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The studied Silurian nodules have hard light cores and dark shells. The cores consist of quartz with disseminated zonal carbonate mineral and pyrite. Zones in the carbonate have a variable composition from Mn-containing siderite, ankerite and dolomite to mixed Fe-Mn carbonate and Fe-containing rhodochrosite. The nodule shells are composed of quartz, chlorite, sericite, goethite, Mn-Fe oxyhydroxides and siderite. Fe-Mn oxyhydroxides in the nodule shells are formed due to an alteration of the carbonate minerals and inherited their composition. The formation of the nodules with Fe- and Mn-carbonates is related to diagenetic processes under reducing conditions of low Eh and high pH values. Later, carbonate minerals were altered into Fe-Mn oxyhydroxides. These alteration changes can be related to the influence of later magmatic activity in the area. An example of this activity is the presence of an igneous bodies established on both sides of the section.

Ninety-eight underground diamond holes (~102 km) drilled by Far Southeast Gold Resources Inc. at the Far Southeast porphyry Cu-Au deposit, Philippines, from 2011 to mid-2013, provide a three-dimensional exposure of the deposit between 700- and –750-m elevation, with surface at ~1,400-m elevation. Far Southeast contains an inferred resource of 891.7 million tonnes (Mt) averaging 0.7 g/t Au and 0.5 wt % Cu, equivalent to 19.8 Moz Au and 4.5 Mt Cu. This contribution reports the spatial and temporal distribution of alteration and mineralization at Far Southeast, notably a white-mica–chlorite-albite assemblage that formed after early secondary biotite and before late quartz–white-mica–pyrite alteration and that is associated with the highest copper and gold grades. Alteration assemblages were determined by drill core logging, short-wavelength infrared (SWIR) spectral analysis, petrographic examination, and a quantitative evaluation of materials by scanning electron microscopy (QEMSCAN) study. Alteration is limited around sparse veins or pervasive where vein density is high and the alteration halos coalesce. The alteration and mineralization zones with increasing depth are as follows: (1) the lithocap of quartz-alunite–dominated advanced argillic-silicic alteration that hosts part of the Lepanto high-sulfidation Cu-Au epithermal deposit (mostly above ~700-m elevation), (2) an aluminosilicate-dominated zone with coexisting pyrophyllite-diaspore ± kandite ± alunite and white mica (~700- to ~100-m elevation), (3) porphyry-style assemblages characterized by stockwork veins (below ~500-m elevation), (4) the 1 wt % Cu equivalent ore shell (~400- to –300-m elevation), and (5) an underlying subeconomic zone (about –300- to –750-m elevation, the base of drilling). The ore shells have a typical bell shape centered on a dioritic intrusive complex. The paragenetic sequence of the porphyry deposit includes stage 1 granular gray to white quartz-rich (± anhydrite ± magnetite ± biotite) veins with biotite-magnetite alteration. These were cut by stage 2 lavender-colored euhedral quartz-rich (± anhydrite ± sulfides) veins, with halos of greenish white-mica–chlorite-albite alteration. The white mica is largely illite, with an average 2,203-nm Al-OH wavelength position. The albite may reflect the mafic nature of the diorite magmatism. The quartz veins of this stage are associated with the bulk of copper deposited as chalcopyrite and bornite, as well as gold. Thin Cu sulfide (chalcopyrite, minor bornite) veins with minor quartz and/or anhydrite (paint veins), with or without a white-mica halo, also occur. These veins were followed by stage 3 anhydrite-rich pyrite-quartz veins with white-mica (avg 2,197 nm, illite)–pyrite alteration halos. Combined with previous studies, we conclude that this porphyry system, including the Far Southeast porphyry and Lepanto high-sulfidation Cu-Au deposits, evolved over a period of 0.1–0.2 m.y. Three diorite porphyry stocks were emplaced, and by ~1.4 Ma biotite-magnetite–style alteration formed with quartz-anhydrite veins and deposition of ≤0.5% Cu and ≤0.5 g/t Au (stage 1); coupled with this alteration style, a barren lithocap of residual quartz with quartz-alunite halo plus kandite ± pyrophyllite and/or diaspore formed at shallower depth (>700-m elevation). Subsequently, lavender quartz and anhydrite veins with bornite and chalcopyrite (high-grade stage, avg ~1 wt % Cu and ~1 g/t Au) and white-mica–chlorite-albite halos formed below ~400-m elevation (stage 2). They were accompanied by local pyrite replacement, the formation of hydrothermal breccias and Cu sulfide (paint) veins. Stage 2 was followed at ~1.3 Ma by the formation of igneous breccias largely along the margins of the high-grade zones and stage 3 pyrite-quartz-anhydrite ± chalcopyrite veins with white-mica (mostly illitic) halos. At shallower depths in the transition to the base of the lithocap, cooling led to the formation of aluminosilicate minerals (mainly pyrophyllite ± diaspore ± dickite) with anhydrite plus high-sulfidation-state sulfides and pyrite veinlets. Consistent with previous studies, it is likely that the lithocap-hosted enargite-Au mineralization formed during this later period.

The Elatsite–Chelopech ore field in the northern part of the Panagyurishte district in Central Bulgaria comprises numerous spatially associated porphyry copper and epithermal gold deposits and prospects. In addition to the mineralization and alteration features, trace elements, lead and sulfur isotope signatures of sulfide minerals from porphyry copper, base metal and gold-base metal deposits/prospects have been studied. LA-ICP-MS analyses of pyrite, arsenopyrite and sulfosalt minerals validate them as major carriers for Au, Ag, Sb, Se and Co. Pyrite from the three types of mineralization has specific geochemical characteristics. Pyrite from the porphyry copper deposits/prospects has generally lower total trace element content compared to pyrite from the epithermal prospects, except for Se, Co and Ni. Pyrite from the base metal and gold-base metal veins is enriched in As, Au, Ag, Sb and Pb. In pyrite from the base metal deposits, Co and Ni have contents comparable to the pyrite from the porphyry copper deposits, while pyrite from the gold-base metal veins shows lower Co and Ni. Arsenopyrite from these deposits shows similar features. Similarly, sphalerite from the gold-base metal veins also has lower Co content compared to sphalerite from the base metal veins but higher In and Cu contents. In addition to the close spatial relationships between the Elatsite and Gorna Kamenitsa porphyry Cu deposits and Negarstitsa-West and Dolna Kamenitsa base metal prospects, as well as similarities in the mineralization and alteration styles, the lead isotopic (206Pb/204Pb = 18.61–18.68, 207Pb/204Pb = 15.64–15.65 for porphyry and 206Pb/204Pb = 18.55–18.67, 207Pb/204Pb = 15.64–15.68 for base metal) and sulfur isotopic (δ34S values of −3 to +1‰ for porphyry and δ34S values of −1.7 to +3.5‰ for base metal) signatures of sulfides support the idea of a genetic link between these two types of deposits. The porphyry and base-metal mineralization result from a common major ore-forming event during the Late Cretaceous, corresponding to deep/higher-temperature and shallower/distal/lower-temperature environments, respectively. In particular, more radiogenic lead (206Pb/204Pb = 18.41–18.47, 207Pb/204Pb = 15.67–15.76) and slightly different sulfur isotopic compositions (δ34S values of +3.5 to +10.6‰) of sulfides from the distal gold-base metal veins of Kordunsko Dere, Svishti Plaz and Shipkite might be a consequence of the interaction of the ore-forming fluids with an external older crustal and isotopically positive S source. Alternatively, a different fluid source/event for the formation of these gold-base metal veins may be suggested., Minerals, 13 (5)

