Boron isotopic composition of subduction-zone metamorphic rocks

Many arc lavas contain material derived from subducted oceanic crust and sediments, but it remains unresolved whether this distinctive geochemical signature is transferred from the subducting slab by aqueous fluids, silicate melts, or both. Boron isotopic measurements have the potential to distinguish between slab transfer mechanisms because ¹¹B fractionates preferentially into aqueous fluids whereas little fractionation may occur during partial melting. Previous studies have shown that δ¹¹B values of island arc lavas (−6 to +7) overlap the range of δ¹¹B values for altered oceanic crust (−5 to +25) and pelagic sediments and turbidites (−7 to +11). Secondary ion mass spectrometry (SIMS) analyses of minerals in subduction-zone metamorphic rocks yield δ¹¹B=−11 to −3 suggesting that slab dehydration reactions significantly lower the δ¹¹B values of subducted oceanic crust and sediments. In order to explain the higher δ¹¹B values reported for arc lavas as compared to subduction-zone metamorphic rocks, the B-bearing component derived from the metamorphosed slab must be enriched in ¹¹B relative to the slab, favoring an aqueous fluid as the slab transfer mechanism.     

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.     

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.     

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.     

The origin of basic rocks of the Korosten AMCG complex, Ukrainian shield: Implication of Nd and Sr isotope data

The Korosten complex is a Paleoproterozoic gabbro–anorthosite–rapakivi granite intrusion which was emplaced over a protracted time interval — 1800–1737 Ma. The complex occupies an area of about 12 000 km² in the north-western region of the Ukrainian shield. About 18% of this area is occupied by various mafic rocks (gabbro, leucogabbro, anorthosite) that comprise five rock suites: early anorthositic A₁ (1800–1780 Ma), main anorthositic A₂ (1760 Ma), early gabbroic G₃ (between 1760 and 1758 Ma), late gabbroic G₄ (1758 Ma), and a suite of dykes D₅ (before 1737 Ma). In order to examine the relationships between the various intrusions and to assess possible magmatic sources, Nd and Sr isotopic composition in mafic whole-rock samples were measured. New Sr and Nd isotope measurements combined with literature data for the mafic rocks of the Korosten complex are consistent and enable construction of Rb–Sr and Sm–Nd isochronous regressions that yield the following ages: 1870 ± 310 Ma (Rb–Sr) and 1721 ± 90 Ma (Sm–Nd). These ages are in agreement with those obtained by the U–Pb method on zircons and indicate that both Rb–Sr and Sm–Nd systems have remained closed since the time of crystallisation. In detail, however, measurable differences in isotopic composition of the Korosten mafic rock depending on their suite affiliation were revealed. The oldest, A₁ rocks have lower Sr (⁸⁷Sr/⁸⁶Sr₍₁₇₆₀₎ = 0.70233–0.70288) and higher Nd (εNd₍₁₇₆₀₎ = 1.6–0.9) isotopic composition. The most widespread A₂ anorthosite and leucogabbro display higher Sr and lower Nd isotopic composition: ⁸⁷Sr/⁸⁶Sr₍₁₇₆₀₎ = 0.70362, εNd₍₁₇₆₀₎ varies from 0.2 to − 0.7. The G₃ gabbro–norite has slightly lower εNd₍₁₇₆₀₎ varying from − 0.7 to − 0.9. Finally, G₄ gabbroic rocks show relatively high initial ⁸⁷Sr/⁸⁶Sr (0.70334–0.70336) and the lowest Nd isotopic composition (εNd₍₁₇₆₀₎ varies from − 0.8 to − 1.4) of any of the mafic rocks of the Korosten complex studied to date. On the basis of Sr and Nd isotopic composition we conclude that Korosten initial melts may have inherited their Nd and Sr isotopic characteristics from the lower crust created during the 2.05–1.95 Ga Osnitsk orogeny and 2.0 Ga continental flood basalt event. Indeed, εNd₍₁₇₆₀₎ values in Osnitsk rocks vary from 0.0 to − 1.9 and from 0.2 to 3.4 in flood basalts. We suggest that these rocks being drawn into the upper mantle might melt and give rise to the Korosten initial melts. ⁸⁷Sr/⁸⁶Sr₍₁₇₆₀₎ values also support this interpretation. We suggest that the Sr and Nd isotopic data currently available on mafic rocks of the Korosten complex are consistent with an origin of its primary melts by partial melting of lower crustal material due to downthrusting of the lower crust into upper mantle forced by Paleoproterozoic amalgamation of Sarmatia and Fennoscandia.     

