Petrology, geochemistry and U-Pb geochronology of magmatic rocks from the high-sulfidation epithermal Au-Cu Chelopech deposit, Srednogorie zone, Bulgaria

The Chelopech deposit is one of the largest European gold deposits and is located 60km east of Sofia, within the northern part of the Panagyurishte mineral district. It lies within the Banat-Srednegorie metallogenic belt, which extends from Romania through Serbia to Bulgaria. The magmatic rocks define a typical calc-alkaline suite. The magmatic rocks surrounding the Chelopech deposit have been affected by propylitic, quartz-sericite, and advanced argillic alteration, but the igneous textures have been preserved. Alteration processes have resulted in leaching of Na2O, CaO, P2O5, and Sr and enrichment in K2O and Rb. Trace element variation diagrams are typical of subduction-related volcanism, with negative anomalies in high field strength elements (HFSE) and light element, lithophile elements. HFSE and rare earth elements were relatively immobile during the hydrothermal alteration related to ore formation. Based on immobile element classification diagrams, the magmatic rocks are andesitic to dacitic in compositions. Single zircon grains, from three different magmatic rocks spanning the time of the Chelopech magmatism, were dated by high-precision U-Pb geochronology. Zircons of an altered andesitic body, which has been thrust over the deposit, yield a concordant 206Pb/238U age of 92.21 ± 0.21Ma. This age is interpreted as the crystallization age and the maximum age for magmatism at Chelopech. Zircon analyses of a dacitic dome-like body, which crops out to the north of the Chelopech deposit, give a mean 206Pb/238U age of 91.95 ± 0.28Ma. Zircons of the andesitic hypabyssal body hosting the high-sulfidation mineralization and overprinted by hydrothermal alteration give a concordant 206Pb/238U age of 91.45 ± 0.15Ma. This age is interpreted as the intrusion age of the andesite and as the maximum age of the Chelopech epithermal high-sulfidation deposit. 176Hf/177Hf isotope ratios of zircons from the Chelopech magmatic rocks, together with published data on the Chelopech area and the about 92-Ma-old Elatsite porphyry-Cu deposit, suggest two different magma sources in the Chelopech-Elatsite magmatic area. Magmatic rocks associated with the Elatsite porphyry-Cu deposit and the dacitic dome-like body north of Chelopech are characterized by zircons with ɛHfT90 values of ∼5, which suggest an important input of mantle-derived magma. Some zircons display lower ɛHfT90 values, as low as −6, and correlate with increasing 206Pb/238U ages up to about 350Ma, suggesting assimilation of basement rocks during magmatism. In contrast, zircon grains in andesitic rocks from Chelopech are characterized by homogeneous 176Hf/177Hf isotope ratios with ɛHfT90 values of ∼1 and suggest a homogeneous mixed crust-mantle magma source. We conclude that the Elatsite porphyry-Cu and the Chelopech high-sulfidation epithermal deposits were formed within a very short time span and could be partly contemporaneous. However, they are related to two distinct upper crustal magmatic reservoirs, and they cannot be considered as a genetically paired porphyry-Cu and high-sulfidation epithermal related to a single magmatic-hydrothermal system centered on the same intrusio

Origin of Nepheline-normative High-K Ankaramites and the Evolution of Eastern Srednogorie Arc in SE Europe

