Section of Earth and Environmental Sciences

The origin of the hypersaline fluids (magmatic or basinal brine?), associated with iron oxide (Cu–U–Au–REE) deposits, is controversial. We report the first chlorine and strontium isotope data combined with Cl/Br ratios of fluid inclusions from selected iron oxide–copper–gold (IOCG) deposits (Candelaria, Raúl–Condestable, Sossego), a deposit considered to represent a magmatic end member of the IOCG class of deposit (Gameleira), and a magnetite–apatite deposit (El Romeral) from South America. Our data indicate mixing of a high δ 37Cl magmatic fluid with near 0‰ δ 37Cl basinal brines in the Candelaria, Raúl–Condestable, and Sossego IOCG deposits and leaching of a few weight percent of evaporites by magmatic-hydrothermal (?) fluids at Gameleira and El Romeral. The Sr isotopic composition of the inclusion fluids of Candelaria, Raúl–Condestable, and El Romeral confirms the presence of a non-magmatic fluid component in these deposits. The heavy chlorine isotope signatures of fluids from the IOCG deposits (Candelaria, Raúl–Condestable, Sossego), reflecting the magmatic-hydrothermal component of these fluids, contrast with the near 0‰ δ 37Cl values of porphyry copper fluids known from the literature. The heavy chlorine isotope compositions of fluids of the investigated IOCG deposits may indicate a prevailing mantle Cl component in contrast to porphyry copper fluids, an argument also supported by Os isotopes, or could result from differential Cl isotope fractionation processes (e.g. phase separation) in fluids of IOCG and porphyry Cu deposits.

Early Cretaceous plutonic rocks exposed south of Copiapó form part of the Coastal Batholith of northern Chile. These rocks intrude arcderived volcanic and volcaniclastic rocks and marine limestones that were deposited in the Early Cretaceous Atacama backarc basin. The Copiapó plutonic complex consists mainly of calc-alkaline, medium-to coarse-grained diorite, granodiorite, tonalite, monzodiorite, and quartz monzonite. The plutonic rocks are subalkaline to alkaline, metaluminous, magnetite-series, volcanic arc, I-type granitoids. Batholithic magmas are a heat, potential fluid, metal, and sulphur source for the hydrothermal iron oxide-rich Cu-Au mineralization in the Candelaria-Punta del Cobre district. Ore-related hydrothermal alteration affected large portions of the Copiapó complex. The least altered batholithic rocks have initial 87 Sr/ 86 Sr of 0.703070 -0.703231; initial 143 Nd/ 144 Nd of 0.512733 -0.512781; and 206 Pb/ 204 Pb, 207 Pb/ 204 Pb, and 208 Pb/ 204 Pb of 18. 428 -18.772, 15.550 -15.603, and 38.127 -38.401, respectively. The d 18 O values for these rocks range from þ 6.9 to þ8.6‰. Isotope signatures and trace element distributions suggest that the magmas are mantle derived. A subduction fluid-modified mantle source may explain the geochemical characteristics of the Copiapó complex. The ascent of magmas occurred along deep-rooted structures without significant crustal contamination, though minor contamination by relatively young (e.g. Jurassic) igneous rocks during ascent is possible. Intrusive rocks with high-K to shoshonitic characteristics probably represent residual liquids of less evolved magmas. The regional geologic context suggests that the plutons of the Copiapó complex were emplaced at a relatively shallow crustal level of 2 -3 km. q

In the Northern Andes of Ecuador, a broad Quaternary volcanic arc with significant across-arc geochemical changes sits upon continental crust consisting of accreted oceanic and continental terranes. Quaternary volcanic centers occur, from west to east, along the Western Cordillera (frontal arc), in the Inter-Andean Depression and along the Eastern Cordillera (main arc), and in the Sub-Andean Zone (back-arc). The adakite-like signatures of the frontal and main arc volcanoes have been interpreted either as the result of slab melting plus subsequent slab melt–mantle interactions or of lower crustal melting, fractional crystallization, and assimilation processes. In this paper, we present petrographic, geochemical, and isotopic (Sr, Nd, Pb) data on dominantly andesitic to dacitic volcanic rocks as well as crustal xenolith and cumulate samples from five volcanic centers (Pululagua, Pichincha, Ilalo, Chacana, Sumaco) forming a NW–SE transect at about 0° latitude and encompassing the frontal (Pululagua, Pichincha), main (Ilalo, Chacana), and back-arc (Sumaco) chains. All rocks display typical subduction-related geochemical signatures, such as Nb and Ta negative anomalies and LILE enrichment. They show a relative depletion of fluid-mobile elements and a general increase in incompatible elements from the front to the back-arc suggesting derivation from progressively lower degrees of partial melting of the mantle wedge induced by decreasing amounts of fluids released from the slab. We observe widespread petrographic evidence of interaction of primary melts with mafic xenoliths as well as with clinopyroxene- and/or amphibole-bearing cumulates and of magma mixing at all frontal and main arc volcanic centers. Within each volcanic center, rocks display correlations between evolution indices and radiogenic isotopes, although absolute variations of radiogenic isotopes are small and their values are overall rather primitive (e.g., εNd = +1.5 to +6, 87Sr/86Sr = 0.7040–0.70435). Rare earth element patterns are characterized by variably fractionated light to heavy REE (La/YbN = 5.7–34) and by the absence of Eu negative anomalies suggesting evolution of these rocks with limited plagioclase fractionation. We interpret the petrographic, geochemical, and isotopic data as indicating open-system evolution at all volcanic centers characterized by fractional crystallization and magma mixing processes at different lower- to mid-crustal levels as well as by assimilation of mafic lower crust and/or its partial melts. Thus, we propose that the adakite-like signatures of Ecuadorian rocks (e.g., high Sr/Y and La/Yb values) are primarily the result of lower- to mid-crustal processing of mantle-derived melts, rather than of slab melts and slab melt–mantle interactions. The isotopic signatures of the least evolved adakite-like rocks of the active and recent volcanoes are the same as those of Tertiary ”normal” calc-alkaline magmatic rocks of Ecuador suggesting that the source of the magma did not change through time. What changed was the depth of magmatic evolution, probably as a consequence of increased compression induced by the stronger coupling between the subducting and overriding plates associated with subduction of the aseismic Carnegie Ridge.