International audience; Pyrite (FeS 2), arsenopyrite (FeAsS) and löllingite (FeAs 2) are exceptional gold concentrators on Earth; yet the exact redox and structural state of this "invisible" gold and the forces driving its intake and release by these minerals remain highly controversial. Here we applied high resolution X-ray absorption spectroscopy to Au-bearing pyrite and iron sulfarsenides from hydrothermal deposits and their synthetic analogues. We show that Au preferentially enters octahedral Fe structural sites [Au(As,S) 6 ] enriched in As, by forming respectively [AuAs 1-3 S 5-3 ], [AuAs 3 S 3 ⋯AuAs 6 ] and [AuAs 6 ] atomic units in arsenian pyrite (>0.1-1.0 wt. % As), arsenopyrite and löllingite, implying a formal oxidation state of Au II in the minerals. In contrast, in As-poor pyrite, Au is dominantly chemisorbed as [Au I S 2 ] moieties in much lower concentrations. Combined with experimental data on Au mineral-fluid partitioning, our findings imply a universal control exerted by arsenic on gold incorporation in iron sulfides and sulfarsenides via coupled Au-As redox reactions. These reactions account for the observed variations in invisible gold contents in the minerals from different hydrothermal deposit types and enable quantitative prediction of iron sulfarsenide ability in controlling gold concentration and distribution in hydrothermal systems.

The world-class San Rafael tin (-copper) deposit (central Andean tin belt, southeast Peru) is an exceptionally large and rich (>1 million metric tons Sn; grades typically >2% Sn) cassiterite-bearing hydrothermal vein system hosted by a late Oligocene (ca. 24 Ma) peraluminous K-feldspar-megacrystic granitic complex and surrounding Ordovician shales affected by deformation and low-grade metamorphism. The mineralization consists of NW-trending, quartz-cassiterite-sulfide veins and fault-controlled breccia bodies (>1.4 km in vertical and horizontal extension). They show volumetrically important tourmaline alteration that principally formed prior to the main ore stage, similar to other granite-related Sn deposits worldwide. We present here a detailed textural and geochemical study of tourmaline, aiming to trace fluid evolution of the San Rafael magmatic-hydrothermal system that led to the deposition of tin mineralization. Based on previous works and new petrographic observations, three main generations of tourmaline of both magmatic and hydrothermal origin were distinguished and were analyzed in situ for their major, minor, and trace element composition by electron microprobe analyzer and laser ablation-inductively coupled plasma-mass spectrometry, as well as for their bulk Sr, Nd, and Pb isotope compositions by multicollector-inductively coupled plasma-mass spectrometry. A first late-magmatic tourmaline generation (Tur 1) occurs in peraluminous granitic rocks as nodules and disseminations, which do not show evidence of alteration. This early Tur 1 is texturally and compositionally homogeneous; it has a dravitic composition, with Fe/(Fe + Mg) = 0.36 to 0.52, close to the schorl-dravite limit, and relatively high contents (10s to 100s ppm) of Li, K, Mn, light rare earth elements, and Zn. The second generation (Tur 2)—the most important volumetrically—is pre-ore, high-temperature (>500°C), hydrothermal tourmaline occurring as phenocryst replacement (Tur 2a) and open-space fillings in veins and breccias (Tur 2b) and microbreccias (Tur 2c) emplaced in the host granites and shales. Pre-ore Tur 2 typically shows oscillatory zoning, possibly reflecting rapid changes in the hydrothermal system, and has a large compositional range that spans the schorl to dravite fields, with Fe/(Fe + Mg) = 0.02 to 0.83. Trace element contents of Tur 2 are similar to those of Tur 1. Compositional variations within Tur 2 may be explained by the different degree of interaction of the magmatic-hydrothermal fluid with the host rocks (granites and shales), in part because of the effect of replacement versus open-space filling. The third generation is syn-ore hydrothermal tourmaline (Tur 3). It forms microscopic veinlets and overgrowths, partly cutting previous tourmaline generations, and is locally intergrown with cassiterite, chlorite, quartz, and minor pyrrhotite and arsenopyrite from the main ore assemblage. Syn-ore Tur 3 has schorl-foititic compositions, with Fe/(Fe + Mg) = 0.48 to 0.94, that partly differ from those of late-magmatic Tur 1 and pre-ore hydrothermal Tur 2. Relative to Tur 1 and Tur 2, syn-ore Tur 3 has higher contents of Sr and heavy rare earth elements (10s to 100s ppm) and unusually high contents of Sn (up to >1,000 ppm). Existence of these three main tourmaline generations, each having specific textural and compositional characteristics, reflects a boron-rich protracted magmatic-hydrothermal system with repeated episodes of hydrofracturing and fluid-assisted reopening, generating veins and breccias. Most trace elements in the San Rafael tourmaline do not correlate with Fe/(Fe + Mg) ratios, suggesting that their incorporation was likely controlled by the melt/fluid composition and local fluid-rock interactions. The initial radiogenic Sr and Nd isotope compositions of the three aforementioned tourmaline generations (0.7160–0.7276 for 87Sr/86Sr(i) and 0.5119–0.5124 for 143Nd/144Nd(i)) mostly overlap those of the San Rafael granites (87Sr/86Sr(i) = 0.7131–0.7202 and 143Nd/144Nd(i) = 0.5121–0.5122) and support a dominantly magmatic origin of the hydrothermal fluids. These compositions also overlap the initial Nd isotope values of Bolivian tin porphyries. The initial Pb isotope compositions of tourmaline show larger variations, with 206Pb/204Pb(i), 207Pb/204Pb(i), and 208Pb/204Pb(i) ratios mostly falling in the range of 18.6 to 19.3, 15.6 to 16.0, and 38.6 to 39.7, respectively. These compositions partly overlap the initial Pb isotope values of the San Rafael granites (206Pb/204Pb(i) = 18.6–18.8, 207Pb/204Pb(i) = 15.6–15.7, and 208Pb/204Pb(i) = 38.9–39.0) and are also similar to those of other Oligocene to Miocene Sn-W ± Cu-Zn-Pb-Ag deposits in southeast Peru. Rare earth element patterns of tourmaline are characterized, from Tur 1 to Tur 3, by decreasing (Eu/Eu*)N ratios (from 20 to 2) that correlate with increasing Sn contents (from 10s to >1,000 ppm). These variations are interpreted to reflect evolution of the hydrothermal system from reducing toward relatively more oxidizing conditions, still in a low-sulfidation environment, as indicated by the pyrrhotite-arsenopyrite assemblage. The changing textural and compositional features of Tur 1 to Tur 3 reflect the evolution of the San Rafael magmatic-hydrothermal system and support the model of fluid mixing between reduced, Sn-rich magmatic fluids and cooler, oxidizing meteoric waters as the main process that caused cassiterite precipitation.