Eastern Srednogorie is part of the Apuseni-Banat-Timok-Srednogorie magmatic belt in SE Europe, the main arc related to the Late Cretaceous subduction and closure of the Tethys Ocean between Africa and Europe. Extrusive and shallow intrusive magmatism in the Eastern Srednogorie is abundant and extremely diverse in composition, covering a wide range from ultramafic volcanic rocks to granites; this provides a unique opportunity to study processes of primitive melt formation and magma evolution in an arc environment. In contrast to other parts of the belt, relatively mafic lavas predominate here. Three magmatic regions are distinguished within Eastern Srednogorie from south to north: Strandzha, Yambol-Burgas and East Balkan. Systematic differences exist between these regions, notably the increased alkalinity of samples from the Yambol-Burgas region in the central part. All rocks display a clear subduction-like signature in their trace-element patterns, particularly the enrichment in large ion lithophile elements and light rare earth elements relative to high field strength elements. A distinct primitive nepheline-normative ankaramite magma type is recognized among the mafic volcanic rocks from the Yambol-Burgas region and melt inclusions entrapped in olivine and clinopyroxene from a cumulitic rock. Lower crustal clinopyroxene and amphibole cumulates carried to the surface as xenoliths in a mafic dike represent a possible source for the ankaramite. Modeling of the melting process suggests that low degrees of batch melting of a clinopyroxene-rich, amphibole-bearing source similar to the cumulate xenoliths at 1 GPa, temperatures of 1240-1300°C, oxidized conditions and a water content of 0·2 wt % reproduce accurately most of the observed major- and trace-element characteristics of the studied ankaramites. The elevated Rb, K2O, Th, Ba content and higher Pb isotope ratios of the predicted liquids compared with the ankaramites are explained by mixing of the ankaramite magma with lherzolite partial melts derived from the subduction-modified mantle wedge. Underplating of such mantle-derived magmas at the crust-mantle boundary in an extensional environment as a response to slab roll-back provides also the necessary heat to melt lower crustal cumulates. Fractional crystallization of mainly clinopyroxene plus olivine and Fe-Ti oxides in a deep (equivalent to 8 kbar pressure) magma chamber produced most of the observed range of shoshonitic basalts and basaltic andesites in Eastern Srednogorie. The more evolved intermediate varieties were probably formed by mixing and crystallization at lower temperatures in lower pressure magma chambers. Whole-rock Sr and Pb isotope compositions indicate variable degrees of admixing of basement rocks to generate the intermediate to acid Late Cretaceous magmas, but assimilation was minimal for magmas with less than 53 wt % SiO2. The proposed model for the evolution of the magmatism in Eastern Srednogorie involves initial formation of the calc-alkaline and high-K arc magmatism in the Strandzha and East Balkan regions, followed by roll-back induced intra-arc rifting and the formation of high-K, shoshonitic and ultra-high-K magmatism, including primitive ankaramites in the Yambol-Burgas regio

The Li-Bearing Pegmatites from the Pampean Pegmatite Province, Argentina: Metallogenesis and Resources

The Li-bearing pegmatites of the Pampean Pegmatite Province (PPP) occur in a rare-element pegmatite belt developed mainly in the Lower Paleozoic age on the southwestern margin of Gondwana. The pegmatites show Li, Rb, Nb ≤ Ta, Be, P, B, Bi enrichment, and belong to the Li-Cs-Ta (LCT) petrogenetic family, Rare-Element-Li (REL-Li) subclass; most of them are of complex type and spodumene subtype, some are of albite-spodumene type, and a few of petalite subtype. The origin of the pegmatites is attributed predominantly to fractionation of fertile S-type granitic melts produced by either fluid-absent or fluid-assisted anatexis of a thick pile of Gondwana-derived turbiditic sediments. Most of the pegmatites are orogenic (530–440 Ma) and developed during two overlapped collisional orogenies (Pampean and Famatinian); a few are postorogenic (~370 Ma), related to crustal contaminated A-type granites. The pegmatites were likely intruded in the hinterland, preferably in medium-grade metamorphic rocks with PT conditions ~200–500 MPa and 400–650 °C, where they are concentrated in districts and groups. Known combined resources add up 200,000 t of spodumene, with variable grades between 5 and 8 wt.% Li2O. The potential for future findings and enlargement of the resources is high, since no systematic exploration program has yet been developed.This research was funded by CONICET grants during several periods and lastly by PIP 1489 from CONICET to M.F.M.-Z. The Spanish Ministry of Economy, Industry and Competitiveness (project no. RTI2018-094097-B-100, with ERDF funds), and the European Union’s Horizon 2020 Innovation Programme (grant agreement no. 869274, project GREENPEG: New Exploration Tools for European Pegmatite Green-Tech Resources) granted E.R.-R

