Interrelations between coeval mafic and A-type silicic magmas from composite dykes in a bimodal suite of southern Israel, northernmost Arabian–Nubian Shield: Geochemical and isotope constraints

Late Neoproterozoic bimodal dyke suites are abundant in the Arabian–Nubian Shield. In southern Israel this suite includes dominant alkaline quartz porphyry dykes, rare mafic dykes, and numerous composite dykes with felsic interiors and mafic margins. The quartz porphyry chemically corresponds to A-type granite. Composite dykes with either abrupt or gradational contacts between the felsic and mafic rocks bear field, petrographic and chemical evidence for coexistence and mixing of basaltic and rhyolitic magmas. Mixing and formation of hybrid intermediate magmas commenced at depth and continued during emplacement of the dykes. Oxygen isotope ratios of alkali feldspar in quartz porphyry (13 to 15‰) and of plagioclase in trachydolerite (10–11‰) are much higher than their initial magmatic ratios predicted by equilibrium with unaltered quartz (8 to 9‰) and clinopyroxene (5.8‰). The elevation of δ¹⁸O in alkali feldspar and plagioclase, and extensive turbidization and sericitization call for post-magmatic low-temperature (≤ 100 °C) water–rock interaction. Hydrous alteration of alkali feldspar, the major carrier of Rb and Sr in the quartz–porphyry, also accounts for the highly variable and unusually high I(Sr) of 0.71253 to 0.73648.

The initial ¹⁴³Nd/¹⁴⁴Nd ratios, expressed by ε_Nd(T) values, are probably unaltered and show small variation in mafic and felsic rocks within a narrow range from + 1.4 to + 3.3. The Nd isotope signature suggests either a common mantle source for the mafic and silicic magmas or a juvenile crustal source for the felsic rocks (metamorphic rocks from the Elat area). However, oxygen isotope ratios of zircon in quartz porphyry [δ¹⁸O(Zrn) = 6.5 to 7.2‰] reveal significant crustal contribution to the rhyolite magma, suggesting that mafic and A-type silicic magmas are not co-genetic, although coeval. Comparison of ¹⁸O/¹⁶O ratios in zircon allows to distinguish two groups of A-type granites in the region: those with mantle-derived source, δ¹⁸O(Zrn) ranging from 5.5 to 5.8‰ (Timna and Katharina granitoids) and those with major contribution of the modified juvenile crustal component, δ¹⁸O(Zrn) varying from 6.5 to 7.2‰ (Elat quartz porphyry dykes and the Yehoshafat alkaline granite). This suggests that A-type silicic magmas in the northern ANS originated by alternative processes almost coevally.     

Two types of gneisses associated with eclogite at Shuanghe in the Dabie terrane: carbon isotope, zircon U–Pb dating and oxygen isotope

There are two types of gneisses, biotite paragneiss and granitic orthogneiss, to be closely associated with UHP eclogite at Shuanghe in the Dabie terrane. Both concentration and isotope composition of bulk carbon in apatite and host gneisses were determined by the EA-MS online technique. Structural carbonate within the apatite was detected by the XRD and FTIR techniques. Significant ¹³C-depletion was observed in the apatite with δ¹³C values of −28.6‰ to −22.3‰ and the carbon concentrations of 0.70–4.98 wt.% CO₂ despite a large variation in δ¹⁸O from −4.3‰ to +10.6‰ for these gneisses. There is significant heterogeneity in both δ¹³C and δ¹⁸O within the gneisses on the scale of several tens meters, pointing to the presence of secondary processes after the UHP metamorphism. Considerable amounts of carbonate carbon occur in some of the gneisses that were also depleted in ¹³C primarily, but subjected to overprint of ¹³C-rich CO₂-bearing fluid after the UHP metamorphism. The ¹³C-depleted carbon in the gneisses is interpreted to be inherited from their precursors that suffered meteoric–hydrothermal alteration before plate subduction. Both low δ¹³C values and structural carbonate in the apatite suggest the presence of ¹³C-poor CO₂ in the UHP metamorphic fluid. The ¹³C-poor CO₂ is undoubtedly derived from oxidation of organic matter in the subsurface fluid during the prograde UHP metamorphism.

Zircons from two samples of the granitic orthogneiss exhibit low δ¹⁸O values of −4.1‰ to −1.1‰, demonstrating that its protolith was significantly depleted in ¹⁸O prior to magma crystallization. U–Pb discordia datings for the ¹⁸O-depleted zircons yield Neoproterozoic ages of 724–768 Ma for the protolith of the granitic orthogneiss, consistent with protolith ages of most eclogites and orthogneisses from the other regions in the Dabie–Sulu orogen. Therefore, the meteoric–hydrothermal alteration is directly dated to occur at mid-Neoproterozoic, and may be correlated with the Rodinia supercontinental breakup and the snowball Earth event. It is thus deduced that the igneous protolith of the granitic orthogneiss and some eclogites would intrude into the older sequences composing the sedimentary protoliths of the biotite paragneiss and some eclogites along the northern margin of the Yangtze plate at mid-Neoproterozoic, and drove local meteoric–hydrothermal circulation systems in which both ¹³C- and ¹⁸O-depleted fluid interacted with the protoliths of these UHP rocks now exposed in the Dabie terrane.     

