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

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

Timing and magma evolution of the Chelopech volcanic complex (Bulgaria)

The Chelopech volcanic complex is located in the Central Srednogorie magmatic zone and hosts one of the largest Cu–Au deposits in Europe. Field observations and sedimentary relationships allow to distinguish three units of the volcanic complex: (I) dome-like bodies, (II) lava to agglomerate flows, and (III) the Vozdol lava breccias and volcanites. The volcanic rocks are porphyritic with plagioclase and amphibole phenocrysts, quartz and biotite are rare. The lava flows contain fully crystallised, fine-grained enclaves of more basic composition. Their mineral chemistry indicates mingling and mixing between two parental magmas. The geochemical evolution of the Chelopech volcanic complex developed from intermediate to basic lavas, but the evolution of the magmatism was more complex including magmatic differentiation, assimilation, mingling and mixing. The trace element distribution is typical for an active continental margin. The magmatic activity commenced at the northern border of the Chelopech region with the intrusion of dome-like bodies at 92.2 ± 0.3 Ma (U–Pb single zircon ID-TIMS dating). The products of the second and the third units are geochronologically indistinguishable within the error uncertainties, and representative samples yield a crystallisation age of 91.3 ± 0.3 Ma. REE abundances reveal a striking positive Ce-anomaly in zircons of unit 2 and zircon core parts of unit 3, which relates to a higher oxidation state of the parental magma. Sr and Nd isotopic compositions suggest a mixed mantle and crustal source of the Turonian magma. Initial Sr ratios range between 0.70470 and 0.70554, and 90(Nd) varies between –2.27 and –3.55. 90(Hf) values of concordant zircons corroborate this data and range between +2.90 to +5.02 in the andesite of the first unit and from +1.06 to +1.38 in the volcanites of the second and third unit

From a long-lived upper-crustal magma chamber to rapid porphyry copper emplacement: Reading the geochemistry of zircon crystals at Bajo de la Alumbrera (NW Argentina)

The formation of world class porphyry copper deposits reflect magmatic processes that take place in a deeper and much larger underlying magmatic system, which provides the source of porphyry magmas, as well as metal and sulphur-charged mineralising fluids. Reading the geochemical record of this large magmatic source region, as well as constraining the time-scales for creating a much smaller porphyry copper deposit, are critical in order to fully understand and quantify the processes that lead to metal concentration within these valuable mineral deposits. This study focuses on the Bajo de la Alumbrera porphyry copper deposit in Northwest Argentina. The deposit is centred on a dacitic porphyry intrusive stock that was mineralised by several pulses of porphyry magma emplacement and hydrothermal fluid injections. To constrain the duration of ore formation, we dated zircons from four porphyry intrusions, including pre-, syn- and post-mineralisation porphyries based on intersection relations between successive intrusion and vein generations, using high precision CA-ID-TIMS. Based on the youngest assemblages of zircon grains, which overlap within analytical error, all four intrusions were emplaced within 29 ka, which places an upper limit on the total duration of hydrothermal mineralisation. Re/Os dating of hydrothermal molybdenite fully overlaps with this high-precision age bracket. However, all four porphyries contain zircon antecrysts which record protracted zircon crystallisation during the ∼200 ka preceding the emplacement of the porphyries. Zircon trace element variations, Ti-in-zircon temperatures, and Hf isotopic compositions indicate that the four porphyry magmas record a common geochemical and thermal history, and that the four intrusions were derived from the same upper-crustal magma chamber. Trace element zoning within single zircon crystals confirms a fractional crystallisation trend dominated by titanite and apatite crystallisation. However, zircon cathodoluminescence imaging reveals the presence of intermediate low luminescent (dark) growth zones in many crystals from all intrusions, characterised by anomalously high Th, U and REE concentrations and transient excursions in trace element ratios. A return to the same fractionation trend after this excursion excludes external compositional forcing such as magma mixing. Instead we interpret the “dark-zones” to record zircon crystallisation during a transient event of rapid growth that resulted from mafic magma injection into the base of the magma chamber, releasing a CO2-rich vapour phase into the dacitic crystal mush. We propose that this vapour phase then migrated upwards to the apical part of the magma chamber from where it was expelled, together with successive batches of magma, to form the porphyry copper deposit within a short time-span of less than a few 10,000 years. The short duration of host rock emplacement, hydrothermal alteration and mineralisation presented in this study provides critical constraints on fluid storage in magma chambers and the genesis of large porphyry copper deposits