U-Pb dating, Hf-isotope characteristics and trace-REE-patterns of zircons from Medet porphyry copper deposit, Bulgaria: implications for timing, duration and sources of ore-bearing magmatism

Precise U-Pb geochronology, Hf isotope compositions and trace element distributions in zircons are combined in the present study to define the timing and sources of the magmatism forming the Medet porphyry copper deposit, Bulgaria. ID-TIMS U-Pb-zircon dating demonstrates that ore-bearing magmatism extended for less than 1.12Ma. As inferred from the field relationships, it started with the intrusion of a quartz-monzodiorite at 90.59 ± 0.29Ma followed by granodiorite porphyries at 90.47 ± 0.30 and 90.27 ± 0.60Ma and by crosscutting aplite dykes at 90.12 ± 0.36Ma. These units were overprinted by potassic alteration and host economic copper-(Mo-Au) mineralization. The main magmatic-hydrothermal activity ceased after that, and a later quartz-granodiorite porphyry dyke, dated at 89.26 ± 0.32Ma, only contains an uneconomic quartz-pyrite mineralization. Assimilation of Lower Paleozoic rocks with a mantle to mantle-crust signature is characteristic of the fertile magma in the Medet deposit, as defined by positive ɛ-Hf values of the inherited zircons. The positive Ce-anomalies and the higher Eu/Eu* ratios of the zircons in the mineralized Cretaceous rocks of Medet deposit argue for crystallization from a generally more oxidized magma compared to the later quartz-granodiorite porphyry dyke. A change in paleostress conditions occurred during the intrusion of the Medet pluton and its dykes. The initial stage reveals E-W extension associated with N-S compression, whereas the younger granodiorite dyke was emplaced during subsequent N-S extension. The large-scale switch of the extensional stress regime during the mineralization was favourable for ore deposition by channelling the fluids and increasing the effective permeabilit

Transect through the Cenozoic magmatism in WSW Bulgaria and Macedonia from Pirin Mountain to Kozhuf: temporal and isotope geochemistry constraints

Closing of Vardar Ocean at the Late Cretaceous to Early Cenozoic was followed by collision which caused thickening of the crust under the Morava-Rhodope zone (in Pirin region nowadays it is 49.5–48 km). We present new, preliminary Sr and Nd isotope data and U-Pb zircon ages for Cenozoic magmatic rocks along a NNE–SSW transect through WSW Bulgaria and SE Macedonia, characterized by highly variable crustal thickness

Adakite-like and Normal Arc Magmas: Distinct Fractionation Paths in the East Serbian Segment of the Balkan-Carpathian Arc

New age and whole-rock 87Sr/86Sr and 143Nd/144Nd isotopic data are used to assess petrogenetic and regional geodynamic processes associated with Late Cretaceous subvolcanic intrusions within the sparsely studied Timok Magmatic Complex (TMC) and Ridanj-Krepoljin Zone (RKZ) of eastern Serbia. The TMC and RKZ form part of the Apuseni-Banat-Timok-Srednogorie (ABTS) magmatic belt, a Cu-Au mineralized calc-alkaline magmatic arc related to closure of the Tethys Ocean that extends through Romania, Serbia, and Bulgaria in SE Europe. Zircon ages based on U-Pb laser ablation inductively coupled plasma mass spectrometry supplemented by existing isotope dilution thermal ionization mass spectrometry data respectively range from 89 to 79 Ma and from 76 to 71 Ma for the TMC and RKZ. This age pattern corresponds to cross-arc younging away from the European continent. Adakite-like trace element signatures (Y ≤18 ppm) are linked with samples that extend across the arc. These overlap in space and time with samples that conform to a normal arc differentiation trend. We performed energy-constrained assimilation-fractional crystallization (EC-AFC) modeling of Sr-La-Nd-Yb concentrations and Sr and Nd isotopic data. Results suggest that the two distinct fractionation trends may be explained in terms of a common mantle-derived parental magma but distinct fractionation and assimilation paths in the lower and upper crust. Petrogenesis of the adakite-like magmas is consistent with extensive high-pressure amphibole fractionation in the lower crust followed by ascent and plagioclase-dominant fractionation and assimilation in the upper crust. In contrast, normal arc signatures appear to have evolved exclusively via an upper-crustal differentiation process. Overall, our interpretation supports mantle wedge melting related to weak extension during progressive rollback of a subducting sla