Post-collisional granitoids from the Dabie orogen in China: Zircon U–Pb age, element and O isotope evidence for recycling of subducted continental crust

While recycling of subducted oceanic crust is widely proposed to be associated with oceanic island, island arc, and subduction-related adakite magmatism, it is less clear whether recycling of subducted continental crust takes place in continental collision belts. A combined study of zircon U–Pb dating, major and minor element geochemistry, and O isotopes in Early Cretaceous post-collisional granitoids from the Dabie orogen in China demonstrates that they may have been generated by partial melting of subducted continental crust. The post-collisional granitoids from the Dabie orogen comprise hornblende-bearing intermediate rocks and hornblende-free granitic rocks. These granitoids are characterized by fractionated REE patterns with low HREE contents and negative HFSE anomalies (Nb, Ta and Ti). Although zircon U–Pb dating gives consistent ages of 120 to 130 Ma for magma crystallization, occurrence of inherited cores is identified by CL imaging and SHRIMP U–Pb dating; some zircon grains yield ages of 739 to 749 Ma and 214 to 249 Ma, in agreement with Neoproterozoic protolith ages of UHP metaigneous rocks and a Triassic tectono-metamorphic event in the Dabie–Sulu orogenic belt, respectively. The granitoids have relatively homogeneous zircon δ¹⁸O values from 4.14‰ to 6.11‰ with an average of 5.10‰ ± 0.42‰ (n = 28) similar to normal mantle zircon. Systematically low zircon δ¹⁸O values for most of the coeval mafic–ultramafic rocks and intruded country rocks preclude an AFC process of mafic magma or mixing between mafic and felsic magma as potential mechanisms for the petrogenesis of the granitoids. Along with zircon U–Pb ages and element results, it is inferred that the granitic rocks were probably derived from partial melting of intermediate lower crust and the intermediate rocks were generated by amphibole-dehydration melting of mafic rocks in the thickened lower crust, coupled with fractional crystallization during magma emplacement. The post-collisional granitoids in the Dabie orogen are interpreted to originate from recycling of the subducted Yangtze continental crust that was thickened by the Triassic continent–continent collision. Partial melting of orogenic lithospheric keel is suggested to have generated the bimodal igneous rocks with the similar crustal heritage. Crustal thinning by post-collisional detachment postdated the onset of bimodal magmatism that was initiated by a thermal pulse related to mantle superwelling in Early Cretaceous.     

A high precision U–Pb age of metamorphic rutile in coesite-bearing eclogite from the Dabie Mountains in central China: a new constraint on the cooling history

This paper first reports a high precision U–Pb age of 218±1.2 Ma for rutile in coesite-bearing eclogite from Jinheqiao in the Dabie Mounteins, east–central China. This work shows that the U–Pb mineral (rutile+omphacite) isochron age of 218±2.5 Ma and conventional rutile U–Pb concordia age of 218±1.2 Ma obtained by common Pb correction based on the Pb isotopic composition of omphacite in the same eclogite sample are consistent, proving that the omphacite with low U/Pb ratio (μ=2.8) can be used for common Pb correction in U–Pb dating of rutile. Oxygen isotope analysis of rutile aliquots gave the consistent δ¹⁸O values of −6.1±0.1%, demonstrating oxygen isotope homogenization in the rutile of different grains as inclusion in garnet and grain in matrix. Oxygen isotope thermometry yields temperatures of 695±35 and 460±15 °C for quartz–garnet and quartz–rutile pairs, respectively. These oxygen isotopic observations suggest that the diffusion of oxygen in rutile as inclusion in garnet is not controlled by garnet. According to field-based thermochronological studies of rutile, an estimate of the T_c of about 460 °C for U–Pb system in rutile under rapid cooling conditions (20 °C/Ma) was advised. Based on this U–Pb age as well as the reported chronological data with their corresponding metamorphic and/or closure temperature, an improved T–t path has been constructed. The T–t path confirms that the UHPM rocks in South Dabie experienced a rapid cooling following the peak metamorphism before 220 Ma and a long isothermal stage from 213 to 180 Ma around 425 °C.     

Petrogenesis of A-type granites and origin of vertical zoning in the Katharina pluton, Gebel Mussa (Mt. Moses) area, Sinai, Egypt

The central pluton within the Neoproterozoic Katharina Ring Complex (area of Gebel Mussa, traditionally believed to be the biblical Mt. Sinai) shows a vertical compositional zoning: syenogranite makes up the bulk of the pluton and grades upwards to alkali-feldspar granites. The latters form two horizontal subzones, an albite–alkali feldspar (Ab–Afs) granite and an uppermost perthite granite. These two varieties are chemically indistinguishable. Syenogranite, as compared with alkali-feldspar granites, is richer in Ca, Sr, K, Ba and contains less SiO₂, Rb, Y, Nb and U; Eu/Eu* values are 0.22–0.33 for syenogranite and 0.08–0.02 for alkali-feldspar granites. The δ¹⁸O (Qtz) is rather homogeneous throughout the pluton, 8.03–8.55‰. The δ¹⁸O (Afs) values in the syenogranite are appreciably lower relative to those in the alkali–feldspar granites: 7.59–8.75‰ vs. 8.31–9.12‰. A Rb–Sr isochron (n = 9) yields an age of 593 ± 16 Ma for the Katharina Ring Complex (granite pluton and ring dikes).

The alkali–feldspar granites were generated mainly by fractional crystallization of syenogranite magma. The model for residual melt extraction and accumulation is based on the estimated extent of crystallization ( 50 wt.%), which approximates the rigid percolation threshold for silicic melts. The fluid-rich residual melt could be separated efficiently by its upward flow through the rigid clusters of crystal phase. Crystallization of the evolved melt started with formation of hypersolvus granite immediately under the roof. Fluid influx from the inner part of the pluton to its apical zone persisted and caused increase of P_H2O in the magma below the perthite granite zone. Owing to the presence of F and Ca in the melt, P_H2O of only slightly more than 1 kbar allows crystallization of subsolvus Ab–Afs granite. Abundance of turbid alkali feldspars and their ¹⁸O/¹⁶O enrichment suggest that crystallization of alkali-feldspar granites was followed by subsolvus fluid–rock interaction; the δ¹⁸O (Fsp) values point to magmatic origin of fluids.