The Altaid orogen was formed by aggregation of Paleozoic subduction–accretion complexes and Precambrian basement blocks between the Late Proterozoic and the Early Mesozoic. Because the Altaids are the site of abundant granitic plutonism and host some of the largest gold deposits in the world, understanding their formation has important implications on the comprehension of Phanerozoic crustal growth and metallogeny. In this study, we present the first extensive lead isotope data on magmatic and metasedimentary rocks as well as ore deposits of the southern part of the Altaids, including the Tien Shan (Tianshan) and southern Altay (Altai) orogenic belts. Our results show that each terrane investigated within the Tien Shan and southern Altay is characterized by a distinct Pb isotope signature and that there is a SW–NE Pb isotope gradient suggesting a progressive transition from a continental crust environment in the West (the Kyzylkum and Kokshaal segments of the Southern Tien Shan) to an almost 100% juvenile (MORB-type mantle-derived) crust environment in the East (Altay). The Pb isotope signatures of the studied ore deposits follow closely those of magmatic and metasedimentary rocks of the host terranes, thus supporting the validity of lead isotopes to discriminate terranes. Whereas this apparently suggests that no unique reservoir has been responsible for the huge gold concentration in this region, masking of a preferential Pb-poor Au-bearing reservoir by mixing with Pb-rich crustal reservoirs during the mineralizing events cannot be excluded.

Vlaykov Vruh–Elshitsa represents the best example of paired porphyry Cu and epithermal Cu–Au deposits within the Late Cretaceous Apuseni–Banat–Timok–Srednogorie magmatic and metallogenic belt of Eastern Europe. The two deposits are part of the NW trending Panagyurishte magmato-tectonic corridor of central Bulgaria. The deposits were formed along the SW flank of the Elshitsa volcano-intrusive complex and are spatially associated with N110-120-trending hypabyssal and subvolcanic bodies of granodioritic composition. At Elshitsa, more than ten lenticular to columnar massive ore bodies are discordant with respect to the host rock and are structurally controlled. A particular feature of the mineralization is the overprinting of an early stage high-sulfidation mineral assemblage (pyrite ± enargite ± covellite ± goldfieldite) by an intermediate-sulfidation paragenesis with a characteristic Cu–Bi–Te–Pb–Zn signature forming the main economic parts of the ore bodies. The two stages of mineralization produced two compositionally different types of ores—massive pyrite and copper–pyrite bodies. Vlaykov Vruh shares features with typical porphyry Cu systems. Their common geological and structural setting, ore-forming processes, and paragenesis, as well as the observed alteration and geochemical lateral and vertical zonation, allow us to interpret the Elshitsa and Vlaykov Vruh deposits as the deep part of a high-sulfidation epithermal system and its spatially and genetically related porphyry Cu counterpart, respectively. The magmatic–hydrothermal system at Vlaykov Vruh–Elshitsa produced much smaller deposits than similar complexes in the northern part of the Panagyurishte district (Chelopech, Elatsite, Assarel). Magma chemistry and isotopic signature are some of the main differences between the northern and southern parts of the district. Major and trace element geochemistry of the Elshitsa magmatic complex are indicative for the medium- to high-K calc-alkaline character of the magmas. 87Sr/86Sr(i) ratios of igneous rocks in the range of 0.70464 to 0.70612 and 143Nd/144Nd(i) ratios in the range of 0.51241 to 0.51255 indicate mixed crustal–mantle components of the magmas dominated by mantellic signatures. The epsilon Hf composition of magmatic zircons (+6.2 to +9.6) also suggests mixed mantellic–crustal sources of the magmas. However, Pb isotopic signatures of whole rocks (206Pb/204Pb = 18.13–18.64, 207Pb/204Pb = 15.58–15.64, and 208Pb/204Pb = 37.69–38.56) along with common inheritance component detected in magmatic zircons also imply assimilation processes of pre-Variscan and Variscan basement at various scales. U–Pb zircon and rutile dating allowed determination of the timing of porphyry ore formation at Vlaykov Vruh (85.6 ± 0.9 Ma), which immediately followed the crystallization of the subvolcanic dacitic bodies at Elshitsa (86.11 ± 0.23 Ma) and the Elshitsa granite (86.62 ± 0.02 Ma). Strontium isotope analyses of hydrothermal sulfates and carbonates (87Sr/86Sr = 0.70581–0.70729) suggest large-scale interaction between mineralizing fluids and basement lithologies at Elshitsa–Vlaykov Vruh. Lead isotope compositions of hydrothermal sulfides (206Pb/204Pb = 18.432–18.534, 207Pb/204Pb = 15.608–15.647, and 208Pb/204Pb = 37.497–38.630) allow attribution of ore-formation in the porphyry and epithermal deposits in the Southern Panagyurishte district to a single metallogenic event with a common source of metals.