Application of precise 142Nd/144Nd analysis of small samples to inclusions in diamonds (Finsch, South Africa) and Hadean Zircons (Jack Hills, Western Australia)

146Sm-142Nd and 147Sm-143Nd systematics were investigated in garnet inclusions in diamonds from Finsch (S. Africa) and Hadean zircons from Jack Hills (W. Australia) to assess the potential of these systems as recorders of early Earth evolution. The stud

Late Cretaceous porphyry Cu and epithermal Cu-Au association in the Southern Panagyurishte District, Bulgaria: the paired Vlaykov Vruh and Elshitsa deposits

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 ± 0.9Ma), which immediately followed the crystallization of the subvolcanic dacitic bodies at Elshitsa (86.11 ± 0.23Ma) and the Elshitsa granite (86.62 ± 0.02Ma). 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 metal

Split-grain 40Ar/39Ar dating : integrating temporal and geochemical data from crystal cargoes

NERC is acknowledged for continued funding of AIF at SUERC, East Kilbride. This work was supported by an ETH research grant (ETH-05 13-2) and funds from Swiss National Science Foundation research grants (SNSF 200021-146268 and SNSF 200021-155923/1) and US National Science Grant 1425491.Large sanidine crystals from the Mesa Falls Tuff (MFT), Yellowstone volcanic field, have been split and individually dated via high-precision 40Ar/39Ar geochronology with the undated portions further analysed for major elements, trace elements, Pb and Sr isotopes in the sanidine and trace elements in the melt inclusions. This allows the geochemical and geochronological identity of an individual sanidine to be combined. Our MFT sanidines return a preferred eruption age of 1.3011 ± 0.0015/0.0016 Ma (2-sigma, n = 56, MSWD 0.8, analytical/full external) with a significant component of subtly older (up to ~ 2 Ma) crystals. Combined with recent results (Rivera et al., 2016, Journal of Petrology 57, 9, 1677–1704) our data define a global mean sanidine 40Ar/39Ar age for the MFT of 1.3022 ± 0.0006/0.0008 Ma (2 sigma, analytical/full external) relative to Alder Creek sanidine at 1.1891 Ma and total λ40Ar 5.5305e-10, which gives RACsMFT: 1.09542 ± 0.00050. The ability to couple geochemistry and geochronology from a single grain allows us, for the first time, to evaluate the origin of the subtly older sanidines present in the same pumices as juvenile sanidines. Melt inclusions from all Mesa Falls sanidines represent extremely fractionated melts with low Sr contents (max. 12 ppm, n = 39), and rare earth element patterns which require that they be formed from an A-type magma rather than the preceding subduction-related Eocene volcanism as previously suggested. 87Sr/86Sr from juvenile and subtly older sanidines shows the same range of 0.7073 to 0.7096, illustrating the susceptibility of such low-Sr melts to slight degrees of assimilation. Pb isotopic compositions are more restricted and identical between the juvenile and subtly older sanidines in the Mesa Falls Tuff (207Pb/206Pb 0.900–0.903, 208Pb/206Pb 2.217–2.226, n = 83) and these compositions rule out the underlying Huckleberry Ridge Tuff member B as a potential source for the subtly older sanidine. LA-ICPMS 206Pb/238U dating of Mesa Falls zircons supports no role for the Huckleberry Ridge Tuff. Rather, these subtly older sanidines are interpreted as containing excess mantle-derived Ar. The ability to couple the geochemical and geochronological records within individual sanidine crystals that we demonstrate here has potential to provide new insights for a variety of petrological studies such as diffusional modelling.PostprintPeer reviewe