The stable and radiogenic isotope data [δ¹⁸O (Zrn) = 5.82 ± 0.06‰, I_Sr = 0.7022 ± 0.0064, ε_Nd (T) values are + 3.6 and + 3.9] indicate that the granite magma was generated from a ‘juvenile’ source, which is typical of the rocks making up most of the Arabian–Nubian shield.     

Zircon megacrysts from basalts of the Venetian Volcanic Province (NE Italy): U–Pb ages, oxygen isotopes and REE data

Mafic alkaline lavas from the Venetian Volcanic Province (NE Italy) contain orange–brown zircon megacrysts up to 15 mm long, subhedral to subrounded and showing equant morphology, with width-to-length ratios of 1:2–1:2.5. U–Pb ages of zircon (51.1 ± 1.5 to 30.5 ± 0.51 Ma) fit the stratigraphic age of the host lava (Middle Eocene and Oligocene) and their oxygen isotope composition (δ¹⁸O = 5.31–5.51‰) is similar to that of zircon formed in the upper mantle. Cathodoluminescence images and crystal chemical features, e.g. depletion of incompatible elements such as REE, Y, U and Th at constant Hf content, indicate that centre-to-edge zircon zoning is not consistent with evolution of the melt by fractional crystallization. All the above features, together with the fact that zircon and host basalts are coeval, indicate that the studied Zr megacrysts crystallised from a primitive alkaline mafic magma, which later evolved to the less alkaline host magma.     

Hydrogen and oxygen isotope evidence for fluid–rock interactions in the stages of pre- and post-UHP metamorphism in the Dabie Mountains

Hydrogen and oxygen isotope studies were carried out on high and ultrahigh pressure metamorphic rocks in the eastern Dabie Mountains, China. The δ¹⁸O values of eclogites cover a wide range of −4.2 to +8.8‰, but the δD values of micas from the eclogites fall within a narrow range of −87 to −71‰. Both equilibrium and disequilibrium oxygen isotope fractionations were observed between quartz and the other minerals, with reversed fractionations between omphacite and garnet in some eclogite samples. The δ¹⁸O values of −4 to −1‰ for some of the eclogites represent the oxygen isotope compositions of their protoliths which underwent meteoric water–rock interaction before the high to ultrahigh pressure metamorphism. Heterogeneous δ¹⁸O values for the eclogite protoliths implies not only the varying degrees of the water–rock interaction before the metamorphism at different localities, but also the channelized flow of fluids during progressive metamorphism due to rapid plate subduction. Retrograde metamorphism caused oxygen and hydrogen isotope disequilibria between some of the minerals, but the fluid for retrograde reactions was internally buffered in the stable isotope compositions and could be derived from structural hydroxyls dissolved in nominally anhydrous minerals.     

Petrogenesis of the Maowu pyroxenite–eclogite body from the UHP metamorphic terrane of Dabieshan: chemical and isotopic constraints

The Maowu eclogite–pyroxenite body is a small (250×50 m) layered intrusion that occurs in the ultra-high-pressure (UHP) metamorphic terrane of Dabieshan, China. Like the adjacent Bixiling complex, the Maowu intrusion was initially emplaced at a crustal level, then subducted along with the country gneisses to mantle depths and underwent UHP metamorphism during the collision of the North and South China Blocks in the Triassic. This paper presents the results of a geochemical and isotopic investigation on the metamorphosed Maowu body. The Maowu intrusion has undergone open system chemical and isotopic behavior three times. Early crustal contamination during magmatic differentiation is manifested by high initial ⁸⁷Sr/⁸⁶Sr ratios (0.707–0.708) and inhomogeneous negative _Nd(T) values of −3 to −10 at 500 Ma (probable protolith age). Post-magmatic and pre-UHP metamorphic metasomatism is indicated by sinusoidal REE patterns of garnet orthopyroxenites, lack of whole-rock (WR) Sm–Nd isochronal relationship, low δ¹⁸O values and an extreme enrichment of Th and REE in a clinopyroxenite. Finally, K and Rb depletion during UHP metamorphism is deduced from the high initial ⁸⁷Sr/⁸⁶Sr ratios unsupported by in situ Rb/Sr ratios. Laser ICP-MS spot analyses on mineral grains show that (1) Grt and Cpx attained chemical equilibrium during UHP metamorphism, (2) Cpx/Grt partition coefficients for REE correlate with Ca, and (3) LREE abundances in whole rocks are not balanced by that of the principal phases (Grt and Cpx), implying that the presence of LREE-rich accessory phases, such as monazite and apatite, is required to account for the REE budget.

