Search

Greece hosts a variety of magmatic-hydrothermal ore deposits/prospects with porphyry- and epithermal styles playing a major role in its total gold endowment. These deposit types are mainly clustered in two areas, the Rhodope- and Attico-Cycladic massifs, and formed from about 33 Ma to the Pleistocene, as a result of back-arc extension in the Aegean Sea, metamorphic core complex formation, and contemporaneous post-subduction and arc magmatism. In the Serbo-Macedonian massif, porphyry Cu-Au deposits include Skouries, Fisoka, Tsikara, Vathi and Gerakario. Causative intrusives are Oligocene to Miocene granodiorites to monzonites. Gold and PGE mineralization is associated with potassic alteration of the intrusives. In the eastern Rhodope massif and the NE Aegean islands, porphyry prospects occur at Pagoni Rachi, Konos Hill, Myli, Melitena (west Thrace), Fakos, Sardes, and Kaspakas (Limnos island) and Stypsi (Lesvos island). Mineralization is associated with Oligocene to Miocene subvolcanics of calc-alkaline to shoshonitic affinity. Feature of these prospects, which they share in common with several porphyry Au-only systems, is their shallow depth of emplacement, the presence of potassic/sodic-calcic and/or phyllic alteration, a strong epithermal overprint, their low Cu content, an extreme Re-enrichment, the multistage introduction of Au, the presence of banded quartz veinlets, and the local presence of tourmaline. New discoveries of porphyry-style mineralization at King Arthur, St. Philippos and Aisymi, increases the gold potential in west Thrace. High-intermediate sulfidation epithermal Au-Ag polymetallic deposits/prospects overprint and/or occur laterally from porphyry-style mineralization, where they are spatially associated with lithocaps of advanced argillic alteration. High-intermediate sulfidation Au-Ag epithermal mineralization at Perama Hill, Mavrokoryfi and Pefka in west Thrace, and at Pterounda, Mesotopos and Megala Therma on Lesvos island is controlled by steeply-dipping extensional faults within volcanic rocks, without any obvious genetic relationship to spatially-related porphyry-style mineralization. Polymetallic epithermal deposits and prospects contain critical and energy critical metals (e.g., Te, Se, Bi, Sb, In, Ge and Ga), which may be considered as by-products. In the Attico-Cycladic area, porphyry Mo-W mineralization occurs as sheeted quartz veins and stockworks cutting a potassic- to sericitic-altered Miocene granodiorite stock in the Lavrion district. Bonanza grade Au- and/or Ag-rich veins with epithermal affinities crosscut metamorphic rocks at Lavrion, and on Syros, Tinos, Antiparos and Anafi islands. Milos island is characterized by shallow submarine volcanic-hosted IS-HS epithermal Au-Ag-Te and base metal deposits. Antimony-As-Ag-Au deposits/prospects on Chios, Samos and Kos islands in the eastern Aegean Sea, indicate the potential for Carlin-style mineralization in Greece. Several factors played a role to the metal endowment of the Aegean porphyry-epithermal systems: magma fertility in the source regions, depth of emplacement of causative intrusives, relative contribution of mantle versus crustal material, redox state of subduction-related magmas, and physico-chemical fluid conditions at the site of ore deposition.