Distal skarns form by the metasomatic reactions of a host rock induced by far-traveled hydrothermal fluids. Physical and structural characteristics and geochemical patterns of distal Pb Zn skarn bodies were studied at the Petrovitsa deposit in southern Bulgaria. Skarn bodies formed from the interaction of hydrothermal fluids with reactive host lithologies (marble and gneiss). These fluids were transported along sub-vertical feeder structures and lithological contacts. Epidote skarn developed in gneiss protolith, and pyroxene (johannsenite) skarn developed in marble. Detailed geological mapping, complimented by measurements of the internal structure of the skarn body using pyroxene growth versors, quantifies the propagation direction of the skarn body: 1) away from the major local fluid conduit (feeder structure), and 2) away from lithological contacts between aluminosilicate rock and marble. Such growth suggests that fluid flow was generally orthogonal to the skarn front propagation direction in the pyroxene skarn. Textural, mineralogical and geochemical data from skarn samples reveal multiple growth generations of major skarn calc-silicates epidote and pyroxene. The epidote skarn is characterized by limited spatial distribution and fine-grained epidote/clinozoisite growth associated with massive replacement and sulfide mineralization. The pyroxene skarn consists of acicular clinopyroxene crystals which form spheroidal aggregates with discrete growth banding. These bands are the physical representation of the cyclic fluid pulses which resulted in rhythmic skarn growth marked by geochemical banding. In situ geochemical analyses in the epidote skarn reveal early Al-rich epidote overprinted by Fe-rich epidote associated with higher Mn and Sr contents and irregular compositional banding. Clinopyroxene (Jo60–95) shows general increase in Na, Al, Mn, and REE + Y with distance from the feeder structure and lithologic contacts. These elements correlate with the distance traveled by the hydrothermal fluid from the feeder to the site of skarnification, which we define using a proxy based on the Al content of pyroxene crystals. This reflects an increasing degree of fluid “contamination” by interaction with the aluminosilicate host rocks and functions as a proxy for fluid transport distance. The spatial distribution of trace-elements in pyroxene on an outcrop scale is indicative of discrete pulses of hydrothermal fluid resulting in precipitation of skarn calc-silicates along the increasingly tortuous fluid pathway between the feeder structure and the skarn front, resulting in both the macro- and micro-scale chemical and textural variability of the skarn body.

We report indium, germanium, gallium, and other minor and trace elements contents in sphalerite, chalcopyrite, galena, and tetrahedrite-tennantite occurring in skarn and skarn-free (“Cordilleran”) polymetallic mantos and vein ore bodies in the Miocene porphyry-related Morococha District, Central Peru. Among the investigated minerals, LA-ICP-MS measurements indicate that In and Ga concentrate mostly in sphalerite (Inter-Quartile Range [IQR] 217–2.7 ppm and up to 4608 ppm In; IQR 61–2.0 ppm and up to 2137 ppm Ga) and chalcopyrite (IQR 109–32 ppm and up to 1070 ppm In; IQR 62–1.5 ppm and up to 630 ppm Ga). In coeval generations of sphalerite and chalcopyrite, the contents of In and Ga in sphalerite are at least two times higher than in chalcopyrite. Germanium content is generally low in the four analyzed minerals (IQR 1.2–0.19 ppm), although late Fe-poor sphalerite may yield much higher values (IQR 129–74 ppm). Certain trace element contents appear to correlate with (i) the evolving characteristics of the hydrothermal fluids during individual mineralization events, and (ii) the location of the studied ore bodies relative to the hydrothermal feeders. The highest In values in sphalerite are found in high-sulfidation assemblages in Cordilleran polymetallic veins and, with lower amounts, in low-sulfidation assemblages in skarn bodies. In intermediate-sulfidation assemblages in Cordilleran mineralization, In content decreases from early to late generations of sphalerite, while that of Ge increases. Spatial trace-element trends in Cordilleran veins and replacement bodies formed during the so-called “Morococha district-scale polymetallic event” include, from porphyry-distal to porphyry-proximal locations: i) In and Cu, and to a lesser extent Ga, enrichment in sphalerite; ii) Se and Hg enrichment and Sn and Ag depletion in chalcopyrite; iii) In enrichment in galena; and iv) Ag depletion in tetrahedrite-tennantite. Our dataset suggests that In is incorporated in the sphalerite crystal lattice via coupled substitutions involving Cu and subordinately also Sn and Ag. Availability of Cu in the mineralizing fluids is therefore key to In enrichment in sphalerite. Progressive dilution of metal-rich magmatic-hydrothermal fluids and Cu precipitation probably account for the progressive In depletion in distal-to-porphyry Zn-Pb-Ag and Ag-Pb Cordilleran polymetallic mineralization and in late sphalerite generations in intermediate-sulfidation assemblages.

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.

The Puy-les-Vignes W deposit, located in the northwestern French Massif Central (FMC), is a rare occurrence of a wolframite-mineralized hydrothermal breccia pipe hosted in high-grade metamorphic gneisses. We present an integrated study of this deposit aiming to characterize the ore-forming hydrothermal system in link with the Variscan late-orogenic evolution of the FMC. Based on a set of representative samples from the host rocks and mineralization, we describe a detailed paragenetic sequence and we provide the major and trace element geochemistry of the granitic rocks and W–Nb–Ta–Sn–Ti oxide minerals, in situ U/Pb and 40Ar/39Ar geochronology, and a fluid inclusion study of quartz and wolframite. We demonstrate that the formation of this W-mineralized breccia pipe results from a multistage development related to four major episodes during the late Carboniferous. The first episode corresponds to the emplacement of an unexposed peraluminous granite at ca. 324 Ma, which generated microgranite dykes exposed at the present-day surface. The second episode is the formation of the quartz-supported breccia pipe and wolframite mineralization at ca. 318 Ma at a paleodepth of 7 km. The mineralizing fluids have a H2O–NaCl–CO2–CH4–N2 composition, a moderate-salinity ( 400 °C) during lithostatic to hydrostatic pressure variations caused by hydrofracturing of the host rocks. Wolframite deposition is interpreted to result from a W-rich intermediate-density magmatic fluid that exsolved from an evolved leucogranite and interacted with volatile-rich metasedimentary country rocks and/or possibly mixed with low-salinity metamorphic fluids of deep origin. The third episode corresponds to magmatic-hydrothermal Nb–Ta mineralization overprinting the W-mineralized system interpreted to be related to the intrusion at ca. 311 Ma of a rare-metal granite, which is part of a regional peraluminous rare-metal magmatism during the 315–310 Ma period. Finally, the last episode corresponds to disseminated Bi ± Au–Ag mineralization emplaced at ca. 300 Ma, which shares similar mineralogical features with late Carboniferous orogenic gold deposits in the FMC. The Puy-les-Vignes W deposit records, therefore, a multistage and long-lived development that extends over a timespan of 25 million years in a regional setting dominated by protracted peraluminous magmatism and high-temperature and low-pressure metamorphism. Although the local environment of ore deposition is atypical, our results show that the mineral assemblages, alteration styles, and fluid characteristics of the Puy-les-Vignes breccia pipe are similar to those of other peri-granitic W deposits in the FMC.