Lead isotope ratios of ores of the Candelaria-Punta del Cobre iron oxide Cu-Au deposits and associated Early Cretaceous volcanic and batholithic rocks have been determined. For the igneous rocks, a whole-rock acid attack technique based on the separate analyses of a leachate and the residual fraction of a sample was used. The lead isotope systematics of leachate–residue pairs are significantly different for unaltered and altered igneous rocks of the Candelaria-Punta del Cobre district. Residues of unaltered igneous rocks likely represent the common lead. In contrast, residues of all the altered igneous rocks except two samples have higher Pb isotope ratios than those of unaltered magmatic rocks and cannot represent common lead. We suggest that this is a result of the hydrothermal alteration suffered by these rocks and that the common lead composition of the altered igneous (volcanic and plutonic) rocks must have been similar to that of the unaltered batholith rocks. The conclusion that the altered volcanic rocks originally had a similar common lead isotope composition as the batholith is consistent with geological and geochemical arguments (e.g., setting, regional geologic evolution, ages and relative distribution of volcanic and intrusive rocks, magmatic affinities), which indicate that these rocks were derived from similar Early Cretaceous parent magmas. The modification of the leachate–residue pair lead isotope systematics of most altered igneous rocks is consistent with a selective removal of lead and uranium from these rocks by an oxidized hydrothermal fluid. The result of the hydrothermal leaching has been to alter magmatic rocks in a way that (1) their leachable fraction is presently a mix of common lead similar to that of the ore event and of radiogenic lead evolved from a source with a consistently high Th/U, and that (2) their residual fraction has less common lead than unaltered rocks. The outcrop area with altered volcanic rocks displaying anomalously high lead isotope ratios extends over 25 km along the eastern margin of the batholith. Since lead of the ores in the Candelaria-Punta del Cobre district has the same isotopic composition as the common lead of unaltered magmatic rocks of the area, the lead isotope data are consistent with a derivation of the ore lead (and by inference of other metals like Cu) both directly from a magmatic fluid exsolved during crystallization of the batholith and/or from hydrothermal leaching of the volcanic rocks originally having similar isotopic compositions as the batholith.

Most of the economic ore deposits of Ecuador are porphyry-Cu and epithermal style gold deposits associated with Tertiary continental arc magmatism. This study presents major and trace element geochemistry, as well as radiogenic isotope (Pb, Sr) signatures, of continental arc magmatic rocks of Ecuador of Eocene to Late Miocene (~50–9 Ma, ELM) and Late Miocene to Recent (~8–0 Ma, LMR) ages. The most primitive ELM and LMR rocks analyzed consistently display similar trace element and isotopic signatures suggesting a common origin, most likely an enriched MORB-type mantle. In contrast, major and trace element geochemistry, as well as radiogenic isotope systematics of the whole sets of ELM and LMR samples, indicate strikingly different evolutions between ELM and LMR rocks. The ELM rocks have consistently low Sr/Y, increasing Rb/Sr, and decreasing Eu/Gd with SiO2, suggesting an evolution through plagioclase-dominated fractional crystallization at shallow crustal levels (SiO2. We explain the adakite-type geochemistry of LMR rocks, rather than by slab melting, by a model in which mantle-derived melts partially melt and assimilate residual garnet-bearing mafic lithologies at deeper levels than those of plagioclase stability (i.e., >20 km), and most likely at sub-crustal levels (>40–50 km). The change in geochemical signatures of Tertiary magmatic rocks of Ecuador from the ELM- to the LMR-type coincides chronologically with the transition from a transpressional to a compressional regime that occurred at ~9 Ma and has been attributed by other investigations to the onset of subduction of the aseismic Carnegie ridge. The major districts of porphyry-Cu and epithermal deposits of Ecuador (which have a small size,