Physicochemical conditions under which early sulfide saturation occurs and the role of this process in the mineralising potential of magmas in different geodynamic settings have been the subject of interest in many recent studies. Here we present new temperature-pressure-fO2 data on sulfide-saturated magmatic enclaves and host lavas from volcanic systems in subduction, post-subduction and intraplate geodynamic settings, some of which are associated with porphyry and epithermal deposits. Petrographic investigations coupled with mineral chemistry of sulfide inclusions and their host minerals and with bulk chemistry of amphibole, plagioclase and pyroxene-rich enclaves and their host lavas indicate that sulfide occurrence, abundance, and composition depend on magma evolution. Sulfides are more abundant and have higher Ni/Cu bulk ratios when found in mafic enclaves compared to sulfide inclusions occurring in more evolved lavas. Thermo-oxibarometry estimates indicate that mafic hornblende-rich cumulates (SiO2 < 45 wt%) occurring at the studied intraplate setting evolve and reach sulfide saturation already in the mantle (61 ± 7 km) at high temperature and pressure conditions (17 kbar and 1135 ± 28 ◦C) and low ΔNNO (< 􀀀 1). These cumulates are associated with a greater sulfide abundance (up to 0.23 area %) compared to other types of enclaves and have Cu-poor sulfides (mostly pyrrhotite, with Cu median = 0.16 wt%) with high Ni/Cu values (up to 65). In contrast, more evolved (SiO2 > 50 wt%) gabbroic plutonic enclaves found in arc settings saturate sulfides at shallower crustal levels (~26 ± 10 km, i.e. ≤ 7 kbar) and at lower temperature (1014 ± 28 ◦C) and higher ΔNNO (> +1), and are characterised by a lower sulfide abundance (down to 0.01 area %), dominated by Cu-rich sulfides (mostly chalcopyrite and bornite with Cu median = 50 wt%). By accounting for the sulfide volume, our results suggest that sulfides can retain significantly higher amounts of metals in the enclaves (Cu = 32–113 ppm) compared to sulfides in the host lavas (Cu < 8 ppm). Considered altogether, our results indicate that alkaline mafic, less oxidised, and barren magmas corresponding to intraplate and back-arc settings saturated in sulfides in the upper mantle. In contrast, calc-alkaline felsic, oxidised and ore-related magmas corresponding to convergent margins started to be saturated in sulfides at the expected depth of the MASH zone and at shallower crustal levels. This seems to be a consequence of the investigated alkaline systems not forming shallow crustal magma chambers allowing magma differentiation, rather than the fact that late and shallow sulfide saturation is necessary for porphyry formation.

Hydrothermal fluids related to the development of the Aracuai Orogen during the Brasiliano Cycle have affected Paleoproterozoic banded iron formation-bearing sequences along the eastern border of the Sao Francisco Craton. Controversy surround the origin of specularite in high-grade schistose iron ore-bodies in the Serpentina Range (“Serpentina-type” ore) versus specularite-rich, S-free Au-PGE quartz veins (“Jacutinga-type”) that occur at the eastern border of the Quadrilatero Ferrifero mining district. Chemical and thermobarometric characteristics of fluid inclusions from Serpentina-type quartz-specularite veins show that metamorphic aqueous-saline fluids of low to moderate temperature (i.e. salinity between 6.3 and 13.7 wt% NaCl eqv and homogenization temperatures from 91° to 228 °C) were responsible for silica leaching and Fe enrichment along shear zones in the Statherian Serra da Serpentina Group. These Serpentina-type fluids present a distinct pattern with Na > Ca ≫ K. The fluids are depleted in Li, Na, Ba, Ca, K, Cu and Mg; and enriched in As and Sr in comparison to the Jacutinga-type fluids. In contrast, other two distinct fluids and chemical processes were involved to precipitate Fe oxides with Au-PGE in Jacutinga-type veins. The first type is an aqueous-carbonic fluid from the Catas Altas and Itabira deposits. These Jacutinga-type fluids present a pattern with Na > K > Ca ≫ Mg and K > Li > Ba > Sr. The fluids are interpreted to be of Brasiliano age and are typically associated with anatectic pegmatites from Santa Maria de Itabira. The high salinity of these brines (23.2–25.3 wt% NaCl eqv ) from the Itabira ore likely originated from their percolation through evaporitic layers, from salt concentration during deformation, or from fluid/rock interactions. Mixing between high-temperature aqueous-carbonic pegmatite-forming fluids and low-temperature aqueous metamorphic brines could have induced an abrupt change in the physical-chemical conditions of the system, which led to Au and PGE precipitation in the Itabira Jacutinga-type deposit. A second Jacutinga-type fluid is observed at the Gongo Soco and Barao de Cocais deposits. This fluid is interpreted as an aqueous-saline metamorphic fluid with the pattern Na > Ca > K ≫ Mg, low-to-moderate-salinity (4.3–16.4 wt% NaCl eqv ) and temperatures of 77° to 305 °C. It is relatively enriched in B; depleted in Li, Ba, Na, Cu, Zn and K; and follows the trend K > Li > Ba. In both types of fluids responsible for Jacutinga-type mineralization, gold was transported as chlorine complexes under acidic and oxidizing conditions. The metal precipitation may have occurred due to a rapid depressurization during failure of shear zones operating in the upper levels of the crust, or variations in the pH and redox conditions during the interaction with the host dolomitic itabirite.