Sm–Nd isotope analyses of minerals yielded three internal isochrons with ages of 221±5 Ma and (T)=−5.4 for an eclogite, 231±16 Ma and (T)=−6.2 for a garnet websterite, and 236±19 Ma and (T)=−6.9 for a garnet clinopyroxenite. The Cpx/Grt chemical equilibrium and the consistent mineral isochron ages indicate that the metasomatic processes mentioned above must have occurred prior to the UHP metamorphism. These Sm–Nd ages agree with published zircon and monazite U–Pb ages and constrain the time of UHP metamorphism to 220–236 Ma. The Maowu and Bixiling layered intrusions are similar in their in situ tectonic relationship with their country gneisses, but the two bodies are distinguished by their magma-chamber processes. The Bixiling magmas were contaminated by the lower crust, whereas the Maowu magmas were contaminated by the upper crustal rocks during their emplacement and differentiation. The two complexes represent two distinct suites of magmatic rocks, which have resided in the continental crust for about 300–400 Ma before their ultimate subduction to mantle depths, UHP metamorphism and return to the crustal level.     

C, O, S and Sr isotope studies on the genesis of Fe-carbonate and barite mineralizations in the Attepe iron district (Adana, Southern Turkey)

The Attepe district consists of Precambrian, Lower–Middle Cambrian, Upper Cambrian–Lower Ordovician and Mesozoic formations. It contains several iron deposits and occurrences. Three types of iron-mineralizations can be distinguished in the area; (i) Sedimentary Fe-sulfide in Precambrian bituminous metapelitic rocks, and Fe-oxides in Precambrian metasandstones (SISO), (ii) vein-type Fe-carbonate and oxides composed of mainly siderite, ankerite and hematite including barite in Lower–Middle Cambrian metacarbonates of the Çaltepe Formation (HICO), (iii) karstic Fe-oxides and hydroxides essentially in the Lower–Middle Cambrian metacarbonates and the unweathered Fe-carbonates (KIO). The latter type is more widespread and located at the upper parts of the most important mineable iron deposits like Attepe deposit.

Oxygen-, carbon-, sulfur- and strontium-isotope studies have been performed on siderites and barites in the vein-type ores, and on calcites in the recrystallized Çaltepe Limestones to investigate the sources and formation mechanism of primary ore-forming constituents. The δ¹³C values of siderites and calcites in limestones of the Çaltepe Formation range from −10.10‰ to −8.20‰, and from −0.8‰ to 2.30‰. Both carbonate minerals show δ¹⁸O values between 17.50–18.30‰ and 16.20–23.00‰, respectively. The δ¹³C and δ¹⁸O isotopic variations do not indicate any direct or linear relations between siderites and limestones. However, it is possible that the carbon and oxygen isotopic compositions of carbonate minerals could be changed to some extent, when limestones were subjected to hydrothermal processes or thermal alterations during metamorphism.

The isotopic values of barites display 32.40–38.30‰ for δ³⁴S and 12.20–14.70‰ for δ¹⁸O. The strontium isotope ratios (0.717169–0.718601) of barites and the sulfur isotope compositions of barites and pyrites suggest that there are no direct linkages of ore-forming compounds neither with a magmatic source nor with sedimentary pyrite formations in the Precambrian bituminous shales of the Attepe formation.

According to the field observations and the stable isotope data, siderites and ankerites should be formed by interaction between iron-rich hydrothermal fluids and Çaltepe limestones, whereas isotope ratios of barites indicate that they were formed by mixing of sulfur-rich meteoric waters and deeply circulated hydrothermal solutions.     

Fluid evolution in the W–Cu–Zn–Pb San Cristobal vein, Peru: fluid inclusion and stable isotope evidence

The Zn–Pb±Ag±Cu San Cristobal district is located 100 km east of Lima in the western cordillera of Peru. It is centred around the Chumpe intrusion and is composed of vein and carbonate replacement ore types. The main San Cristobal vein presents a paragenesis that can be divided into three stages: (a) an early wolframite–quartz–pyrite stage, (b) a quartz–base metal stage, and (c) a late quartz–carbonate–barite stage.

Fluid inclusions in quartz from the tungsten stage are biphase (LV) at room temperature and homogenise to the liquid phase between 146 and 257 °C. Their salinities range between 2.1 and 5.1 wt.% NaCl equiv. Rare inclusions contain an additional crystal of halite and have salinities of 46–54 wt.% NaCl equiv. Data of the first two stages show a decrease in homogenisation temperatures concomitant with a salinity decline. Fluid inclusions in quartz from the late stage homogenise at higher temperatures, between 252 and 323 °C, with salinities ranging between 4.6 and 6.7 wt.% NaCl equiv.

Hydrogen and oxygen isotope data indicate a two-stage evolution. Isotopic compositions of the fluid associated with the first two stages define a trend with constant δ¹⁸O values and decreasing δD values (δ¹⁸O=3.2‰ to 5.0‰ V-SMOW and δD=−60‰ to −112‰ V-SMOW), which is interpreted as mixing of a dominantly magmatic component with minor meteoric water that had equilibrated with the host rocks. This interpretation is supported by sulphur and lead isotopic data from previous studies. By contrast, the quartz–carbonate–barite stage bears isotopic characteristics defining a trend with a coupled decrease of δ¹⁸O and δD (δ¹⁸O=−8.1‰ to 2.5‰ V-SMOW and δD=−57‰ to −91‰ V-SMOW) and is explained by addition of meteoric water to the system and subsequent mixing with a less important magmatic component.

Different fluid origins are confirmed by laser ablation ICP-MS analyses of the triphase (LVH) and biphase (LV) primary inclusions. The concentrations of the major ore elements, i.e., W, Cu, Zn and Pb, decrease throughout the paragenesis; W, and to a lesser extent Cu, show significant variations, associated with a steep decrease in their concentration. The decreasing concentrations can be explained by mineral deposition and dilution by the meteoric fluid; differences in the rate of decrease indicate selective precipitation of W. Fluid inclusions of the quartz–carbonate stages show an abrupt increase in Ba and Sr concentrations. This is interpreted to reflect a higher volume of host rock silicate alteration, probably due to the increasing size of the fluid flow cell and is explained by the input of a third fluid of unknown origin. LA-ICP-MS analyses show that the fluids were already depleted in W and Cu before reaching the emplacement of carbonate replacement ore type, whereas Zn and Pb were still present in considerable amounts. This is again due to selective precipitation and is consistent with the interpretation that the economically interesting metals were dominantly introduced by magmatic fluids.     