Basaltic magmatism occurred only rarely within the extensive Eocene-Oligocene volcanic activity in the Eastern Rhodope Mts., SE Bulgaria. The earliest mafic volcanism started at ca. 34 Ma with K-rich trachybasalts strongly enriched in large ion lithophile elements (LILE), particularly Ba, Sr, Pb, Th, and light rare earth elements (REE) relative to the high field strength elements (HFSE). They have high 87 Sr/ 86 Sr ratios (0.70688-0.70756), low 144 Nd/ 144 Nd (0.51252-0.51243), and very high 207 Pb/ 204 ) and 208 Pb/ 204 Pb (39.07-39.14) at low 206 Pb/ 204 Pb (18.72-18.73) ratios, reflecting high degrees of crustal contamination. Shoshonitic basalts and absarokites and calc-alkaline and high-K calc-alkaline magmas, which erupted between 33 and 31 Ma, have decreasing Sr isotope initial ratios from west (0.70825) to east (0.70647) at approximately constant 143 Nd/ 144 Nd isotopic compositions (0.51252-0.51243) and slightly decreasing 207 Pb/ 204 Pb (15.66-15.72) and 208 Pb/ 204 Pb (38.80-38.96) and increasing 206 Pb/ 204 in comparison with the trachybasalts. All these rocks are characterized by negative Nb-Ti and Eu anomalies. They resulted from different degrees of partial melting of enriched asthenosphere, and the magmas were later contaminated by the Rhodopian crust. The end of the magmatic activity (28-26 Ma) was marked by emplacement of alkaline dykes, spatially associated with metamorphic core complexes. They are characterized by low 87 Sr/ 86 Sr (0.70323-0.70338), high 144 Nd/ 144 Nd (0.51290-0.51289), and 206 Pb/ 204 Pb (18.91-19.02) at lower 207 Pb/ 204 Pb (15.52-15.64) and 208 Pb/ 204 Pb (38.59-38.87) ratios, consistent with an origin from a source similar to OIB-like European Asthenospheric reservoir contaminated by depleted mantle lithosphere. (P. Marchev). Tectonophysics 393 (2004) 301 -328 www.elsevier.com/locate/tecto metamorphism which record mantle perturbation. The Eo-Oligocene stage started with block faulting, sedimentary basin formation, and extensive acid-intermediate and basic volcanism over the entire Eastern Rhodope area.

Rhenium–osmium ages were determined for two molybdenite samples and a Pb–Pb age was derived from bornite–chalcopyrite–magnetite at the Salobo iron oxide copper–gold deposit to determine the timing of mineralization and its relation to the nearby Old Salobo Granite. Rhenium–osmium dating of molybdenite spatially associated with copper sulfide minerals yields ages with weighted means of 2576±8 and 2562±8 Ma. Removing the error multiplier introduced by the decay constant uncertainty, appropriate for comparing ages from the same isotopic system, these data convincingly argue for two temporally separated pulses of molybdenite deposition at 2576.1±1.4 Ma (n=2) and 2561.7±3.1 Ma (n=3). The 2576±8 Ma age coincides with a previously published U–Pb age of 2573±2 Ma for the Old Salobo Granite, suggesting that main stage ore formation may have been contemporaneous with granite magmatism. The slightly younger 2562 Ma age most likely represents new molybdenite precipitation associated with the development or reactivation of local shear zones. Lead–lead stepwise leaching of copper sulfide minerals yields a less precise isochron age of 2579±71 Ma, and supports an Archean age for the Salobo ores. This is the first documentation of an Archean iron oxide copper–gold deposit, and the Re–Os and Pb–Pb geochronology herein support 2580–2550 Ma estimates for basement reactivation and regional granite magmatism associated with the development of brittle–ductile shear zones.

The Fortuna oxidized gold skarn deposit is located in the northern part of the Nambija gold district, southern Ecuador. It has been subdivided into four mineralized sites, covering a distance of 1 km, which are named from north to south: Cuerpo 3, Mine 1, Mine 2, and Southern Sector. Massive skarn bodies occur in K–Na metasomatized volcanic and volcaniclastic rocks of the Triassic Piuntza unit. They appear to result from selective replacement of volcaniclastic rocks. Very minor presence of bioclast relicts suggests the presence of subordinate limestone. Endoskarn type alteration with development of Na-rich plagioclase, K-feldspar, epidote, actinolite, anhedral pyroxene, and titanite affects a quartz–diorite porphyritic intrusion which crops out below the skarn bodies in Mine 2 and the Southern Sector. Endoskarn alteration in the intrusion grades into a K-feldspar ± biotite ± magnetite assemblage (K-alteration), suggesting that skarn formation is directly related to the quartz–diorite porphyritic intrusion, the latter being probably emplaced between 141 and 146 Ma. The massive skarn bodies were subdivided into a dominant brown garnet skarn, a distal green pyroxene–epidote skarn, and two quartz-rich varieties, a blue-green garnet skarn and light green pyroxene–garnet skarn, which occur as patches and small bodies within the former skarn types. The proximal massive brown garnet skarn zone is centered on two 060° trending faults in Mine 2, where the highest gold grades (5–10 g/t) were observed. It grades into a distal green pyroxene–epidote skarn zone to the North (Cuerpo 3). Granditic garnet shows iron enrichment from the proximal to the distal zone. Diopsidic pyroxene exhibits iron and manganese enrichment from proximal to distal zones. The retrograde stage is weakly developed and consists mainly of mineral phases filling centimeter-wide veins, vugs, and interstices between garnet and pyroxene grains. The main filling mineral is quartz, followed by K-feldspar, epidote, calcite, and chlorite, with minor sericite, apatite, titanite, hematite, pyrite, chalcopyrite, and gold. Metal and sulfur contents are low at Fortuna, and the highest gold grades coincide with high hematite abundance, which suggests that retrograde stage and gold deposition took place under oxidizing conditions. Fluid inclusions from pyroxene indicate precipitation from high temperature—high to moderate salinity fluids (400 to 460°C and 54- to 13-wt% eq. NaCl), which result probably from boiling of a moderately saline (∼8-wt% eq. NaCl) magmatic fluid. Later cooler (180 to 475°C) and moderate to low saline fluids (1- to 20-wt% eq. NaCl) were trapped in garnet, epidote, and quartz, and are interpreted to be responsible for gold deposition. Chlorite analysis indicates temperature of formation between 300 and 340°C in accordance with fluid inclusion data. It appears, thus, that gold was transported as chloride complexes under oxidizing conditions and was deposited at temperatures around 300°C when transport of chloride complexes as gold carriers is not efficient.