In the magmatic-hydrothermal environment, fluids with similar metal concentrations and sources may yield contrasting mineral assemblages in successive stages of sulphide mineralization. These differences are linked to the physico-chemical conditions of the mineralizing fluids (e.g., T, pH, fS2, fO2) acquired during their interaction with country rocks and/or by mixing with groundwater. Here, we integrate petrography and osmium (Os) isotope (187Os/188Os) sulphide geochemistry, and discuss novel constraints on magmatic fluid-rock interaction and magmatic fluid-groundwater mixing that are deemed to govern sulphide deposition in magmatic-hydrothermal systems. We studied pyrite (FeS2) and enargite (Cu3AsS4) from the porphyry-related polymetallic Cerro de Pasco (14.54–14.41 Ma) and Colquijirca (10.83–10.56 Ma) epithermal deposits in the Central Andes, Peru. Sulphide mineralization is genetically associated with Miocene magmatism and includes breccia and replacement bodies of carbonate country rocks, and veins cutting the magmatic and sedimentary country rocks. At both deposits, pyrite is followed by enargite in the paragenesis. Pyrite has a radiogenic initial 187Os/188Os isotopic composition (187Os/188Osi-pyrite or Osi-pyrite = 0.80 to 1.45). Enargite (I) enclosing pyrite or filling in cracks in pyrite also has a radiogenic initial 187Os/188Os isotopic composition (Osi-enargite I = 0.56 to 1.24). Conversely, enargite (II) that formed on irregular surfaces on earlier pyrite has an unradiogenic 187Os/188Os isotopic composition (Osi-enargite II = 0.13 to 0.17). Our data show that the paragenetic evolution from pyrite to enargite records a sharp change in the osmium isotope composition within these sulphides. Pyrite and enargite (I) record radiogenic initial 187Os/188Os isotopic compositions, indicating interaction of magmatic hydrothermal fluids with the sedimentary country rocks. However, the unradiogenic initial 187Os/188Os isotopic composition of enargite (II) suggests that magmatic fluids with a mantle-like 187Os/188Os signature ascended from parental magmatic chambers to the epithermal environment without incorporation of crustal Os via fluid-rock interaction or mixing with groundwater. This difference may be due to the country rocks being altered during previous stages, with the radiogenic crustal Os signature being flushed by earlier magmatic pulses. Our findings imply that ore metals (i.e., Cu, Au) are magma-derived, whereas the Os isotopic composition of pyrite and some enargite in epithermal deposits may capture the signature of the interaction of magmatic fluids with country rock lithologies (e.g., the Eifelian black shale in the study area) and/or groundwater. Thus, the isotopic composition of the siderophile and chalcophile trace element Os in sulphides may act as a tracer of metal source, and degree of wall-rock interaction. © 2020 The Author(s), Chemical Geology, 564, ISSN:0009-2541, ISSN:1872-6836