Ore precipitation in mineral deposits formed in the upper parts of a porphyry system, at shallow crustal level (< 1.5 km), such as epithermal Au-Ag-(Cu)-(As) and polymetallic deposits is often triggered by fluid cooling and/or mixing between fluids from different sources. Commonly, in such deposits, two main fluid sources are identified a deeply sourced magmatic fluid and a shallow meteoric water stored in a surficial aquifer. Oxygen and hydrogen isotope compositions of gangue and alteration minerals using conventional bulk isotopic methods support the existence of mixing between these two fluid types. However, bulk isotope analysis provides only limited information on the exact mixing mechanisms and on the changing proportions of the involved fluids. Due to their high spatial resolution, SIMS in-situ oxygen isotope and LA-ICP-MS trace element analyses, in transects across growth zones of single crystals are adequate tools to trace the dynamics of this fluid mixing. In this study, in-situ SIMS oxygen isotope and LA-ICP-MS trace element analyses were performed on 10 selected quartz crystals from the giant Cerro de Pasco porphyry-related epithermal polymetallic deposit in central Peru. The results, combined with previous microthermometric and LA-ICP-MS fluid inclusion studies on the same or equivalent crystals, allow quantifying and documenting the mixing between different types of fluids that formed the large Cerro de Pasco epithermal polymetallic deposit. The δ 18 O quartz values range between 4‰ and 20‰ and display variations up to 11.5‰ inside single crystals that cannot be only, nor mainly ascribed to fluid temperature changes. Rather, these variations record variable mixing proportions of a rising moderate-salinity magmatic fluid with a δ 18 O H2O around 10‰ and a low-salinity fluid with a δ 18 O H2O between 0 and 4‰, the latter stored below the paleo-water table. Each analyzed quartz crystals also display important variation of their trace element content, with Al (43 to 2098 ppm), Li (0.7 to 18 ppm), Ge (1.1 to 24ppm) and Ti (0.8 to 10 ppm). These variations do not systematically correlate with oxygen isotope compositions. This suggests that quartz trace element content is controlled by a complex interplay of fluid composition, temperature, pressure, and growth rate. Application of published Ti-in-quartz geothermometers on quartz grains from which the precipitation temperature is well constrained by fluid inclusion microthermometry, shows that it can lead to overestimation or underestimation of precipitation temperatures by more than 50 • C. The obtained δ 18 O quartz patterns measured along profiles in the studied quartz crystals, and less clearly the in-situ trace element compositions, reveal abrupt changes and suggest that mixing between magmatic and surface-derived low-salinity fluids was not a continuous process. It rather took place through the influx of multiple short-lived pulses of magmatic fluid into the surface-derived low-salinity fluid surface aquifer.

We present a high-resolution in situ study of oxygen and boron isotopes measured in tourmaline from the world-class San Rafael Sn (–Cu) deposit (Central Andean tin belt, Peru) aiming to trace major fluid processes at the magmatic-hydrothermal transition leading to the precipitation of cassiterite. Our results show that late-magmatic and pre-ore hydrothermal tourmaline has similar values of δ 18 O (from 10.6‰ to 14.1‰) and δ 11 B (from −11.5‰ to −6.9‰). The observed δ 18 O and δ 11 B variations are dominantly driven by Rayleigh fractionation, reflecting tourmaline crystallization in a continuously evolving magmatic-hydrothermal system. In contrast, syn-ore hydrothermal tourmaline intergrown with cassiterite has lower δ 18 O values (from 4.9‰ to 10.2‰) and in part higher δ 11 B values (from −9.9‰ to −5.4‰) than late-magmatic and pre-ore hydrothermal tourmaline, indicating important contribution of meteoric groundwater to the hydrothermal system during ore deposition. Quantitative geochemical modeling demonstrates that the δ 18 O- δ 11 B composition of syn-ore tourmaline records variable degrees of mixing of a hot Sn-rich magmatic brine with meteoric waters that partially exchanged with the host rocks. These results provide thus direct in situ isotopic evidence of fluid mixing as a major mechanism triggering cassiterite deposition. Further, this work shows that combined in situ δ 18 O and δ 11 B analyses of tourmaline is a powerful approach for understanding fluid processes in dynamic magmatic-hydrothermal environments.

The late Palaeocene to the middle Eocene (57.5 to 46.5 Ma) recorded a total of 39 hyperthermals – periods of rapid global warming documented by prominent negative carbon isotope excursions (CIEs) as well as peaks in iron content – have been recognized in marine cores. Documenting how the Earth system responded to rapid climatic shifts during hyperthermals provides fundamental information to constrain climatic models. However, while hyperthermals have been well documented in the marine sedimentary record, only a few have been recognized and described in continental deposits, thereby limiting our ability to understand the effect and record of global warming on terrestrial systems. Hyperthermals in the continental record could be a powerful correlation tool to help connect marine and continental deposits, addressing issues of environmental signal propagation from land to sea. In this study, we generate new stable carbon isotope data (δ13C values) across the well-exposed and time-constrained fluvial sedimentary succession of the early Eocene Castissent Formation in the south central Pyrenees (Spain). The δ13C values of pedogenic carbonate reveal – similarly to the global records – stepped CIEs, culminating in a minimum δ13C value that we correlate with the hyperthermal event “U” at ca. 50 Ma. This general trend towards more negative values is most probably linked to higher primary productivity leading to an overall higher respiration of soil organic matter during these climatic events. The relative enrichment in immobile elements (Zr, Ti, Al) and higher estimates of mean annual precipitation together with the occurrence of small iron oxide and iron hydroxide nodules during the CIEs suggest intensification of chemical weathering and/or longer exposure of soils in a highly seasonal climate. The results show that even relatively small-scale hyperthermals compared with their prominent counterparts, such as PETM, ETM2, and ETM3, can leave a recognizable signature in the terrestrial stratigraphic record, providing insights into the dynamics of the carbon cycle in continental environments during these events.

International audience; Rare metals (Ge, Ga, In, Cd) are key resources for the development of green technologies and are commonly found as trace elements in base-metal mineral deposits. Many of these deposits are in orogenic belts and the impact of recrystallization on rare metal content and distribution in sphalerite needs to be evaluated. Based on laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses, and micro-imaging techniques such as laser-induced breakdown spectroscopy (LIBS) and electron backscattered diffraction (EBSD), we investigate the minor and trace element composition related to sphalerite texture for three types of mineralization from the Pyrenean Axial Zone (PAZ). Vein mineralization (type 2b) appears significantly enriched in Ge and Ga compared to disseminated and stratabound mineralizations (type 1 and type 2a, respectively). In vein mineralization, the partial recrystallization induced by deformation led to the remobilization of Ge, Ga, and Cu from the sphalerite crystal lattice into accessory minerals. We propose that the association of intragranular diffusion and fluid-rock reaction were likely responsible for the formation of patchy-oscillatory zoning in sphalerite, and the crystallization of Ge-rich accessory minerals. Chemical and textural heterogeneity is common in sphalerite from various world-class deposits and a full understanding of these heterogeneities is now crucial to assess the rare metal potential, and associated extraction processes of deformed base-metal ores.