Basalt magma genesis and fractionation in collision- and extension-related provinces: A comparison between eastern, central and western Anatolia

Experimental studies of synthetic and natural basalt systems suggest that conditions of magma genesis and fractionation depend fundamentally on mantle temperatures and lithospheric stress fields. In general, compressional settings are more conducive to polybaric fractionation than extensional settings and in this regard, the Anatolian magmatic province offers a natural laboratory for comparing near-coeval basalt eruptions as a function of regional tectonics — compressional (collision-related) régimes dominating in eastern Anatolia and extensional tectonics characterizing a western province related to Aegean Sea opening. Projection of Plio-Quaternary basalt normative compositions from the Western Anatolia Extensional Province (WAEP), the Central Anatolian ‘Ova’ Province (CAOP), and Eastern Anatolia Compressional Province (EACP) are projected onto Ol–Ne–Cpx and Pl–Cpx–Ol planes in the simplified basalt system (Ne–Cpx–Ol–Qz), each showing distinctive liquid lines of descent. WAEP basalts are mostly constrained by low-pressure (< 0.5 GPa) cotectics while CAOP and EACP compositions conform to moderate and/or high-pressure (0.8–3.0 GPa) cotectics. Overall, a quasi-linear shift from moderate and/or high-pressure to low-pressure equilibria matches the westward transgression from compressional east Anatolia to the extensional west Anatolian–Aegean region. Comparison of their respective primary (mantle-equilibrated) magmas–simulated by normalizing their compositions to MgO = 15 wt.% (Mg-15)–with parameterized anhydrous and H₂O-undersaturated experimental melts suggests they segregated from spinel- to garnet-lherzolite mantle facies at pressures between c. 2 and 3 GPa (c. 70–100 km depth) under H₂O-undersaturated conditions. Interpolated potential temperatures (T_p) and lithospheric stretching factors (β) range as follows: (1) eastern Anatolian basalts associated with the Arabian foreland show T_p varying between 1250 and 1400 °C (except for the Karacalidag alkali basalts, south of the Bitlis–Zagros fracture zone, for which T_p ranges up to 1450 °C), for β values of 1.2–1.8. T_p values for central Anatolia (e.g. Sivas) range between 1300 and 1375 °C (except for Karapinar, Egrikuyu and Hasandag, which show < 1150 °C), and β values of 1.3–1.4. For western Anatolian basalts, T_p range mostly between 1250 and 1330 °C, except for a single value for Canakkale of 1400 °C and Kula sample showing T_p < 1200 °C, and β values of 1.3–2.0. Variation of these conditions is as great or greater than that between provinces, although there are clearly significant constraints on the inferred polybaric to low-pressure isobaric fractionation régimes. Covariation of total FeO, TiO₂, La/Yb, Ce/Sm, Zr/Y and Zr/Nb reflects small but significant differences in bulk composition and ambient melt fraction while the covariance of Ce/Sm and Sm/Yb is consistent with the segregation of primitive melts at the spinel- to garnet-lherzolite transition.     

The isotopic composition of zircon and garnet: A record of the metamorphic history of Naxos, Greece