Recently identified occurrences of porphyry-style mineralization evidence the link of the world's second largest known epithermal base metal Cerro de Pasco deposit (Peru) to a porphyry system emplaced at depth. They consist of (i) quartz-monzonite dykes and (ii) the south-western part of the large diatreme-dome complex adjacent to the main ore bodies of Cerro de Pasco, and (iii) stockwork of banded quartz-magnetite-chalcopyrite-(pyrite) porphyry-type veinlets crosscutting trachyte porphyritic intrusion cropping out at surface in the central part of the diatreme-dome complex. The latter porphyry-type mineralization observed at the same erosion level as the main epithermal base metal carbonate-replacement ore bodies is the subject of this work. Geological constraints indicate a shallow emplacement level (depth < 1 km, P < 270 bar), implying rather unusual low-pressure and high-temperature environment for the formation of porphyry-style mineralization. The banded porphyry-type veinlets record a multiphase history of formation with two successive high-temperature (N600 °C) stages, followed by a lower-temperature (b350 °C) stage.More than 90% of the quartz in veinlets precipitates during the first two high-temperature stages. Stage 1 is characterized by the entrapment in hydrothermal quartz of inclusions containing variable proportions of both silicate melt and metal-rich hypersaline (N90 wt% NaCl eq.) liquid, hereafter referred to as heterogeneous silicate melt inclusions (HSMIs). The latter are rarely described in porphyry-type mineralization. We suggest that during stage 1, the inclusions result from heterogeneous entrapment of an evolved hydrous rhyolitic melt mixed with a hypersaline fluid phase at low pressure (270 bar) and high temperature (N600 °C). The stage 2 is marked by the entrapment of metaland sulfur-rich hypersaline liquid inclusions, with salinity around 70 wt% NaCl eq., originated from the adiabatic ascent of magmatic hypersaline fluids transferred fromdeeper parts of the system. The lower-temperature stage 3 is characterized by an important temperature drop from N600 °C to b350 °C as revealed bymicrothermometry of aqueous two-phase liquid-vapor (L-V) inclusions. Quartz textures revealed by SEM-CL imaging allowascribing the sulfide precipitation to the low-temperaturemineralization stage 3. In-situ SIMS 18O/16O isotope analyses of quartz across the veinlets are indicative of a magmatic signature of the fluids during the first two stages; while quartz from stage 3 has oxygen isotopic compositions suggestive of minor contribution of meteoric waters to a predominantly magmatic aqueous fluid (~10 vol.% of meteoric input), which probably triggered Cu-Fe sulfide precipitation in the stockwork. High metal and sulfur contents of HSMIs and hypersaline liquid inclusions determined by LA-ICP-MS are interpreted to represent the fluid composition prior to the main sulfide precipitation event. The similar Pb-Zn ratio of the bulk ore extracted from the epithermal ore bodies at Cerro de Pasco and the HSMIs and hypersaline liquid inclusions suggest a common source of the fluids associated with the different mineralization styles at Cerro de Pasco.

The Cerro de Pasco district in central Peru hosts one of the world largest porphyry-related epithermal polymetallic deposits. The district is centered onto a large diatreme-dome complex crosscut by numerous dacite to rhyodacite bodies showing domal structures and quartz-monzonite dykes. Three temporally distinct high-temperature porphyry-type mineralization events have been recognized (PM1, PM2, and PM3). Dating of the latter by molybdenite Re-Os and by zircon U-Pb (LA-ICP-MS and CA-ID-TIMS) geochronology complements the already available dataset of zircon U-Pb ages of the subvolcanic and volcanic rocks mostly dacitic in composition occurring in the district and shows the existence of successive short-lived episodes (50%) at pressures between 0.9 and 3.4 kbar and at temperatures between ~680 °C and ~725 °C. At such conditions, magma is beyond the point of rheological lock-up and is not eruptible. The emplacement of the mostly dacitic subvolcanic and volcanic rocks has required a series of rejuvenation events of the upper crustal high-crystallinity silicic magma reservoir. Field relationships and geochronology indicate that emplacement of the subvolcanic and volcanic rocks is preceded each time by high-temperature (>600 °C) quartz-pyrite-magnetite ± chalcopyrite and quartz-molybdenite veining forming the three recognized porphyry-type mineralization events. Hydrothermal quartz of these veins host silicate melt inclusions, a rare feature in hydrothermal veins. Their composition determined by LA-ICP-MS analysis indicates that the mineralizing fluids, potentially sourced from intermediate magma recharges, have circulated in a magma reservoir in which the residual interstitial melt was more evolved than the melt trapped as inclusions in the magmatic quartz. The combined geochemical and geochronological data obtained show that several episodes of rejuvenation of a highly crystallized upper-crustal silicic magma reservoir, probably triggered by intermediate magma recharges and by circulation of CO2- and S-rich fluids exsolved from them, are at the origin of the large diatreme-dome complex and porphyry-type mineralization events at Cerro de Pasco.