This study aims to identify the dominant fast pathways for 39Ar loss during step-heating 40Ar/39Ar analysis of alkali feldspar from the Shap granite (UK). In our analysis we combined step-heating 40Ar/39Ar data acquired from variably sized feldspar fragments (0.4 to 2.2 mm in the shortest dimension) and optical and electron microscopy observations of microtextural modifications caused by heating in a muffle furnace in air. Our optical and electron microscopy results suggest that laboratory heating of the Shap feldspar causes it to fracture. The resulting cracks form an interconnected network, which may link with some of previously documented nanoscale defects such as nanotunnels, slots, pull aparts and bubbles. Our step-heating 40Ar/39Ar analyses yielded non-linear Arrhenius trajectories of 39Ar release. The non-linearity is best explained by heating-induced reduction of the effective diffusion length due to fracturing, likely with some contribution from nanotunnels, pull-aparts, slots and bubbles. Incoherent grain boundaries apparently played a minor role in providing fast pathways for 39Ar loss, if any. Importantly, unambiguous evidence for a reduction of the diffusion length during step-heating was only observed in experiments with large fragments (≥1 mm in the shortest dimension). The Arrhenius trajectory obtained from the smaller fragments (≤0.5 mm in the shortest dimension) appears to be consistent with the presence of variably-sized non-interacting intra-grain diffusion domains that existed prior to mineral separation. Heating-induced fracturing must be taken into account when interpreting 40Ar/39Ar dates of alkali feldspar, with particular focus on the following two points. First, this process is clearly inconsistent with the underlying assumptions of commonly utilised multi-diffusion domain (MDD) theory, although it can result in 39Ar release patterns that appear consistent with them. Therefore, it is important to identify on a case by case basis the dominant fast pathways for 39Ar loss from alkali feldspar during step-heating before applying MDD theory. Second, if heating-induced fracturing is ubiquitous in alkali feldspar and affects even gem-quality samples, then presently available diffusion parameters of Ar in alkali feldspar structure may be inaccurate to some degree, since all of them were obtained without considering the presence of cracks.

The Passa Três granite is a 5 km2 intrusion in southern Brazil with an NNE–SSW-elongated shape, hosting gold-bearing quartz veins with fluorite, carbonates, sulphides (pyrite, chalcopyrite, aikinite, molybdenite) and native gold. Orebodies are hosted by the pluton roof zone, which is marked by various textures indicating magmatic–hydrothermal transition processes. Mineralisation formed between 613 and 608 Ma in extensional pull-apart structures controlled by two conjugated N–S and E–W fault systems. We report results from petrography, quantitative evaluation of minerals by scanning electron microscopy (QEMSCAN), scanning electron microscopy (SEM), electron probe microanalyses (EPMA), X-ray fluorescence (XRF), trace element analyses of pyrite by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), sulphur isotope (δ34S) analyses, and fluid inclusion microthermometry. Hydrothermal alteration is dominantly developed as phengite–quartz–carbonate and sericite–carbonate–chlorite assemblages along mineralised structures. Fluid inclusion study indicates mineralising fluids with H2O-CO2-NaCl composition, low to moderate salinity (0.2–12.84 wt % NaCl eq.), and temperatures from 400 to 150 °C. The sulphur isotopic composition of pyrite (−0.1 to 1.1‰) suggests magmatic origin. These data, in conjunction with structurally controlled mineralisation enriched in Au-Bi minerals shortly post-dating the granite emplacement, appoint towards similarities between the Passa Três deposit and intrusion-related gold systems. The specific location of the mineralisation in the core (and in the roof zone, regarding its vertical position) of the Passa Três granitic intrusion defines it as “granite-hosted” thus, it is representative of a specific model that can be used for exploration of other intrusion-related/hosted gold deposits near the studied area or in other locations.

The composite Meghri-Ordubad pluton (MOP) is located in the southernmost Lesser Caucasus and outcrops over ~1000 km2 in southern Armenia and Nakhitchevan. It is characterized by nested intrusions incrementally emplaced over ~30 Myr from the Middle Eocene to Early Miocene, coeval with the closure of the Neotethyan Ocean and the regional Arabia-Eurasia continental collision. We recognize three compositionally distinct intrusive series in the MOP: a medium- to high-K calc-alkaline series 1 dominated by gabbro, quartz diorite and tonalite, a shoshonitic to high-K calc-alkaline series 2 including gabbro, monzogabbro, monzodiorite, monzonite and syenite, and a high-K calc-alkaline adakitic series 3 characterized by the emplacement of lamprophyre dikes followed by porphyritic granodioritic intrusions and dikes. Thermobarometry calculations together with detailed petrography, mineral chemistry and experimental mineral stability P-T diagrams indicate a polybaric crystallization history and magma emplacement at mid- to upper crustal levels (0.1-0.3 GPa). Mineral textures and compositions reveal open-system magmatic processes such as mafic magma replenishment and reactivation of crystal mushes prior to transport towards shallower crustal levels in the MOP. The evolution of magma chemistry (calc-alkaline vs shoshonitic) and mineral assemblages (amphibole-bearing vs amphibole-free) indicate fluctuation in primary melt alkali and water contents over time. Such chemical evolution is ascribed to a decrease in the degree of partial melting of a chemically heterogeneous, but isotopically homogeneous, mantle source. Overall, the MOP is characterized by the successive emplacement of hydrous magma batches in the mid- to upper crust and petrological processes that were dominated by fractional crystallization (± crustal assimilation) upon cooling and, or, decompression (± degassing). We propose a new temporal and spatial petrogenetic model for the MOP, encompassing three long-lived, chemically distinct magmatic series incrementally assembled over 30 Myr within a pre-, syn- and post-collisional geodynamic setting.

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.

The Takidani pluton represents one of a few locations where melt extraction from a crystal mush is preserved in the natural rock record, making it an extremely good case study for investigating the generation of evolved melt reservoirs in the upper crust. Located in the Japan Alps, the Takidani pluton shows a clear vertical zonation consisting of granite and granodiorite in the lower and mid- dle section, a fine-grained porphyritic granitic unit in the upper section and a marginal granodiorite at the roof contact with the host-rock. We present a detailed petrographic and geochemical study using samples collected along a section that traverses the entire vertical section of the pluton. No sharp contacts are found between units. Instead, gradual changes in rock fabric and mineralogy are observed between the lower granodiorite and overlying porphyritic unit. Major and trace elem- ent bulk-rock compositions show sigmoidal variations from the bottom to top of the pluton. Incompatible elements and silica contents increase roofwards within the porphyritic unit. Plagioclase chemistry reveals three main crystal populations (P1, P2 and P3) with Fe contents increasing towards the base of the pluton. Comparison with existing crystallization experiments, thermobarometry and hygrometry indicate that the magmas were emplaced at around 200 MPa, 850–900 C and bulk water contents of 3–4wt %. Whole-rock major and trace element analyses to- gether with mineral chemistry and textural observations suggest that the fine-grained porphyritic unit was extracted from the underlying granodiorite at temperatures between 800 and 740 C and crystallinities of 45–65 wt %. Radiogenic isotopes indicate only minor assimilation (2–6 wt %) and support melt evolution through crystal fractionation. The fine-grained matrix of the porphyritic unit may have been the result of pressure quenching associated with a volcanic eruption.