Growth of zircon with respect to that of garnet has been studied using a combination of petrography, U–Pb dating and oxygen isotope analysis. The aim is to document the mechanism and pressure–temperature conditions of zircon growth during metamorphism in order to better constrain the Tertiary metamorphic history of Naxos, Greece. Two metamorphisms are recognised: (1) an Eocene Franciscan metamorphism (M1) and (2) a widespread Miocene Barrovian metamorphism (M2) that increases from greenschist facies up to partial melting. An amphibolite sample contains zircon crystals characterised by a magmatic core and two metamorphic rims, denoted as A and B, dated at 200–270, 42–69, and 14–19 Ma, respectively. The first metamorphic rim A (δ¹⁸O = 7 ± 1‰) preserves the δ¹⁸O value of the magmatic core (6.2 ± 0.8‰), whereas rim B is characterised by higher δ¹⁸O values (7.8 ± 1.8‰). These observations indicate the formation of A rims by solid-state recrystallisation in a closed system with regard to oxygen and those of B in an open system. Compositional zoning in garnet is interpreted as the result of decompressional heating. Zircon B rims and garnet rims display similar δ¹⁸O values which indicates a contemporaneous growth of garnet and zircon rims during the Miocene Barrovian event (M2). Calcic gneiss and metapelite samples contain zircon crystals with single metamorphic overgrowths aged 41–57 Ma. δ¹⁸O values measured in zircon overgrowths (11.8 ± 1.4‰) from the calcic gneiss are similar to those measured in garnet rims (11.4 ± 1.1‰) from the same rock. This suggests that garnet rims and zircon overgrowths grew during the high pressure–low temperature event in equilibrium with prograde fluids. In the metapelite sample, δ¹⁸O values are similar in garnet cores (14.8 ± 0.2‰) and in zircon metamorphic overgrowths (14.2 ± 0.5‰). As zircon overgrowths have been dated at ca. 50 Ma by U–Pb, garnet cores and zircon overgrowths are interpreted to have grown during the high pressure event.

As demonstrated here for the island of Naxos, correlating the crystallisation of zircon with that of metamorphic index minerals such as garnet using stable isotope composition and U–Pb determination is a powerful tool for deciphering the mechanism of zircon growth and pin-pointing zircon crystallisation within the metamorphic history of a terrain. This approach is potentially hampered by an inability to verify the degree of textural equilibrium of zircon with other mineral phases, and the possible preservation (in metamorphic rims) of isotopic signatures from pre-existing zircon when they form by recrystallisation. Nevertheless, this study illustrates the application of this approach in providing key constraints on the timing and mechanism of growth of minerals important to understanding metamorphic petrogenesis.     

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.     

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.     

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.     

Geochemistry and petrology of Tertiary volcanic rocks and related ultramafic xenoliths from the central and eastern Oman Mountains

The Tertiary volcanic rocks of the central and the eastern parts of the Oman Mountains consist mainly of basanites with abundant upper mantle ultramafic xenoliths. The lavas are alkaline (42–43 wt.% SiO₂; 3.5–5.5 wt.% Na₂O + K₂O). They include primitive (11–14 wt.% MgO) features with strong OIB-like geochemical signatures. Trace element and Sr–Nd isotope data for the basanites suggest mixing of melts derived from variable degrees of melting of both garnet- and spinel lherzolite-facies mantle source. The associated xenolith suite consists mainly of spinel and Cr-bearing diopside wehrlite, lherzolite and dunite with predominantly granuloblastic textures. No significant difference in chemistry was found between the basanites and xenoliths from the central and eastern Oman Mountains, which indicate a similar mantle source. Calculated oxygen fugacity indicates equilibration of the xenoliths at − 0.43 to − 2.2 log units above the fayalite–magnetite–quartz (FMQ) buffer. Mantle xenolith equilibration temperatures range from 910–1045 + 50 °C at weakly constrained pressures between 13 and 21 kbar. Xenolith data and geophysical studies indicate that the Moho is located at a depth of  40 km. A geotherm substantially hotter (90 mW m^− 2) than the crust–mantle boundary (45 mW m^− 2) is indicated and probably relates to tectonothermal events associated with the local and regional Tertiary magmatism. The petrogenesis of the Omani Tertiary basanites is explained by partial melting of an asthenospheric mantle protolith during an extension phase predating opening of the Gulf of Aden and plume-related alkaline volcanic rocks.     

Provenance of the Neoproterozoic Maricá Formation (Sul-rio-grandense Shield, Southern Brazil): Petrographic and Sm–Nd isotopic constraints