Combining trace element compositions, U-Pb geochronology and Hf isotopes in zircons to unravel complex calcalkaline magma chambers in the Upper Cretaceous Srednogorie Zone (Bulgaria)

Precise U–Pb geochronology and Hf isotope tracing of zircon is combined with whole-rock geochemical and Sr and Nd isotope data in order to unravel processes affecting mafic to felsic calcalkaline magmas prior to and during their crystallization in crustal magma chambers along the southern border of Central Srednogorie tectonic zone in Bulgaria (SE Europe). ID-TIMS U–Pb dating of single zircons from felsic and mixed/mingled dioritic to gabbroic horizons of single plutons define crystallization ages of around 86.5–86.0, 85.0–84.5 and 82 Ma. Concordia age uncertainties are generally less than 0.3 Ma (0.35%–2σ), and as good as 0.08 Ma (0.1%), when the weighted mean 206Pb/238U value is used. Such precision allows the distinction of magma replenishment processes if separated by more than 0.6–1.0 Ma and when they are marked by newly saturated zircons. We interpret zircon dates from a single sample that do not overlap to reflect new zircon growth during magma recharge in a long-lived crustal chamber. Mingling/mixing of the basaltic magma with colder granitoid mush at mid- to upper-crustal levels is proposed to explain zircon saturation and fast crystallization of U- and REE-rich zircons in the hybrid gabbro. Major and trace-element distribution and Sr and Nd whole-rock isotope chemistry define island arc affinities for the studied plutons. Slab derived fluids and a sediment component are constrained as enrichment sources for the mantle wedge-derived magma, though Hf isotopes in zircon suggest crustal assimilation was also important. Inherited zircons, and their corresponding ε-Hf, from the hybrid gabbroic rocks trace the lower crust as possible source for enrichment of the mantle magma. These inherited zircons are about 440 Ma old with ε-Hf of − 7 at 82 Ma, whereas newly saturated concordant Upper Cretaceous zircons reveal mantle ε-Hf values of + 7.2 to + 10.1. The upper and middle crusts contribute in the generation of the granitoid rocks. Their zircon inheritance is Lower Palaeozoic or significantly older and crustal dominated with 82–85 Ma corrected ε-Hf values of − 28. The Cretaceous concordant zircons in the granitoids are mantle dominated with a ε-Hf values spreading from + 3.9 to + 7

A Fluid Inclusion and Critical/Rare Metal Study of Epithermal Quartz-Stibnite Veins Associated with the Gerakario Porphyry Deposit, Northern Greece

The Gerakario Cu-Au porphyry deposit in the Kilkis ore district, northern Greece, contains epithermal quartz-stibnite veins on the eastern side of the deposit, which crosscut a two-mica gneiss. Metallic mineralization in these veins consists of stibnite + berthierite + native antimony + pyrite + arsenopyrite, and minor marcasite, pyrrhotite, chalcopyrite, löllingite, and native gold. Bulk geochemical analyses of the ore reveal an enrichment in critical and rare metals, including Ag, Au, Bi, Ce, Co, Ga, La, and Sb. Analysis of stibnite with LA-ICP-MS showed an enrichment in base metals (As, Cu, Pb), as well as weak to moderate contents of critical and rare metals (Ag, Bi, Ce, La, Re, Sm, Th, Ti, Tl). A statistical analysis of the trace elements show a positive correlation for the elemental pairs Ce-La, Ce-Sb, and La-Sb, and a negative correlation for the pair Bi-Sb. Fluid inclusions in the A-type veins of the porphyry-style mineralization show the presence of fluid boiling, resulting in a highly saline aqueous fluid phase (35.7 to 45.6 wt.% NaCl equiv.) and a moderately saline gas phase (14 to 22 wt.% NaCl equiv.) in the system H2O-NaCl-KCl at temperatures varying between 380◦ and 460◦C and pressures from 100 to 580 bar. Mixing of the moderate saline fluid with meteoric water produced less saline fluids (8 to 10 wt.% NaCl equiv.), which are associated with the epithermal quartz-stibnite vein mineralization. This process took place under hydrostatic pressures ranging from 65 to 116 bar at a depth between 600 and 1000 m, and at temperatures mainly from 280◦ to 320◦C. © 2022 by the authors. Licensee MDPI, Basel, Switzerland