During the late Palaeocene to the middle Eocene (57.5 to 46.5 Ma) a total of 39 hyperthermals – periods of rapid global warming recorded by prominent negative carbon isotope excursions (NCIEs) as well as peaks in iron content – have been recognized in marine cores. Understanding how the Earth system responded to rapid warming during these hyperthermals is fundamental because they represent potential analogues, in the geological record, to the ongoing anthropogenic modification of global climate. However, while hyperthermals have been well documented in the marine sedimentary record, only few have been recognized and described in continental deposits, thereby limiting our ability to understand the effect and record of global warming on terrestrial surficial systems. Hyperthermals in the continental record could be a powerful correlation tool to help connect marine and continental records, addressing issues of environmental signal propagation from land to sea. In this study, we generate new stable carbon isotope data (δ13C values) across the well-exposed and time-constrained fluvial sedimentary succession of the early Eocene Castissent Formation in the South-Central Pyrenees (Spain). The δ13C values of pedogenic carbonate reveal – similarly to the global records – stepped NCIEs, culminating in a minimum δ13C value that we correlate with the hyperthermal event U at ca. 50 Ma. This general trend towards more negative values is most probably linked to higher primary productivity leading to an overall higher respiration of soil organic matter during these climatic events. The relative enrichment in immobile elements (Zr, Ti, Al) and higher estimates of mean annual precipitation together with the occurrence of small iron-oxides/hydroxides nodules during the NCIEs suggest intensification of chemical weathering and/or longer exposure of soils in a highly seasonal climate. The results show that even relatively small-scale hyperthermals compared with their prominent counterparts, such as PETM, ETM2 and 3, have left a recognizable trace in the stratigraphic record, providing insights into the dynamics of the carbon cycle in continental environments during these events.

International audience; This paper aims at providing new insights into W-Sn ore-forming processes within one of the largest granitic provinces in the world (Nanling Range, South China), which was emplaced during the Jurassic-Cretaceous period. The origin, composition and pressure-temperature conditions of fluids involved in the W-Sn ore-forming processes have been investigated by microthermometry, Raman spectroscopy, LA-ICPMS, hydrogen isotope analyses of fluid inclusions and oxygen isotope analyses of minerals from the Maoping and Piaotang W-Sn deposits. For each deposit, pre- (quartz), syn- (wolframite and cassiterite) and post-ore (quartz, topaz and fluorite) minerals were studied. In both deposits, the vast majority of fluid inclusions are aqueous with salinities between 0.0 and 12.6 wt. % equiv. NaCl and homogenization temperatures between 136 and 349 °C. A minor proportion (~5%) of inclusions observed in the ore-stage quartz from Maoping have aquo-carbonic compositions. For both deposits, four compositional groups are defined. Early quartz fluid inclusions are characterized by salinities between 0.4 and 9.0 wt. % equiv. NaCl, trapping temperatures between 150 and 350 °C, and pressures between 20 and 150 MPa. LA- ICPMS analyses of these fluid inclusions reveal a wide range of Na, K and Li concentrations, as well as relatively low metal contents (W < 40 ppm). Values of δ18O in quartz range from -3.6 to 5.3 ‰ VSMOW while δD values of the fluid inclusions range from -59 to -51 ‰ VSMOW. The salinity of fluid inclusions in wolframite, cassiterite, topaz and fluorite is between 2.4 and 11.2 wt. % equiv. NaCl, trapping temperatures are between 200 and 600 °C, and pressures range from 20 to 250 MPa. LA-ICPMS analyses of these fluid inclusions reveal higher concentrations of Na, K and Li as well as Cs and metals (e.g. between 10 and 220 ppm W). Values of δ18O in wolframite, cassiterite, topaz and fluorite crystals range from -3.0 to 3.3 3 ‰ VSMOW while δD values of fluid inclusions in these mineral phases range from -78 to -72 ‰ VSMOW. At Piaotang, fluid inclusions in wolframite as well as in post-ore quartz and fluorite have salinities of 5.6 to 12.6 wt.% eq. NaCl, trapping temperatures between 150 and 400 °C and pressures of 20 to 150 MPa. LA-ICPMS analyses of these fluid inclusions reveal similar compositions to early quartz fluid inclusions. Values of δ18O in wolframite and quartz crystals range from -0.8 to 5.2 ‰ VSMOW, while the δD values of fluid inclusions range from -66 to -62 ‰ VSMOW. Collectively, the data suggest the involvement of four aqueous fluid end-members, mixed episodically in the mineralization process: (A) a low-salinity, low-temperature, metal-poor, low-δ18O, low-δD fluid derived from meteoric water; (B) a high-salinity, high-temperature, metal-poor, high-δ18O, low-δD fluid derived from a differentiated peraluminous granitic magma; (C) a high-salinity, high-temperature, metal-rich, lower δD magmatic fluid derived from a more differentiated peraluminous granitic magma; and (D) a high-salinity, high-temperature, metal-rich, high-δ18O, low-δD magmatic fluid. This study shows that multiple fluids with distinct magmatic and meteoric origins were involved in the formation of these W-Sn deposits and that the dilution of metal-bearing magmatic fluids by meteoric fluids was probably the main driver for ore deposition. The common fluid history of the two deposits studied, as well as similarities with other deposits in the Jiangxi province, points towards common ore-forming processes at the regional scale.

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.

Active and inactive hydrothermal chimneys composed almost entirely of enargite and luzonite, rare minerals in seafloor hydrothermal deposits, were found at the summits of two submarine volcanoes, North Su and Kaia Natai, in the Manus Back-Arc Basin. Detailed mineralogical and geochemical studies revealed that most probably these deposits precipitated at T = 200°–330 °C and high fS2. The negative δ34S values (− 8.58 to − 3.70‰) of the enargite-luzonite are best explained by disproportionation reactions of magmatic SO2 and suggest that the high fS2 is likely provided by direct magmatic input of SO2 into the hydrothermal system. Fractionation of Cu stable isotopes during the precipitation of enargite-luzonite (δ65Cu ranges from − 0.20 to + 0.35‰) is inferred to be associated with either Rayleigh-type fractionation, or redox processes (Cu+ oxidation to Cu2 +) and the mass balance of dissolved Cu+ and Cu2 + species in the hydrothermal fluid. The trace element composition of enargite and luzonite indicates a temporal fluctuation of the chemistry of the ore-forming fluid with an increase of Fe, Ga, Tl, Au, Hg, Pb and Ag, and decrease of Sb, Sn, Te, Ge and V concentrations with time and points out that this type of deposits is the richest in Au (average 11.9 ppm) and Te (average 169 ppm) among all other types of seafloor metal deposits. In addition to the widespread inorganic precipitation of enargite and luzonite in this setting, there is evidence that this mineralization may be biogenically mediated on the external surfaces of the active vents. Fungi-like filaments mineralized by luzonite imply that the fungi (Dikarya subkingdom) may be implicated in a mechanism of bio-sequestration of As, S and Cu, and provide the initial substrate for luzonite precipitation. The studied enargite-luzonite deposits have characteristics similar to those of subaerial high-sulfidation epithermal mineralization: back-arc basin setting; acid-sulfate and boiling ore-forming fluids; altered (advanced argillic stage) dacitic host rocks; major enargite-luzonite and minor pyrite, barite and S0; δ34S < 0‰. Therefore, they may be considered as submarine analogues of subaerial high-sulfidation epithermal deposits with the potential for concealed porphyry Cu(single bondAu) mineralization at depth.