This paper reports the integrated application of petrographic and Sm–Nd isotopic analyses for studying the provenance of the Neoproterozoic Maricá Formation, southern Brazil. This unit encompasses sedimentary rocks of fluvial and marine affiliations. In the lower fluvial succession, sandstones plot in the “craton interior” and “transitional continental” fields of the QFL diagram. Chemical weathering probably caused the decrease of the ¹⁴⁷Sm/¹⁴⁴Nd ratios to 0.0826 and 0.0960, consequently lowering originally > 2.0 Ga T_DM ages to 1.76 and 1.81 Ga. ¹⁴³Nd/¹⁴⁴Nd ratios are also low (0.511521 to 0.511633), corresponding to negative ε_Nd present-day values (− 21.8 and − 19.6). In the intermediate marine succession, sandstones plot in the “dissected arc” field, reflecting the input of andesitic clasts. Siltstones and shales reveal low ¹⁴³Nd/¹⁴⁴Nd ratios (0.511429 to 0.511710), ε_Nd values of − 18.1 and − 23.6, and T_DM ages of 2.16 and 2.37 Ga. Sandstones of the upper fluvial succession have “dissected arc” and “recycled orogen” provenance. ¹⁴³Nd/¹⁴⁴Nd isotopic ratios are also relatively low, from 0.511487 to 0.511560, corresponding to ε_Nd values of − 22.4 and − 21.0 and T_DM of 2.07 Ga. A uniform granite–gneissic basement block of Paleoproterozoic age, with subordinate volcanic rocks, is suggested as the main sediment source of the Maricá Formation.     

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.     

Diamonds and their mineral inclusions from the A154 South pipe, Diavik Diamond Mine, Northwest territories, Canada

Mineral inclusions recovered from 100 diamonds from the A154 South kimberlite (Diavik Diamond Mines, Central Slave Craton, Canada) indicate largely peridotitic diamond sources (83%), with a minor (12%) eclogitic component. Inclusions of ferropericlase (4%) and diamond in diamond (1%) represent “undetermined” parageneses.

Compared to inclusions in diamonds from the Kaapvaal Craton, overall higher CaO contents (2.6 to 6.0 wt.%) of harzburgitic garnets and lower Mg-numbers (90.6 to 93.6) of olivines indicate diamond formation in a chemically less depleted environment. Peridotitic diamonds at A154 South formed in an exceptionally Zn-rich environment, with olivine inclusions containing more than twice the value (of  52 ppm) established for normal mantle olivine. Harzburgitic garnet inclusions generally have sinusoidal rare earth element (REE_N) patterns, enriched in LREE and depleted in HREE. A single analyzed lherzolitic garnet is re-enriched in middle to heavy REE resulting in a “normal” REE_N pattern. Two of the harzburgitic garnets have “transitional” REE_N patterns, broadly similar to that of the lherzolitic garnet. Eclogitic garnet inclusions have normal REE_N patterns similar to eclogitic garnets worldwide but at lower REE concentrations.

Carbon isotopic values (δ¹³C) range from − 10.5‰ to + 0.7‰, with 94% of diamonds falling between − 6.3‰ and − 4.0‰. Nitrogen concentrations range from below detection (< 10 ppm) to 3800 ppm and aggregation states cover the entire spectrum from poorly aggregated (Type IaA) to fully aggregated (Type IaB). Diamonds without evidence of previous plastic deformation (which may have accelerated nitrogen aggregation) typically have < 25% of their nitrogen in the fully aggregated B-centres. Assuming diamond formation beneath the Central Slave to have occurred in the Archean [Westerlund, K.J., Shirey, S.B., Richardson, S.H., Gurney, J.J., Harris, J.W., 2003b. Re–Os systematics of diamond inclusion sulfides from the Panda kimberlite, Slave craton. VIIIth International Kimberlite Conference, Victoria, Canada, Extended Abstracts, 5p.], such low aggregation states indicate mantle residence at fairly low temperatures (< 1100 °C). Geothermometry based on non-touching inclusion pairs, however, indicates diamond formation at temperatures around 1200 °C. To reconcile inclusion and nitrogen based temperature estimates, cooling by about 100–200 °C shortly after diamond formation is required.     

Geochemical and Sr–Nd–Pb isotopic compositions of the Eocene Dölek and Sariçiçek Plutons, Eastern Turkey: Implications for magma interaction in the genesis of high-K calc-alkaline granitoids in a post-collision extensional setting