Spinel granulite in Odesan area, South Korea: Tectonic implications for the collision between the North and South China blocks

Spinel granulite formed in the Fe–Al-rich layers in migmatitic gneiss adjacent to a late Paleozoic collision-related mangerite intrusion in the Odesan area, eastern Gyeonggi Massif, South Korea, contains the high-temperature (HT) assemblage Crd + Spl + Crn. Spinel and cordierite compositions indicate peak metamorphic conditions of 914–1157 °C. Retrograde metamorphism reached amphibolite facies where garnet and cordierite broke down to biotite, sillimanite and quartz. These conditions, and the reactions inferred from mineral textures, are consistent with a clockwise P–T path. Metamorphic zircon overgrowths in the spinel granulite and enclosing migmatitic gneiss, dated by SHRIMP U–Pb, yield Permo-Triassic ages of 245 ± 10 and 248 ± 18 Ma respectively, consistent with the metamorphism being a product of the late Paleozoic collision between the North and South China blocks within South Korea. The zircon core ages and textures suggest that the ultimate source of the spinel granulite was a Paleoproterozoic (1852 ± 14 Ma) igneous rock. The protolith of the host migmatitic gneiss was a sediment derived principally from 2.49, 2.16 and 1.86 Ga sources. The age and conditions of spinel granulite metamorphism are similar to those of spinel-bearing granulite in the Higo terrane in west-central Kyushu (250 Ma, > 950 °C at 8–9 kbar), consistent with a continuation of the Dabie-Sulu collision zone into Japan through the Odesan area.     

Neo-Proterozoic rift-related syenites (Northern Damara Belt, Namibia): Geochemical and Nd–Sr–Pb–O isotope constraints for mantle sources and petrogenesis

Major element, trace element and Nd–Sr–Pb–O isotope data for a suite of Neo-Proterozic, pre-orogenic, rift-related syenites from the Northern Damara orogen (Namibia) constrain their sources and petrogenesis. New U–Pb ages obtained on euhdreal titanite of inferred magmatic origin constrain the age of intrusion of the Lofdal and Oas syenites to ca. 750 Ma compatible with previous high-precision zircon analyses from the Oas complex. Major rock types from Lofdal and Oas are mildly sodic nepheline-normative and quartz-normative syenites and were primarily generated by fractional crystallization from a mantle-derived alkaline magma. Primitive samples from Lofdal and Oas show depletion of Rb, K and Th relative to Ba and Nb together with variable negative anomalies of P and Ti on a primitive mantle-normalized diagram. Evolved samples from Oas develop significant negative Ba, Sr, P and Ti anomalies and positive U and Th anomalies mainly as a function of crystal fractionation processes. The lack of a pronounced negative Nb anomaly in samples from Lofdal suggests that involvement of a crustal component is negligible. For the nepheline-normative samples from Lofdal, the unradiogenic Sr and radiogenic Nd isotope composition and low δ¹⁸O values suggest derivation of these samples from a moderately depleted lithospheric upper mantle with crustal-like U/Pb ratios (⁸⁷Sr/⁸⁶Sr: 0.7031–0.7035, ε Nd: ca. + 1, δ¹⁸O: 7‰, ²⁰⁶Pb/²⁰⁴Pb: ca.18.00, ²⁰⁷Pb/²⁰⁴Pb: 15.58–15.60). Primitive samples of the Oas quartz-normative syenites have identical isotope characteristics (⁸⁷Sr/⁸⁶Sr: 0.7034, ε Nd: ca. + 1, δ¹⁸O: 6.5‰, ²⁰⁶Pb/²⁰⁴Pb: ca.18.00, ²⁰⁷Pb/²⁰⁴Pb: 15.59) whereas more differentiated samples have higher ⁸⁷Sr/⁸⁶Sr ratios (0.709–0.714), slightly higher δ¹⁸O values (7.0–7.1‰), less radiogenic ε Nd values (− 1.1 to − 1.4) and more radiogenic ²⁰⁶Pb/²⁰⁴Pb ratios up to 18.27. These features together with model calculations using Sr–Nd–Pb isotopes suggest modification of a primary syenite magma by combined AFC processes involving ancient continental crust. In this case, high Nb abundances of the parental syenite liquid prevent the development of significant negative Nb anomalies that may be expected due to interaction with continental crust.     