The Seridó Belt, located in the Borborema Province, northeastern Brazil, is well known for its pegmatites and granites. The pegmatites intrude the Seridó Group and show no signs of deformation. They were emplaced along a major NE-trending shear zone during a post-Brasiliano extensional event (550-500 Ma). Homogeneous bodies of pegmatite are barren, whereas the heterogeneous ones have been mined for columbite-tantalite, beryl, gem tourmaline (elbaite), and kaolin. Electron-microprobe analyses reveal that columbite-group minerals have a composition between ferrocolumbite and manganocolumbite. Our U-Pb age determinations on these minerals show that the pegmatites were emplaced between 509.5 ± 2.9 Ma and 514.9 ± 1.1 Ma. As the pegmatites are not deformed, these ages are interpreted as a minimum age for the Brasiliano orogeny in the Seridó Belt. Our U-Pb data on monazite from a spatially related coarse-grained peraluminous granite give an age of 528 ± 12 Ma. The pegmatites are clearly younger than that granite. Lead isotopes from K-feldspar show that the coarse-grained granite and the pegmatites are derived from several separate batches of magma that received variable amounts of Pb from the distinct host-rocks. The heterogeneity in the Pb isotopic compositions is due to in situ Pb growth and the geochemically variable host-rocks.

Separate lead isotope analyses of leachate and residue fractions are applied to a broad spectrum of rocks commonly investigated in metallogenic studies. Resulting data highlight a systematic behavior of leachate and residue fractions with respect to lead isotope compositions, which essentially depends on the mineralogical composition of the rock. Granitoid and high-grade metamorphic rocks have residue compositions virtually identical to common lead. In contrast, low-grade metasedimentary rocks may have residue compositions swamped by radiogenic lead of leach-resistant zircons. Mafic magmatic rocks have residues that are often more radiogenic than leachates, depending on the ratio of leach-refractory zircons to common lead in the residual fraction of these rocks. Separate leachate and residue analyses of source rocks provide two lead isotope end members whose mixture may represent lead with the appropriate ore fluid composition. Our leaching experiments indicate that hot acid solutions (and by inference hydrothermal fluids) preferentially leach radiogenic lead from medium- to high-grade metamorphic and granitoid rocks, whereas they preferentially leach common lead from low-grade metasedimentary and mafic magmatic rocks. The method presented in this study provides a reliable alternative to other methods (i.e., age-correction of bulk-rock compositions) for the determination of the common lead signature of felsic to intermediate magmatic rocks. This may be preferable to age-corrected bulk-rock analyses, where ages to apply for corrections of bulk-rock data are not known or where moderately to highly altered rocks must be used. Case studies of orogenic gold and MVT districts of Peru (Pataz and San Vicente, respectively) show that separate leachate and residue lead isotope analyses carried out systematically on whole rocks allow a more thorough evaluation of metal source reservoirs than does the standard method of age-corrected or uncorrected bulk-rock analyses.

New U-Pb, Re-Os, and 40 Ar/ 39 Ar dates are presented for magmatic and hydrothermal mineral phases in skarn-and porphyry-related ores from the Nambija and Pangui districts of the Subandean zone, southeastern Ecuador. Nambija has been one of the main gold-producing centers of Ecuador since the 1980s due to exceptionally high-grade ores (average 15 g/t, but frequently up to 300 g/t Au). Pangui is a recently discovered porphyry Cu-Mo district. The geology of the Subandean zone in southeastern Ecuador is dominated by the I-type, subduction-related, Jurassic Zamora batholith, which intrudes Triassic volca-nosedimentary rocks. The Zamora batholith is in turn cut by porphyritic stocks, which are commonly associated with skarn formation and/or porphyry-style mineralization. High precision U-Pb and Re-Os ages for porphyritic stocks (U-Pb, zircon), associated prograde skarn (U-Pb, hydrothermal titanite), and retrograde stage skarn (Re-Os, molybdenite from veins postdating gold deposition) of the Nambija district are all indistinguishable from each other within error (145 Ma) and indicate a Late Jurassic age for the gold mineralization. Previously, gold mineralization at Nambija was considered to be Early Tertiary based on K-Ar ages Miner Deposita (2009) 44:371-387 obtained on various hydrothermal minerals. The new Jurassic age for the Nambija district is slightly younger than the 40 Ar/ 39 Ar and Re-Os ages for magmatic-hydrothermal minerals from the Pangui district, which range between 157 and 152 Ma. Mineralization at Nambija and Pangui is associated with porphyritic stocks that represent the last known episodes of a long-lived Jurassic arc magmatism (∼190 to 145 Ma). A Jurassic age for mineralization at Nambija and Pangui suggests that the Northern Andean Jurassic metallogenic belt, which starts in Colombia at 3°N, extends down to 5°S in Ecuador. It also adds a new mineralization style (Au-skarn) to the metal endowment of this belt.