The major and trace elements and Sr–Nd–Pb isotopes of the host rocks and the mafic microgranular enclaves (MME) gathered from the Dölek and Sariçiçek plutons, Eastern Turkey, were studied to understand the underlying petrogenesis and geodynamic setting. The plutons were emplaced at  43 Ma at shallow depths ( 5 to 9 km) as estimated from Al-in hornblende geobarometry. The host rocks consist of a variety of rock types ranging from diorite to granite (SiO₂ = 56.98–72.67 wt.%; Mg# = 36.8–50.0) populated by MMEs of gabbroic diorite to monzodiorite in composition (SiO₂ = 53.21–60.94 wt.%; Mg# = 44.4–53.5). All the rocks show a high-K calc-alkaline differentiation trend. Chondrite-normalized REE patterns are moderately fractionated and relatively flat [(La/Yb)_N = 5.11 to 8.51]. They display small negative Eu anomalies (Eu/Eu = 0.62 to 0.88), with enrichment of LILE and depletion of HFSE. Initial Nd–Sr isotopic compositions for the host rocks are ε_Nd(43 Ma) = − 0.6 to 0.8 and mostly I_Sr = 0.70482–0.70548. The Nd model ages (T_DM) vary from 0.84 to 0.99 Ga. The Pb isotopic ratios are (²⁰⁶Pb/²⁰⁴Pb) = 18.60–18.65, (²⁰⁷Pb/²⁰⁴Pb) = 15.61–15.66 and (²⁰⁸Pb/²⁰⁴Pb) = 38.69–38.85. Compared with the host rocks, the MMEs are relatively homogeneous in isotopic composition, with I_Sr ranging from 0.70485 to 0.70517, ε_Nd(43 Ma) − 0.1 to 0.8 and with Pb isotopic ratios of (²⁰⁶Pb/²⁰⁴Pb) = 18.58–18.64, (²⁰⁷Pb/²⁰⁴Pb) = 15.60–15.66 and (²⁰⁸Pb/²⁰⁴Pb) = 38.64–38.77. The MMEs have T_DM ranging from 0.86 to 1.36 Ga. The geochemical and isotopic similarities between the MMEs and their host rocks indicate that the enclaves are of mixed origin and are most probably formed by the interaction between the lower crust- and mantle-derived magmas. All the geochemical data, in conjunction with the geodynamic evidence, suggest that a basic magma derived from an enriched subcontinental lithospheric mantle, probably triggered by the upwelling of the asthenophere, and interacted with a crustal melt that originated from the dehydration melting of the mafic lower crust at deep crustal levels. Modeling based on the Sr–Nd isotope data indicates that  77–83% of the subcontinental lithospheric mantle involved in the genesis. Consequently, the interaction process played an important role in the genesis of the hybrid granitoid bodies, which subsequently underwent a fractional crystallization process along with minor amounts of crustal assimilation, en route to the upper crustal levels generating a wide variety of rock types ranging from diorite to granite in an extensional regime.     

Age and emplacement of late-Variscan granites of the western Bohemian Massif with main focus on the Hauzenberg granitoids (European Variscides, Germany)

The Variscan Hauzenberg pluton consists of granite and granodiorite that intruded late- to postkinematically into HT-metamorphic rocks of the Moldanubian unit at the southwestern margin of the Bohemian Massif (Passauer Wald). U–Pb dating of zircon single-grains and monazite fractions, separated from medium- to coarse-grained biotite-muscovite granite (Hauzenberg granite II), yielded concordant ages of 320 ± 3 and 329 ± 7 Ma, interpreted as emplacement age. Zircons extracted from the younger Hauzenberg granodiorite yielded a ²⁰⁷Pb–²⁰⁶Pb mean age of 318.6 ± 4.1 Ma. The Hauzenberg granite I has not been dated. The pressure during solidification of the Hauzenberg granite II was estimated at 4.6 ± 0.6 kbar using phengite barometry on magmatic muscovite, corresponding to an emplacement depth of 16-18 km. The new data are compatible with pre-existing cooling ages of biotite and muscovite which indicate the Hauzenberg pluton to have cooled below T = 250–400 °C in Upper Carboniferous times. A compilation of age data from magmatic and metamorphic rocks of the western margin of the Bohemian Massif suggests a west- to northwestward shift of magmatism and HT/LP metamorphism with time. Both processes started at > 325 Ma within the South Bohemian Pluton and magmatism ceased at ca. 310 Ma in the Bavarian Oberpfalz. The slight different timing of HT metamorphism in northern Austria and the Bavarian Forest is interpreted as being the result of partial delamination of mantle lithosphere or removal of the thermal boundary layer.     