Cenozoic “radiobarite” occurrences in the Ohře (Eger) Rift, Bohemian Massif: Mineralogical and geochemical revision

Barite occurrences related to the Cenozoic (Late Alpine) low-temperature hydrothermal activity are present in the continental Ohře (Eger) Rift area. A specific, Ra-bearing type of barite has been known under the name “radiobarite” from this area since 1904. Revision of 12 localities revealed the presence of alleged radiobarite only in the Teplice (Lahošť–Jeníkov) and Karlovy Vary areas. Barite from other localities is radium-poor. Barite crystals showing concentric oscillation colour zoning totally prevail. Isomorphous substitution of Sr (X×10⁻¹ to X×wt%), Ca (X×10⁻² wt%) and Fe (X×10⁻¹ wt%) for Ba was proved. Average SrO contents of 0.4 wt% are markedly exceeded in some samples from Lahošť–Jeníkov (max. 3.2 wt%) and Karlovy Vary (max. 4.9 wt%). Besides inclusions of stoichiometric iron disulphide, the same samples also contain iron disulphides with unusual high contents of Co (max. 12.2 wt%) and Ni (max. to 8.4 wt%). Specific activity of ²³⁸U in the studied barites is very low while that of ²²⁶Ra reaches 8 Bq/g in several samples. Therefore, ²²⁶Ra is not in equilibrium with its parent uranium. These “radiobarites” or their parts must be therefore relatively young, not older than 10–15 ka. Very low uranium contents (<0.4 ppm) were also confirmed by neutron activation analyses of barite samples.

Unit-cell dimensions refined from X-ray powder diffraction data do not show any systematic variation with the measured chemical composition. Their values agree with the data given in the literature. Reflection half-widths, however, seem to correlate with chemistry. Peaks are wider in samples from Lahošť–Jeníkov and Karlovy Vary.

Sulphur and oxygen stable isotope compositions of the Cenozoic barite mineralization of Teplice area are very uniform (δ³⁴S values between 3.9‰ and 7.1‰ CDT, and δ¹⁸O values between 6.1‰ and 7.7‰ SMOW), while the barites of Děc˘ín area show more variable sulphur sources. Sulphate derived from sediments of the Tertiary Most Basin seems to dominate for the Teplice area, while Cretaceous sediments are a more probable sulphur source in the Děc˘ín area. Calculation of oxygen isotope composition of hydrothermal fluids based on fluid inclusion homogenization temperatures and barite δ¹⁸O data shows δ¹⁸O_fluid values in the range of meteoric waters or δ¹⁸O – shifted deep circulating meteoric or basinal waters.     

Isotopic (O, Sr, Nd) and trace element geochemistry of the Laouni layered intrusions (Pan-African belt, Hoggar, Algeria): evidence for post-collisional continental tholeiitic magmas variably contaminated by continental crust

The three layered intrusions studied in the Laouni area have been emplaced within syn-kinematic Pan-African granites and older metamorphic rocks. They have crystallized at the end of the regional high-temperature metamorphism, but are free from metamorphic recrystallization, revealing a post-collisional character. The cumulate piles can be interpreted in terms of two magmatic liquid lines of descent: one is tholeiitic and marked by plagioclase–olivine–clinopyroxene cumulates (troctolites or olivine bearing gabbros), while the other is calc-alkaline and produced orthopyroxene–plagioclase rich cumulates (norites). One intrusion (WL (West Laouni)-troctolitic massif), shows a Lower Banded Zone where olivine-chromite orthocumulates are interlayered with orthopyroxene-rich and olivine–plagioclase–clinopyroxene cumulates, whereas the Upper Massive Zone consists mainly of troctolitic and gabbroic cumulates. The other two massifs are more homogeneous: the WL-noritic massif has a calc-alkaline differentiation trend whereas the EL (East Laouni)–troctolitic massif has a tholeiitic one. Separated pyroxene and plagioclase display similar incompatible trace element patterns, regardless of the cumulate type. Calculated liquids in equilibrium with the two pyroxenes for both noritic and troctolitic cumulates are characterized by negative Nb, Ta, Zr and Hf anomalies and light REE enrichment inherited from the parental magmas. Troctolitic cumulates have mantle-derived δ¹⁸O (+5 to +6‰), initial ⁸⁷Sr/⁸⁶Sr (Sr_i=0.7030 to 0.7054), _Nd (+5 to −1) values whereas noritic cumulates are variably enriched in δ¹⁸O (+7 to +9‰), show negative _Nd (−7 to −12) and slightly higher Sr_i (0.7040–0.7065). Based on field, isotopic ratios are interpreted as resulting from a depleted mantle source (Sr_i=0.7030; _Nd=+5.1; δ¹⁸O=+5.1‰) having experience short term incompatible element enrichment and variable crustal contamination. The mantle magma was slightly contaminated by an Archaean lower crust in troctolitic cumulates, more strongly and with an additional contamination by an Eburnian upper crust in noritic cumulates. Lower crust input is recorded mainly by Sr and Nd isotopes and upper crust input by O isotopes. This is probably due to the different water/rock ratios of these two crust types. Assimilation of low amounts (<10%) of quartz-bearing felsic rocks, coming from both lower and upper crust, can explain the rise of SiO₂ activity, the enrichment in ¹⁸O and ⁸⁷Sr and the lowering of _Nd in the noritic cumulates compared to troctolitic ones. The geodynamic model proposed to account for the Laouni tholeiitic magmatism involves a late Pan-African asthenospheric rise due to a rapid lithospheric thinning associated with functioning of shear zones, which allowed tholeiitic magmas to reach high crustal levels while experiencing decreasing degrees of crustal contamination with time.     

Geochemistry of microgranular enclaves and host granite from Telões (Vila Pouca de Aguiar), Northern Portugal

At Telões, a subaluminous medium- to coarse-grained porphyritic biotite granite, crops out along the Vila Real NNE–SSW fault. It is a post-tectonic granite of 299±3 Ma old given by U–Pb isotopic data on zircon. It contains metaluminous to subaluminous tonalitic, granodioritic and monzogranitic enclaves. All granitoids have Fe²⁺-biotite and some enclaves contain magnesiohornblende and subsolidus actinolite. Monzogranitic enclaves show obvious similarities to the host granite. Linear array between enclaves and host granite is observed in Rb–Sr typical isochron diagram and gives the age of 286±11 Ma and (⁸⁷Sr/⁸⁶Sr)₀=0.7063±0.0011. Microgranular enclaves have δ¹⁸O values similar to those of the hosting granite. Microgranular enclaves are hybrid rocks probably formed by mixing between a tonalitic enclave magma and a host granite magma as supported by the modelling of major and trace elements. The similar isotopic signatures suggest a subsequent partial equilibration of the enclaves and granite magmas.     