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 1.12 Ma. As inferred from the field relationships, it started with the intrusion of a quartz-monzodiorite at 90.59 ± 0.29 Ma followed by granodiorite porphyries at 90.47 ± 0.30 and 90.27 ± 0.60 Ma and by crosscutting aplite dykes at 90.12 ± 0.36 Ma. 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 ± 0.32 Ma, 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 permeability

Rare and critical metals in pyrite, chalcopyrite, magnetite, and titanite from the vathi porphyry cu‐au±mo deposit, northern greece

The Vathi porphyry Cu‐Au±Mo deposit is located in the Kilkis ore district, northern Greece. Hydrothermally altered and mineralized samples of latite and quartz monzonite are enriched with numerous rare and critical metals. The present study focuses on the bulk geochemistry and the mineral chemistry of pyrite, chalcopyrite, magnetite, and titanite. Pyrite and chalcopyrite are the most abun-dant ore minerals at Vathi and are related to potassic, propylitic, and sericitic hydrothermal alterations (A‐ and D‐veins), as well as to the late‐stage epithermal overprint (E‐veins). Magnetite and titanite are found mainly in M‐type veins and as disseminations in the potassic‐calcic alteration of quartz monzo-nite. Disseminated magnetite is also present in the potassic alteration in latite, which is overprinted by sericitic alteration. Scanning electron microscopy and laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) analyses of pyrite and chalcopyrite reveal the presence of pyrrhotite, ga-lena, and Bi‐telluride inclusions in pyrite and enrichments of Ag, Co, Sb, Se, and Ti. Chalcopyrite hosts bornite, sphalerite, galena, and Bi‐sulfosalt inclusions and is enriched with Ag, In, and Ti. Inclusions of wittichenite, tetradymite, and cuprobismutite reflect enrichments of Te and Bi in the mineralizing fluids. Native gold is related to A‐ and D‐type veins and is found as nano‐inclusions in pyrite. Titanite inclusions characterize magnetite, whereas titanite is a major host of Ce, Gd, La, Nd, Sm, Th, and W. © 2021 by the authors. Licensee MDPI, Basel, Switzerland

Megacrystic zircon with planar fractures in miaskite-type nepheline pegmatites formed at high pressures in the lower crust (Ivrea Zone, southern Alps, Switzerland)

Trace element, Hf, and O isotopic composition and U-Pb geochronological data are reported for zircon megacrysts found in miaskitic (zircon, biotite, plagioclase-bearing) nepheline syenite pegmatites from the Finero complex in the Northeastern part of the Ivrea-Verbano Zone, southern Alps. Zircon from these pegmatites was reported to reach up to 9 cm in length and is characterized by ~100 μm spaced planar fractures in different directions. Small volumes of these highly evolved alkaline melts intruded into the lower crust and were emplaced within amphibole peridotites and gabbros between 212.5 and 190 Ma. A zircon crystal of 1.5 cm size records a systematic core-to-rim younging of 4.5 Ma found by high-precision CA-ID-TIMS 206Pb/238U dating of fragments, and of 8.7 Ma detected by laser ablation ICP-MS spot dating. Volume diffusion at high temperatures was found to be insufficient to explain the observed within-grain scatter in dates, despite the fact that the planar fractures would act as fast diffusion pathways and thus reduce effective diffusion radii to 50 μm. The U-Pb system of zircon is therefore interpreted to reflect an episodic protracted growth history. These high-pressure miaskites probably formed by episodic, low-degree decompression melting of a metasomatically enriched mantle source and subsequent crystallization in the lower crust at volatile saturation with explosive volatile release, evidenced by their brecciated texture in the field and by the occurrence of planar fractures in zircon. They point to the existence of a long-lived period of heat advection in the deep crust by highly differentiated melts from enriched, lithospheric mantl