This study focuses on the Elbeyli-Ordu, Emeksen-Giresun, Güzelyayla-Trabzon and Ulutaş-Ispir porphyry-type prospects located in the Eastern Pontides, Turkey. Our new LA-ICP-MS U-Pb zircon age data reveal that the Elbeyli-Ordu Mo-Cu mineralization is hosted by a 77.0±1.3 Ma-old monzonite/monzodiorite with a shoshonitic character. The Emeksen Mo mineralization, located ~40km southeast of the Elbeyli-Ordu prospect, consists of NW-and NE-striking quartz veins crosscuting a high-K calc-alkaline to shoshonitic granite dated at 78.5±0.8 Ma, a granodiorite dated at 78.7±0.5 Ma and porphyry granite dated at 77.7±0.5 Ma. The Güzelyayla porphyry Cu-Mo prospect consists of a stockwork-type Cu-Mo mineralization crosscutting a calc-alkaline 81.4±1.1 Ma-old dacite porphyry and Late Cretaceous calc-alkaline andesite. The Ispir-Ulutaş mineralization is hosted within a highly sericitized 131.1±0.9 Ma-old quartz-porphyry that intruded into a 132.9±0.6 Ma-old calc-alkaline granite porphyry. Our new U-Pb zircon ages, lithogeochemical and radiogenic isotopic data of the host rocks associated with the porphyry-type prospects in the Eastern Pontides indicate that they formed in an arc-related environment during Cretaceous subduction of the Neotethys Ocean, and the Ispir-Ulutaş prospect is attributed to the main stage of the northward subduction of the Neotethys during the Early Cretaceous. We conclude that the Güzelyayla and Emeksen hydrothermal systems were formed during a transitional compressional to extensional tectonic evolution, whereas the Late Cretaceous Elbeyli hydrothermal system was emplaced during an extensional arc magmatic event. Highlyoxidized, high-K calc-alkaline to shoshonitic magmas at Emeksen and Elbeyli were derived from a metasomatised, heterogeneous and enriched lithospheric mantle, with variable degrees of partial melting of the mantle wedge and variable crustal contamination. Mixing/mingling processes between mafic magmas derived from the lower crust and acidic magmas at upper crustal levels played an important role in the formation of Cu-Mo porphyry-type mineralization in the Eastern Pontides.