A SHRIMP U–Pb and LA-ICP-MS trace element study of the petrogenesis of garnet–cordierite–orthoamphibole gneisses from the Central Zone of the Limpopo Belt, South Africa

The Central Zone of the Limpopo Belt (South Africa) underwent high-grade metamorphism at 2.7–2.5 and 2.03 Ga. Quartz-rich, garnet-, cordierite-, biotite- and orthoamphibole-bearing, feldspar-free gneisses from the western Central Zone reached granulite-facies conditions (800 °C at 8–10 kbar) followed by decompression. Garnet from one such sample shows significant zonation in trace elements but little zonation in major elements. Zoning patterns suggest that the early prograde breakdown of REE-rich accessory phases contributed to the garnet trace element budget. Monazite from the sample yields a SHRIMP weighted mean ²⁰⁷Pb–²⁰⁶Pb age of 2028 ± 3 Ma, indistinguishable from a SHRIMP zircon age of 2022 ± 11 Ma previously measured on metamorphic overgrowths on 2.69 Ga igneous zircon cores. New zircon and monazite formed before, or at, the metamorphic peak, and occur as inclusions in garnet. Monazite appears to have formed through the breakdown of early allanite ± xenotime ± apatite. Trace element zoning patterns in garnet and the age of accessory phases are most consistent with a single tectonometamorphic event at 2.03 Ga.

The plagioclase and K-feldspar-free composition of the garnet–cordierite–orthoamphibole gneisses requires open system processes such as intense hydrothermal alteration of protoliths or advanced chemical weathering. In the studied sample, the 2.69 Ga igneous zircons show a prominent negative Eu anomaly, suggesting equilibrium with plagioclase, or plagioclase fractionation in the precursor magma. In contrast, the other minerals either show small negative (2.03 Ga monazite), no (2.02 Ga zircon and garnet) or positive Eu anomalies (orthoamphibole). This suggests that the unusual bulk compositions of these rocks were set in after 2.69 Ga but before the peak of the 2.03 Ga event, most probably while the protoliths resided at shallow or surficial crustal levels.     

Petrogenesis of tourmaline rocks associated with Fe-carbonate–graphite metapelite, metabasite and strata-bound polymetallic sulphide mineralisation, Peloritani Mountains, Sicily, Southern Italy

Tourmalinite and tourmaline-rich rocks associated with Fe-carbonate–graphite phyllite, strata-bound polymetallic sulphide deposits, metabasite and marble were studied, for information on the mechanism of tourmaline formation in the pre-Hercynian low-grade metamorphic sequence of the Mandanici Unit in the Peloritani Mountains of Sicily, southern Italy. The major and trace element compositions of the tourmaline rocks suggest the existence of a sedimentary protolith with pre-metamorphic black shale and bedded chert. Boron was interpreted to be accumulated in a restricted sedimentary basin, between platform carbonate formations, with abundant organic matter and Fe–Al–Ti-rich laterite–bauxite soil-derived clastic supply, under a continental volcano-tectonic extensional regime accompanied by a local convective hydrothermal system along faults. Petrographic, crystal–chemical and δ¹¹B isotopic data are compatible with a model of marine sediment dewatering at temperatures below 200 °C, which caused the removal of boron from clay. Metamorphism led to the development of tourmaline in an Al–Ti-rich environment, in equilibrium with other minerals such as ilmenite, albite and muscovite. The upper temperature of metamorphism (almost 375 °C), estimated on the basis of δ¹¹B, fits geothermometric results from Δ¹³C_{carbonate–graphite} on associated rocks. The estimated value of δ¹¹B in the tourmalinite protolith, − 7.5‰ , is also compatible with continental-derived Al-rich sediments.     

Stable isotope study of cave percolation waters in subtropical Brazil: Implications for paleoclimate inferences from speleothems

We analyze the interannual monthly variability of oxygen isotope ratios in data from IAEA stations along the Atlantic coast of South America between 23° and 34° S to evaluate the influence of parameters such as temperature, rainfall amount and moisture source contribution on meteoric water recharging two karst systems in subtropical Brazil. In addition, a 2 year monitoring program performed on soil and cave drip and rimstone pool waters from sampling sites with contrasting discharge values and located at 100 and 300 m below the surface in the Santana Cave System (24°31′ S; 48°43′ W), is used to test the influence of hydrologic and geologic features on the temporal variations of seepage water δ¹⁸O.

Interannual monthly variations in δ¹⁸O of rainfall reflect primarily regional changes in moisture source contribution related to seasonal shifts in atmospheric circulation from a more monsoonal regime in summer (negative values of δ¹⁸O) to a more extratropical regime in winter (positive values of δ¹⁸O). Variations in groundwater δ¹⁸O indicate that the climatic signal of recent rainfall events is rapidly transmitted through the relatively deep karst aquifer to the cave drip waters, regardless of location of collection in the cave. In addition, the data also suggest that water replenishment in the system is triggered by the increase in hydraulic head during periods when recharge exceeds the storage capacity of the soil and epikarst reservoirs. Significant perturbations in the groundwater composition, characterized by more positive values of δ¹⁸O, are probably connected to an increased Atlantic moisture contribution associated with extratropical precipitation. This implies that the δ¹⁸O of speleothems from caves in this region may be a suitable proxy for studying tropical–extratropical interactions over South America, a feature that is intrinsically related to the global atmospheric circulation.     