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.

Heating of quartz crystals in order to study melt and high-temperature fluid inclusions is a common practice to constrain major physical and chemical parameters of magmatic and hydrothermal processes. Diffusion and modification of trace element content in quartz and its hosted melt inclusions have been investigated through step-heating experiments of both matrix-free quartz crystals and quartz crystals associated with sulfides and other minerals using a Linkam TS1500 stage. Magmatic and hydrothermal quartz were successively analyzed after each heating step for Cu, Al, and Ti using electron probe micro-analyzer. After the last heating step, quartz crystals and their hosted melt inclusions were analyzed by laser ablation inductively coupled plasma mass spectrometry and compared to unheated samples. Heated samples reveal modification of Cu, Li, Na, and B contents in quartz and modification of Cu, Li, Ag, and K concentrations in melt inclusions. Our results show that different mechanisms of Cu, Li, and Na incorporation occur in magmatic and hydrothermal quartz. Heated magmatic quartz records only small, up to a few ppm, enrichment in Cu and Na, mostly substituting for Li. By contrast, heated hydrothermal quartz shows enrichment up to several hundreds of ppm in Cu, Li, and Na, which substitute for originally present H. This study reveals that the composition of both quartz and its hosted melt inclusions may be significantly modified upon heating experiments, leading to erroneous quantification of elemental concentrations. In addition, each quartz crystal also becomes significantly enriched in Cu in the sub-surface layer during heating. We propose that sub-surface Cu enrichment is a direct indication of Cu diffusion in quartz externally sourced from both the surrounding sulfides as well as the copper pins belonging to the heating device. Our study shows that the chemical compositions of both heated quartz and its hosted inclusions must be interpreted with great caution to avoid misleading geological interpretations.

International audience; Chemical and isotopic compositions of magmatic crystals provide important information to distinguish between deep juvenile and crustal contributions. In this work, high-resolution multicollector secondary ion mass spectrometry data reveal strong variations of δ18O values in three plagioclase crystals (800 – 1700 μm) from two representative basaltic andesite samples of the 2010 Merapi eruption (Central Java, Indonesia). The δ18O values (from 4.6 to 7.9 ‰) are interpreted to reflect oxygen isotope heterogeneity in the melt composition during plagioclase growth. The lowest δ18O values (4.6 – 6.6 ‰) are found in anorthite-rich cores (An82–97), whereas higher δ18O values (5.7 to 7.9 ‰) are found in anorthite-poorer zones (An33–86), typically in crystal rims. Combining these new plagioclase δ18O data with δ18O of calc-silicate crustal xenoliths erupted between 1994 – 1998, the composition of glass inclusions hosted by the anorthite-rich plagioclase (An82-92), available experimental data, and the results of thermodynamic modelling using the Magma Chamber Simulator code, we conclude that the abundant anorthite-rich cores crystallized from a mantle-derived hydrous basaltic to basaltic trachyandesite melt that recharged a deeper (200-600 MPa) magma storage zone, whereas lower anorthite zones crystallized at shallower levels (100-200 MPa). The oxygen isotope variations in the plagioclase are explained by a two-stage model of interaction of the hydrous, mafic mantle-derived magma (1) with old crustal rocks depleted in 18O due to high temperature alteration that yielded the low δ18O values in the anorthite-rich cores at deep levels (13 – 20 km), and later (2) with 18O-enriched carbonate material that yielded the high δ18O values in anorthite-poorer zones at shallow levels (∼4.5 – 9 km). Thermodynamic modelling is consistent with ∼18 wt.% assimilation of crustal calc-silicate material at 925 – 950°C and 100 – 200 MPa by the 2010 Merapi basaltic andesite magma prior to eruption. Timescales for plagioclase phenocryst growth and residence in the magmatic plumbing system are ⩽34 years. The combined data thus reveal efficient magma recharge and crustal assimilation processes that characterize the open-system magma storage and transport systems associated with the 2010 Merapi eruption.

The breccia-hosted epithermal Au-Ag deposit of Rosia Montana is located 7 km northeast of Abrud, in the northern part of the South Apuseni Mountains, Romania. Estimated total reserves of 214.91 million metric tons (Mt) of ore at 1.46 g/t Au and 6.9 g/t Ag (10.1 Moz of Au and 47.6 Moz of Ag) make Rosia Montana one of the largest gold deposits in Europe. At this location, Miocene calc-alkaline magmatic and hydrothermal activity was associated with local extensional tectonics within a strike-slip regime related to the indentation of the Adriatic microplate into the European plate during the Carpathian orogenesis. The host rocks of the magmatic complex consist of pre-Mesozoic metamorphosed continental crust covered by Cretaceous turbiditic sediment (flysch). Magmatic activity at Rosia Montana and its surroundings occurred in several pulses and lasted about 7 m.y. Rosia Montana is a breccia-hosted epithermal system related to strong phreatomagmatic activity due to the shallow emplacement of the Montana dacite. The Montana dacite intruded Miocene volcaniclastic material (volcaniclastic breccias) and crops out at Cetate and Cârnic Hills. Current mining is focused primarily on the Cetate open pit, which was mapped in detail, leading to the recognition of three distinct breccia bodies: the dacite breccia with a dominantly hydrothermal matrix, the gray polymict breccia with a greater proportion of sand-sized matrix support, and the black polymict breccia, which reached to the surface, contains carbonized tree trunks and has a dominantly barren clastic matrix. The hydrothermal alteration is pervasive. Adularia alteration with a phyllic overprint is ubiquitous; silicification and argillic alteration occur locally. Mineralization consists of quartz, adularia, carbonates (commonly Mn-rich), pyrite, Fe-poor sphalerite, galena, chalcopyrite, tetrahedrite, and native gold and occurs as disseminations, as well as in veins and filling vugs within the Montana dacite and the different breccias. The age of mineralization (12.85 ± 0.07 Ma) was determined by 40 Ar- 39 Ar dating on hydrothermal adularia crystals from vugs in the dacite breccia in the Cetate open pit. Microthermometric measurements of fluid inclusions in quartz phenocrysts from the Montana dacite revealed two fluid types that are absent from the hydrothermal breccia and must have been trapped at depth prior to dacite dome emplacement: brine inclusions (32–55 wt % NaCl equiv, homogenizing at T h > 460°C) and intermediate density fluids (4.9–15.6 wt % NaCl equiv, T h between 345°–430°C). Secondary aqueous fluid inclusion assemblages in the phenocrysts have salinities of 0.2 to 2.2 wt percent NaCl equiv and T h of 200° to 280°C. Fluid inclusion assemblages in hydrothermal quartz from breccias and veins have salinities of 0.2 to 3.4 wt percent NaCl equiv and T h from 200° to 270°C. The oxygen isotope composition of several zones of an ore-related epithermal quartz crystal indicate a very constant δ 18 O of 4.5 to 5.0 per mil for the mineralizing fluid, despite significant salinity and temperature variation over time. Following microthermometry, selected fluid inclusion assemblages were analyzed by laser ablation-inductively coupled-plasma mass spectrometry (LA-ICPMS). Despite systematic differences in salinity between phenocryst-hosted fluids trapped at depth and fluids from quartz in the epithermal breccias, all fluids have overlapping major and trace cation ratios, including identical Na/K/Rb/Sr/Cs/Ba. Consistent with the constant near-magmatic oxygen isotope composition of the hydrothermal fluids, these data strongly indicate a common magmatic component of these chemically conservative solutes in all fluids. Cu, Pb, Zn, and Mn show variations in concentration relative to the relatively non-reactive alkalis, reflecting the precipitation of sulfide minerals together with Au in the epithermal breccia, and possibly of Cu in an inferred subjacent porphyry environment. The magmatic-hydrothermal processes responsible for epithermal Au-Ag mineralization at Rosia Montana are, however, not directly related to the formation of the spatially associated porphyry Cu-Au deposit of Rosia Poieni, which occurred about 3 m.y. later.