Altar (31º 29' S, 70º 28' W) is a large porphyry Cu-(Au-Mo) deposit with associated epithermal Au-(Ag-Cu) veins located in the Cordillera Principal of SW San Juan Province (Argentina). Altar is a complex magmatic-hydrothermal system formed from several magmatic and hydrothermal pulses during the middle-late Miocene. New LA-ICPMS U-Pb ages in zircons from the Altar porphyries indicate four discrete events of intrusions over an extended magmatic life time of ca. 3 m.y. It comprises a pre-mineralization porphyry (11.75 ± 0.24 Ma), three mineralized porphyries (11.62 ± 0.21 Ma and 11.68 ± 0.27 Ma, 11.13 ± 0.26 Ma, 10.35 ± 0.32 Ma) related to hydrothermal breccias, two post-mineralization intrusions, and a post-mineralization breccia (8.9 ± 0.4 Ma). The three mineralized porphyries (porphyries 2, 3 and 4) were emplaced within ~0.7-1.3 m.y. Amphibole phenocrysts from the porphyries crystallized from oxidized magmas (fO 2 = NNO +1 to +2) at temperatures of 780 to 850°C and pressures between 0.9 and 1.8 kbar corresponding to depths of ~4-7 km. Anorthite and Fe-rich rims in the plagioclase phenocrysts suggest that the magmatic chambers were episodically recharged by a less evolved magma. The middle-late Miocene intrusions are interpreted to have been derived from a deeper and relatively large magmatic reservoir that supplied magmas to smaller chambers located in the upper crust. The focused magmatic output to shallow levels during a period of a few million years in the Altar area has been a main requirement in the formation of this large porphyry copper deposit. Tectonic setting Altar is located in the southern portion of the flat-slab segment (~27°-33° 30'S) of the Central Andes. In this region, the Nazca plate is subducting nearly horizontally beneath the South American plate at ~100 km depth (Gans et al., 2011). The flat-slab segment presents a smooth transition to the north, toward the Central Volcanic Zone (CVZ), and an abrupt transition to the south, to the Southern Volcanic Zone (SVZ; Fig. 1; Cahill and Isacks, 1992; Anderson et al., 2007; Gans et al., 2011). Several studies have documented the Miocene to recent evolution of the flat-slab segment (Allmendinger et al. 1990; Kay and Abbruzzi, 1996; Kay and Mpodozis, 2002). During the Early Miocene (27-20 Ma) this segment had a slab geometry similar to that currently observed in the normal-slab segment at 35ºS, and a crustal thickness of 35-40 km (Kay and Abbruzzi, 1996; Kay and Mpodozis, 2002). The shallowing of the subduction zone progressed from Middle to Late Miocene (20-5 Ma). It was accompanied by crustal thickening, subduction of the Juan Fernández ridge (e.g., Yáñez et al., 2001), a substantial decrease in the astenospheric wedge thickness and eastward migration, and broadening of the arc (Kay et al., 2005). Cessation of magmatic activity over the Miocene flat-slab occurred at 5 Ma. At this time, magmatism occurred in the back-arc, in the Farallón Negro, Pocho and San Luis magmatic centers (Kay and Mpodozis, 2002). Local Geology The Altar area was poorly known geologically until the mid-1990s, when CRA Exploration Argentina outlined a broad zone of alteration and mineralization. Between 1999 and 2003, Río Tinto tested this target with 2,841 m of diamond drilling. Since 2005, Peregrine Metals Ltd. has completed 140 diamond drill holes (55,688 meters). Recently, the project has been acquired by Stillwater Mining Company, which is conducting a comprehensive drilling campaign, metallurgical testwork program, environmental baseline study, and preliminary economic evaluations for a copper-gold mining and concentrating project at Altar. Maydagán et al. (2011) presented the first field mapping and data on magmatic rocks of the Altar region. The authors grouped the igneous rocks into two sequences: the early Miocene lower volcanic complex and the middle-late Miocene upper subvolcanic suite. The lower volcanic complex is an early Miocene arc in which mantle-derived magmas evolved at low pressures through plagioclase-and pyroxene-dominated fractional crystallization and assimilation of crustal rocks (AFC; Maydagán et al., 2011). The Altar porphyry Cu-(Au-Mo) deposit is partially hosted and related to the upper subvolcanic suite, a series of porphyritic stocks, dikes, and breccias that intruded the lower volcanic complex in the central and east ridges of the Altar district (Fig. 2). Magmas of the upper subvolcanic suite require a hornblende-bearing residual mineral assemblage that is interpreted to reflect their higher water contents (Maydagán et al., 2011). Analytical Techniques and Sampling Methodology Over 200 samples representatives of the different porphyritic rocks and breccias of the upper subvolcanic suite were collected from surface exposures and drill core from the Altar region. The samples were studied by transmitted and reflected light petrography at the Universidad Nacional del Comahue (Neuquén, Argentina) and twenty samples were selected for analysis. Three radiometric ages of the subvolcanic stocks were determined by U-Pb LA-ICPMS on zircons at the PCIGR-Pacific Center for Isotopic and Geochemical Research at the University of British Columbia (Canada). Another radiometric age of the late breccia was determined by U-Pb LA-ICPMS on zircons at the Arizona LaserChron Center, University of Arizona, U.S.A. Details of the dating methods and results of LA-ICPMS analyses of zircons from the porphyries and late breccia are provided in digital appendices A5-A10. Major, trace and rare earth elements were analyzed by inductively coupled plasmaemission spectrometry and ICP mass spectrometry (Group 4A-4B combined package) at Acme Analytical Laboratories Ltd., Canada (Table 4). Seven samples were analyzed for Sr and Nd isotopes and ten for Pb isotopes at the Mineralogy Department at the University of Geneva (Switzerland) following the method of Chiaradia et al. (2009a; Table 5). Chemical compositions of magmatic minerals (plagioclase (n = 74), ulvöspinel (n = 17), amphibole (n = 20), biotite (n=16), and magnetite (n = 8) from different subvolcanic intrusions were determined with electron microprobe at three different laboratories with some samples analyzed in duplicate at more than one laboratory. The full data set of microprobe analysis is provided in the digital appendices A1-A4. Altar subvolcanic intrusions At least five porphyritic intrusions and three breccias have been recognized in the Altar district. They are distinguished based on their textures, phenocryst abundances, related veins,