Contrasting response of monazite and zircon to a high-T thermal overprint

Contact metamorphism in the aureole of the 1322 Ma Makhavinekh Lake Pluton, northern Labrador, affected monazite and zircon in the adjacent 1850 Ma metapelitic gneisses. Transformation of regional garnet and sillimanite to lower-pressure symplectitic intergrowths of cordierite, orthopyroxene, and spinel was accompanied by resorption of inherited monazite inclusions in garnet coupled with the appearance of coronitic high-Y monazite rims. In situ ion-microprobe dating is used to show that high-Y rims formed during contact metamorphism. Liberation of Y and HREE from garnet also gave rise to new xenotime growth. The coronitic nature of monazite overgrowths reflects the diffusion-controlled nature of net-transfer reactions whereas its higher Y composition reflects equilibration with xenotime at peak T (> 800 °C) conditions in the inner aureole. Very thin overgrowths on inherited zircon were also encountered, but only where zircon is surrounded by the symplectitic assemblage, reflecting liberation of Zr from garnet. Although these overgrowths are too thin to date using conventional ion-microprobe techniques, well-developed triple junctions between zircon and orthopyroxene suggests that they grew in textural equilibrium with the contact metamorphic assemblage.

In contrast to monazite, inherited zircon remained intact during contact metamorphism, exhibiting no change in morphology (other than the growth of thin rims) or internal zoning throughout the aureole. However, inherited sector-zoned zircons of anatectic origin display evidence for intracrystalline Pb redistribution in the inner aureole. In these samples, ion-microprobe analyses encountered heterogeneous Pb signals and a dispersion of ²⁰⁷Pb / ²⁰⁶Pb dates away from the well constrained 1850 Ma age of regional metamorphism. Whereas analyses from the outer aureole faithfully record the age of regional metamorphism, those from the inner aureole are normally and reversely discordant and distributed along a line collinear with a 1850 to 1322 Ma discordia. This disturbance is correlated with proximity to the pluton implying that Pb was mobile in the zircon lattice during contact metamorphism. Most grains are characterized by apparent Pb loss from low-U domains and apparent Pb gain in higher-U domains. These data are interpreted to reflect recovery of strained crystalline domains leading to expulsion of Pb* that was able to efficiently diffuse into higher-U domains that were partly amorphous prior to rapid reheating in the inner aureole.     

A zircon study from the Rhodope metamorphic complex, N-Greece: Time record of a multistage evolution

Zircons from an eclogite and a diamond-bearing metapelite near the Kimi village (north-eastern Rhodope Metamorphic Complex, Greece) have been investigated by Micro Raman Spectroscopy, SEM, SHRIMP and LA-ICPMS to define their inclusion mineralogy, ages and trace element contents. In addition, the host rocks metamorphic evolution was reconstructed and linked to the zircon growth domains.

The eclogite contains relicts of a high pressure stage (ca. 700 °C and > 17.5 kbar) characterised by matrix omphacite with Jd_40–35. This assemblage was overprinted by a lower pressure, higher temperature metamorphic event (ca. 820 °C and 15.5–17.5 kbar), as indicated by the presence of clinopyroxene (Jd_35–20) and plagioclase. Biotite and pargasitic amphibole represent a later stage, probably related to an influx of fluids. Zircons separated from the eclogite contain magmatic relicts indicating Permian crystallization of a quartz-bearing gabbroic protolith. Inclusions diagnostic of the high temperature, post-eclogitic overprint are found in metamorphic zircon domain Z2 which ages spread over a long period (160 – 95 Ma). Based on zircon textures, zoning and chemistry, we suggest that the high-temperature peak occurred at or before ca. 160 Ma and the zircons were disturbed by a later event possibly at around 115 Ma. Small metamorphic zircon overgrowths with a different composition yield an age of 79 ± 3 Ma, which is related to a distinct amphibolite-facies metamorphic event.

The metapelitic host rock consists of a mesosome with garnet, mica and kyanite, and a quartz- and plagioclase-bearing leucosome, which formed at granulite-facies conditions. Based on previously reported micro-diamond inclusions in garnet, the mesosome is assumed to have experienced UHP conditions. Nevertheless, (U)HP mineral inclusions were not found in the zircons separated from the diamond-bearing metapelite. Inclusions of melt, kyanite and high-Ti biotite in a first metamorphic zircon domain suggest that zircon formation occurred during pervasive granulite-facies metamorphism. An age of 171 ± 1 Ma measured on this zircon domain constrains the high-temperature metamorphic event. A second, inclusion-free metamorphic domain yielded an age of 160 ± 1 Ma that is related to decompression and melt crystallization.

The similar age data obtained from the samples indicate that both rock types recorded a high-T metamorphic overprint at granulite-facies conditions at ca. 170 – 160 Ma. This age implies that any high pressure or even ultra-high pressure metamorphism in the Kimi Complex occurred before that time. Our findings define new constraints for the geodynamic evolution for the Alpine orogenic cycle within the northernmost Greek part of the Rhodope Metamorphic Complex. It is proposed that the rocks of the Kimi Complex belong to a suture zone squeezed between two continental blocks and result from a Paleo-ocean basin, which should be located further north of the Jurassic Vardar Ocean.