence of meteoric or magmatic fluids and their interaction with metamorphic fluids could have played an important role in the development of the complex mineralogy evidenced in the deposit. Figure 47 shows the hypothetical metalogenic model approach for the studied mineralized veins. 71 7. CONCLUSIONS Based on the mineralizing fluid system characterized by H2O – CO2 + CH4 + N2 volatile phases, low salinities ranging from 1.21 to 7.86 wt. % NaCl , and high amounts of CO2 that are represented by “double ring” fluid inclusions; the mineralization that occurs in the “El Gran Porvenir del Libano” mine correspond to an orogenic gold deposit. Additionally, estimated homogenization temperatures, fluid evolution patterns, ore mineralogy, alteration assemblages, vein textures and tectonic setting are consistent with this deposit type. Mineralization is emplaced at mesozonal depths hosted by graphitic schists and chloritic schists in greenschist facies. The crack & seal mineralized veins formed during multiple fluid flow mixing events with interaction of metamorphic and probably meteoric fluids. Also, the mineralization is controlled by the “Chucula” third order fault system related to the Palestina first order fault zone. Alteration is characterized by a development of proximal alteration zones adjacent to veins with sericite, calcite, white micas, chlorite, tourmaline, and rutile. Additionally, sericitization and carbonatization are the main alteration processes that took place on the host rocks, dykes and porphyritic rocks. Four mineralization events were recognized. The first one is characterized by the injection of great volumes of quartz, cubic pyrite, scheelite and carbonates. The second event represents the beginning of the formation of banded veins with crystallization of wolphramates, carbonates, pyrite and sphalerite. The third mineralization event represents the late deposition of gold accompanied by sulphides such as pyrite, sphalerite, galena, chalcopyrite, arsenopyrite and pyrrhotite. The fourth mineralization event is characterized by native silver and complex silver sulfosalts accompanied by pyrite, cadmium-rich sphalerite and galena. Finally, supergenic enrichment of copper minerals locally occurs in the deposit. 72 8. RECOMMENDATIONS In order to complement this work, dating of mineralization and intrusive igneous bodies such as dykes and porphyries are needed to elucidate genetic relationships between mineralization and igneous rocks. Additionally, detailed fluid inclusion analysis of the different mineralization events could be required for defining temperature and pressure paths for the development of the mineral deposit. Additionally, stable isotope analysis like Oxygen and Deuterium would be another approach for distinguishing the source of the mineralizing fluids. 9. AKWNOLEDGMENTS I want to acknowledge to all of those who were directly or indirectly involved in this project. Particularly to professors Julián Andrés López, Yamirka Rojas, Juan Carlos Molano, Andrés Rodriguez, Adriana Delgado, Alba Marina Suarez, and Ana Ibis Despaigne, for their immense support and patience during the development of this work. Moreover, Nicolas Bedoya, Sergio Silva, Jimmy Torres and specially Valentina Carmona since without them this work would have never been possible. To my family…mom, dad, brothers, aunts and grandparents, as you give me strength to continue. Thanks to, Ruben Gaitán, Ivette Cucunubo and Leonardo Santacruz. Also, thanks to my friends. I appreciate you all very much and once again thanks for everything! 73 10. REFERENCES ACEVEDO, A. (2010): Petrografía y microtermometría de la Mina Las Animas, Santa Isabel, Tolima. Trabajo de grado, pp 1 -20. Departamento de Geociencias, Universidad Nacional de Colombia, Bogotá. Barrero, D., & Vesga, C. J. (1976). 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Electrum SEM composition Sample 5A_1 5A_2 9S_1 9S_2 OA 5B_1 5B_2 5B_3 5B_4 5B_5 9N_1 9N_2 9N_3 9N_4 Au wt% 75.18 73.86 45.13 73.11 55.26 57.23 53.85 55.84 54.04 52.76 53.57 56.33 42.54 41.65 Ag wt% 24.82 26.14 54.87 26.89 42.37 42.77 46.15 44.16 45.96 47.24 46.43 40.57 53.38 58.35 Table 23. Electrum wt% composition. 2. Sphalerite SEM composition Sample Host 10N_1 10N_2 5B_1 5B_2 9B_1 9N_1 9N_2 9R_1 9R_2 9Ag_1 9Ag_2 9Ag_3 9Ag_4 Fe wt% 8.21 7.42 3.57 6.83 5.5 5.49 8.77 6.97 3.75 6.44 2.61 2.15 2.36 3.05 Zn wt% 55.93 58.24 62.65 58.05 55.94 57.23 54.55 54.25 60.32 56.05 60.67 61.25 61.29 62.38 Cd wt% 2.76 3.05 1.44 1.52 1.79 3.06 2.19 2.79 2.96 2.24 3.05 S wt% 35.86 34.34 33.79 32.36 35.51 35.84 35.16 36.98 32.87 35.32 33.93 33.64 34.11 33 Table 24. Sphalerite wt% composition. 78