Ecuador consists of terranes having both continental (Chaucha, Tahuin, Loja terranes) and oceanic (Macuchi, Alao, Salado terranes) affinity, which were accreted to the Amazon craton from Late Jurassic to Eocene. Four main magmatic arcs were formed by the subduction of the Farallon/Nazca plate since the Jurassic: a Jurassic continental arc on the western margin of the Amazon craton, a Jurassic island arc (Alao terrane), an early Tertiary island arc (Macuchi terrane), and a middle-late Tertiary continental arc encompassing the terranes of Macuchi, Chaucha, Tahuin, Loja, and Alao after complete assembly of the Ecuadorian crust. Mineral deposits formed during these magmatic arc activities include porphyry-Cu and gold skarn deposits in association with the Jurassic continental arc, polymetallic volcanic-hosted massive sulfide deposits (VHMS) in association with the Jurassic island arc of Alao, Au-Cu-Zn VHMS deposits in association with the early Tertiary island arc of Macuchi, and porphyry-Cu and precious-metal epithermal deposits in association with the middle-late Tertiary continental-arc magmatism on the newly assembled crust of Ecuador (Macuchi, Chaucha, Tahuin, Loja, and Alao terranes). In this study, we have compiled 148 new and 125 previously published lead isotope analyses on Paleozoic to Miocene metamorphic, intrusive, volcanic, and volcanosedimentary rocks, as well as on Jurassic to Miocene magmatic-related ore deposits of Ecuador. Lead isotope compositions of the magmatic rocks of the four main arc events derive from mixing of various sources including mantle, variably enriched by pelagic sediments and/or by a high 238 U/ 204 Pb component, and heterogeneous continental crust rocks. Lead isotope compositions of the Ecuadorian ore deposits display a broad range of values (206 Pb/ 204 Pb = 18.3-19.3, 207 Pb/ 204 Pb = 15.54-15.74, 208 Pb/ 204 Pb = 38.2-39.2), which is as large as the range previously reported for all magmatic-related ore deposits of the Central Andean provinces I and II combined. Ore deposits formed before complete assembly of the Ecuadorian crust through complete accretion of the several terranes (i.e., pre-Eocene) have lead isotope compositions overlapping those of the associated magmatic rocks, suggesting a largely magmatic origin for their lead. In contrast, post-assembly ore deposits (i.e., post-Eocene) have lead isotope compositions that only partly overlap those of the coeval magmatic rocks of the continental arc. In fact, several ore deposits have lead isotope compositions shifted toward those of the basement rocks that host them, suggesting that lead derives from a mixture of magmatic lead and basement-rock lead leached by hydrothermal fluids. Most Ecuadorian ores have high 207 Pb/ 204 Pb values (>15.55), suggesting a dominant continental crust or pelagic sediment origin of the lead. However, we caution against concluding that chalcophile metals (for example, Cu and Au) also have a continental crust origin. Ore deposits of the different terranes of Ecuador, irrespective of their age, plot in distinct isotopic fields, which are internally homogeneous. This suggests that lithologic factors had an important control on the lead isotope compositions. Ultimately, lead isotope compositions of the ore deposits of Ecuador mirror the isotopic compositions of the rocks of the host terranes and are consistent with the multiterrane nature of the Ecuadorian crust.

Raúl-Condestable is a >32 million metric ton (Mt) iron oxide-copper-gold (IOCG) deposit located on the Peruvian coast, 90 km south of Lima. The ore occurs as veins, replacement "mantos," and disseminations consisting of a chalcopyrite-pyrite-pyrrhotite-magnetite-amphibole mineral association. The geology of the studied area comprises a series of superposed volcanic edifices of Late Jurassic to Early Cretaceous age, which are part of a larger volcanic island to continental arc system. Particularly good exposures of the tilted host sequence allow the mapping of the Raúl-Condestable IOCG deposit in a nearly complete oblique cross section, from its associated volcanic edifice down to a paleodepth of about 6 km. U-Pb zircon ages indicate that in the deposit area felsic magmatic activity took place between 116.7 ± 0.4 and 114.5 ± 1 Ma, defining a new Raúl-Condestable superunit, the oldest so far, of the Peruvian Coastal batholith. This superunit is located west of the main part of the batholith and includes a dacite-andesite volcanic dome and a subvolcanic quartz-diorite porphyry sill-dike complex that were emplaced at 116.7 ± 0.4 and 116.4 ±0.3 Ma, respectively, followed by tonalite stocks and dikes emplaced between 115.1 ± 0.4 and 114.5 ± 1 Ma. All these rocks contain hornblende and/or biotite but no pyroxene and correspond to silica-and waterrich magmas following a calcic differentiation trend. Hf isotope data on zircons (εHf(115 Ma) = 5.2-7.5) and Pb isotope data on whole rock, combined with lithogeochemical results, suggest that magmas were generated by partial melting of the upper mantle, enriched through hydrous metasomatism and/or melting of subducted pelagic sediments. The lack of zircon inheritance suggests that there was no direct involvement of continental crust. The Raúl-Condestable IOCG deposit is connected in space and time with the magmatism of the Raúl-Condestable superunit. The mineralization was emplaced in the core of the dacite-andesite volcanic dome at a paleodepth of 2 to 3 km, surrounding two tonalitic intrusions formed at 115.1 ± 0.4 and 114.8 ± 0.4 Ma. The U-Pb age of hydrothermal titanite from IOCG veins at 115.2 ± 0.3 Ma indicates that the mineralization was coeval with (or more probably just followed) the emplacement of the tonalites. Re-Os geochronology on molybdenite did not yield reliable ages due to apparent Re loss. Copper ore is associated with a zoned alteration pattern, which surrounds the tonalite intrusions. It consists of a core of biotite alteration and quartz stockwork,

The Jurassic (approximately 145 Ma) Nambija oxidized gold skarns are hosted by the Triassic volcanosedimentary Piuntza unit in the sub-Andean zone of southeastern Ecuador. The skarns consist dominantly of granditic garnet (Ad 20-98) with subordinate pyroxene (Di 46-92 Hd 17-42 Jo 0-19) and epidote and are spatially associated with porphyritic quartz-diorite to granodiorite intrusions. Endoskarn is developed at the intrusion margins and grades inwards into a potassic alteration zone. Exoskarn has an outer K-and Na-enriched zone in the volcanosedimentary unit. Gold mineralization is associated with the weakly developed retrograde alteration of the exoskarn and occurs mainly in sulfide-poor vugs and milky quartz veins and veinlets in association with hematite. Fluid inclusion data for the main