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.

Porphyry systems supply most copper and significant gold to our economy. Recent studies indicate that they are frequently associated with high Sr/Y magmatic rocks, but the meaning of this association remains elusive. Understanding the association between high Sr/Y magmatic rocks and porphyry-type deposits is essential to develop genetic models that can be used for exploration purposes. Here we present results on a Pleistocene volcano of Ecuador that highlight the behaviour of copper in magmas with variable (but generally high) Sr/Y values. We provide indirect evidence for Cu partitioning into a fluid phase exsolved at depths of ~15 km from high Sr/Y (>70) andesitic magmas before sulphide saturation. This lends support to the hypothesis that large amounts of Cu- and S-bearing fluids can be accumulated into and released from a long-lived high Sr/Y deep andesitic reservoir to a shallower magmatic-hydrothermal system with the potential of generating large porphyry-type deposits.

The Coka Marin polymetallic (Cu-Au-Ag-Zn-Pb) deposit belongs to the world-class Bor ore district in Serbia and consists of three lens-shaped orebodies hosted by Late Cretaceous andesitic volcanic rocks. Pyrite is the dominant mineral in the deposit and shows a great variety of textures and zoning. It occurs as fine- to coarse-grained crystals and massive, spongy, colloform, framboidal, oolitic, and replacement aggregates. Complex relationships with other minerals and the presence of microscale mineral inclusions and micro- to nanoscale porosity are common features of the pyrite at Coka Marin. Minor amounts of Cu (up to 7.9 wt.%), Pb (up to 7 wt.%), As (up to 4 wt.%), Ag (up to 1 wt.%), Te (up to 0.07 wt.%), and rarely Sb (up to 0.11 wt.%) were detected in pyrite using an electron microprobe. Zoning and heterogeneity in pyrite is mainly caused by variable copper content. Structurally bound Cu in pyrite from this deposit reported in a previous study was confirmed by our new electron microprobe analyses. Distinct Pb-bearing zones frequently occur in pyrite following oscillatory zoning and crystal shapes. These zones also contain lesser amounts of the other elements mentioned above. Using the focused ion beam (FIB) technique to prepare electron-transparent foils and transmission electron microscopy (TEM), we found that these elements form nanoscale Pb-(±As, Ag, Cu)-bearing inclusions (mosty

Chemical Geology, 281 (3-4), ISSN:0009-2541, ISSN:1872-6836

Mineralium Deposita, 44 (6), ISSN:0026-4598, ISSN:1432-1866

International audience; A characteristic feature of the nuclear microprobe using a 3 MeV proton beam is the long range of particles (around 70 μm in light matrices). The PIXE method, with EDS analysis and using the multilayer approach for treating the X-ray spectrum allows the chemistry of an intra-crystalline inclusion to be measured, provided the inclusion roof and thickness at the impact point of the beam (Z and e, respectively) are known (the depth of the inclusion floor is Z + e). The parameter Z of an inclusion in a mineral can be measured with a precision of around 1 μm using a motorized microscope. However, this value may significantly depart from Z if the analyzed inclusion has a complex shape. The parameter e can hardly be measured optically. By using combined RBS and PIXE measurements, it is possible to obtain the geometrical information needed for quantitative elemental analysis. This paper will present measurements on synthetic samples to investigate the advantages of the technique, and also on natural solid and fluid inclusions in quartz. The influence of the geometrical parameters will be discussed with regard to the concentration determination by PIXE. In particular, accuracy of monazite micro-inclusion dating by coupled PIXE-RBS will be presented.

The crystal morphology of vacuoles of fluid inclusions in some transparent, low-iron and relatively low-temperature sphalerites from the vein and replacement Pb-Zn ore deposits of the Madan ore district, Bulgaria, was studied both by optical microscopy in oriented thin sections and by SEM on open cleavage surfaces. The vacuoles represent negative crystals bounded by faces of d {110}, o {111} and - o {111} forms together with small faces of a {100}, e {210}, n {211}, p {221}, - n {211} and - p {221} forms. Their corners and edges are rounded. The primary inclusions, formed mainly at 200–220 °C, have an isometric, elongated, tubular, spindle-like or acute-angled habit depending on their position and the influence of the growth defects (growth zones, subgrain and sector boundaries, twin planes, etc .). The secondary fluid inclusions, healing fractures in sphalerite crystals mainly at 160–185 °C, are strongly controlled by the thickness and local configuration of the crack surfaces. They are flat, irregular or isometric in shape. It is suggested that the fluid inclusions in the low-T sphalerite usually preserve their initial high-energy and non-equilibrium crystal morphology formed during periods of rapid growth.

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

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) in combination with near-infrared microscopy of fluid inclusions hosted by ore minerals that are opaque to visible light can provide the composition of ore-precipitating fluids. We applied the two techniques to well-constrained fluid inclusion assemblages hosted by pyrite, enargite, and quartz to trace the source and evolution of the fluids in high-sulfidation epithermal veins overprinting a porphyry copper deposit at Rosia Poieni, Romania. Despite some analytical limitations caused by the sulfide host minerals, the data demonstrate that fluids trapped in apparently cogenetic quartz and ore minerals are chemically different. Systematic changes in major and trace element ratios between liquid-vapor, vapor-rich, and brine fluid inclusion assemblages in the three minerals record an evolving fluid source at the porphyry to epithermal transition. Regarding their Cs/(Na + K) ratios, most of epithermal quartz-hosted fluid inclusion assemblages form a well-defined cluster, which coincides with the narrow range of the porphyry-stage fluids trapped in early quartz of the porphyry stockwork veins. Their Cu/(Na + K) ratios are 10 to 100 times lower compared to the pyrite-hosted inclusions and correspond to the lowest Cu/(Na + K) ratios recorded for the porphyry-stage fluids. By contrast, pyrite-hosted, vapor-rich fluid inclusions have the highest Cu/(Na + K) similar to the highest Cu/(Na + K) ratios measured in the porphyry-stage fluid inclusions. The results led to the conclusion that the gangue and ore minerals in the high-sulfidation epithermal veins at Rosia Poieni formed by successive pulses of chemically distinct hydrothermal fluids that were successively exsolved from residual melt batches of a progressively crystallizing magma at greater depth. These results are consistent with detailed textural observations, but petrography alone could not have led to this unambiguous conclusion.