The Inner Carpathians comprise several distinct Neogene late-stage orogenic Pb–Zn–Cu–Ag–Au ore districts. The mineral deposits in these districts are closely related to volcanic and subvolcanic rocks, and represent mainly porphyry and epithermal vein deposits, which formed within short periods of time in each district. Here, we discuss possible geodynamic and structural controls that suggest why some of the Neogene volcanic districts within the Carpathians comprise abundant mineralization, while others are barren. The Neogene period has been characterized by an overall geodynamic regime of subduction, where primary roll-back of the subducted slab and secondary phenomena, like slab break-off and the development of slab windows, could have contributed to the evolution, location and type of volcanic activity. Structural features developing in the overlying lithosphere and visible in the Carpathian crust, such as transtensional wrench corridors, block rotation and relay structures due to extrusion tectonics, have probably acted in focusing hydrothermal activity. As a result of particular events in the geodynamic evolution and the development of specific structural features, mineralization formed during fluid channelling within transtensional wrench settings and during periods of extension related to block rotation. In the Slovakian ore district of the Western Carpathians, Neogene volcanism and associated mineralization were localized by sinistral, NE-trending wrench corridors, which formed part of the extruding Alcapa block. The Baia Mare ore district, in the Eastern Carpathians, reflects a transtensional wrench setting on distributed oversteps close to the termination of the Dragos Voda fault. There, mineralization was spatially controlled by the transtensional Dragos Voda master fault and associated cross-fault systems. The Golden Quadrangle Cu–Au ore district of the Southern Apuseni Mountains reflects an unusual rotated transtensional/extensional setting close to the termination of a graben system. There, fluid flow was probably localized by fault propagation at the inner tip of the graben system. The spatial and temporal evolution of the magmatism and its changing geochemical signature from (N)W to (S)E strongly suggests a link with the contemporaneous northeastward roll-back of the subducted slab and a progressive southeastward detachment during accelerating roll-back. This geodynamic evolution is further supported by the present-day overall and detailed mantle lithospheric density images, the present-day heat flow patterns, the crustal architecture and its interpreted evolution, and the spatial and temporal evolution of depocentres around the Carpathian arc. In contrast to all these features, the mineral deposits in the West Carpathians, East Carpathians and Apuseni Mountains are too synchronous with respect to their individual volcanic history and contrast too much with younger volcanics of similar style, but barren, in southeastern parts of the Carpathians to simply link them directly to the slab evolution. In all three districts, the presence of magmatic fluids released from shallow plutons and their mixing with meteoric water were critical for mineralization, requiring transtensional or extensional local regimes at the time of mineralization, possibly following initial compressional regimes. These three systems show that mineralization was probably controlled by the superposition of favourable mantle lithospheric conditions and partly independent, evolving upper crustal deformation conditions. In the 13 to 11 Ma period the dominant mineralization formed all across the Carpathians, and was superimposed on structurally favourable crustal areas with, at that time, volcanic–hydrothermal activity. The period may reflect the moment when the (upper part of the) crust failed under lithospheric extension imposed by the slab evolution. This crustal failure would have fragmented the overriding plate, possibly breaking up the thermal lid, to provoke intensive fluid flow in specific areas, and allowed subsequent accelerated tectonic development, block rotation and extrusion of a “family of sub-blocks” that are arbitrarily regarded as the Tisia–Dacia or Alcapa blocks, even though they have lost their internal entity.

1–1: Porphyry Cu–Au and epithermal Au–Ag deposits in the southern Apuseni Mountains, Romania South Apuseni Mountains district: Lat. 46°03’ N, Long. 22°58’ E K. Kouzmanov*, P. Ivascanu, G. O’Connor a Isotope Geology and Mineral Resources, ETH, Sonneggstrasse 5, 8092 Zurich, Switzerland b Geological Institute of Romania, Caransebes Str.1, 78344 Bucharest, Romania c Gabriel Resources Ltd, Suite 1501, 110 Yonge St, Toronto, ON, M5C 1T4, Canada Received 19 November 2004, accepted 1 May 2005

1–2: Epithermal Pb–Zn–Cu(–Au) deposits in the Baia Mare district, Eastern Carpathians, Romania Baia Mare district: Lat. 47°40’ N, Long. 23°34’ E K. Kouzmanov*, L. Bailly, C. Tamas , P. Ivascanu a Isotope Geology and Mineral Resources, ETH, Sonneggstrasse 5, 8092 Zurich, Switzerland b BRGM, REM/MESY, 3, Av. Claude Guillemin, BP 6009, 45060 Orleans, France c Dept. of Mineralogy, Babes-Bolyai University, 400084 Cluj-Napoca, Romania d Geological Institute of Romania, Caransebes Str.1, 78344 Bucharest, Romania Received 19 November 2004, accepted 1 May 2005