Geochronological, geochemical and geothermal constraints on petrogenesis of the Indosinian peraluminous granites in the South China Block: A case study in the Hunan Province

The Indosinian granites in the South China Block (SCB) have important tectonic significance for the evolution of East Asia. Samples collected from Hunan Province can be geochemically classified into two groups. Group 1 is strongly peraluminous (A/CNK > 1.1), similar to S-type granites, and Group 2 has A/CNK = 1.0–1.1, with an affinity to I-type granites. Group 1 has lower FeOt, Al₂O₃, MgO, CaO, TiO₂ and ε_Nd(t) values but higher K₂O + Na₂O, Rb/Sr, Rb/Ba and ⁸⁷Sr/⁸⁶Sr(t) than those of Group 2. Samples of both groups have similar LREE enriched pattern, with (Eu/Eu) = 0.19–0.69, and strongly negative Ba, Sr, Nb, P and Ti anomalies. Geothermobarometry study indicates that the precursor magmas were emplaced at high-level depth with relatively low temperature (734–827 °C). Geochemical data suggest that Group 1 was originated from a source dominated by pelitic composition and Group 2 was from a mixing source of pelitic and basaltic rocks with insignificant addition of newly mantle-derived magma. Eight granitic samples in Hunan Province are dated at the cluster of 243–235 and 218–210 Ma by zircon U–Pb geochronology. Together with recent zircon U–Pb ages for other areas in the SCB, two age-clusters, including 243–228 Ma just after peak-metamorphism ( 246–252 Ma) and 220–206 Ma shortly after magma underplating event (224 Ma), are observed. It is proposed that in-situ radiogenic heating from the over-thickened crust induced dehydrated reaction of muscovite and epidote/zoisite to form the early Indosinian granites in response to the isostatic readjustments of tectonically thickened crust. Conductive heating from the underplating magma in the postcollisional setting triggered the formation of late Indosinian granites. Such a consideration is supported by the results from FLAC numerical simulation.     

Granulite facies xenoliths from Prindle volcano, Alaska: Implications for the northern Cordilleran crustal lithosphere

Xenoliths collected from Prindle volcano, Alaska (Lat. 63.72°N; Long. 141.82°W) provide a unique opportunity to examine the lower crust of the northern Canadian Cordillera. The cone's pyroclastic deposits contain crustal and mantle-derived xenoliths. The crustal xenoliths include granulite facies metamorphic rocks and charnockites, comprising orthopyroxene (opx)–plagioclase (pl)–quartz (qtz) ± mesoperthite (msp) and clinopyroxene (cpx). Opx–cpx geothermometry yields equilibrium temperatures (T) from 770 to 1015 °C at 10 kbar. Pl–cpx–qtz geobarometry yields pressures (P) of  6.6–8.0 kbar. Integrated mesoperthite compositions suggest minimum temperatures of 1020–1140 °C at 10 kbar using solvus geothermometry. The absence of garnet in these rocks indicates a range of maximum pressure of 5–11.3 kbar, and calculated solidi constrain upper temperature limits. We conclude that the granulite facies assemblages represent relatively dry metamorphism at pressures indicative of crustal thicknesses similar to present day ( 36 km). Zircon separates from a single crustal xenolith yield mainly Early Tertiary (48–63 Ma) U–Pb ages which are considerably younger than the cooling ages of the high-pressure amphibolites exposed at the surface. The distribution of zircon ages is interpreted as indicating zircon growth coincident with at least two different thermal events as expressed at surface: (i) the eruption of the Late Cretaceous Carmacks Group volcanic rocks in western Yukon and adjacent parts of Alaska, and (ii) emplacement of strongly bimodal high level intrusions across much of western Yukon and eastern Alaska possibly in an extensional tectonic regime. The distributions of zircon growth ages and the preservation of higher-than-present-day (> 25 ± 3 °C km^− 1) geothermal gradients in the granulite facies rocks demonstrate the use of crustal xenoliths for recovering records of past, lithospheric-scale thermal–tectonic events.     

Sveconorwegian crustal underplating in southwestern Fennoscandia: LAM-ICPMS U–Pb and Lu–Hf isotope evidence from granites and gneisses in Telemark, southern Norway

Laser ablation ICPMS U–Pb and Lu–Hf isotope data on granitic-granodioritic gneisses of the Precambrian Vråvatn complex in central Telemark, southern Norway, indicate that the magmatic protoliths crystallized at 1201 ± 9 Ma to 1219 ± 8 Ma, from magmas with juvenile or near-juvenile Hf isotopic composition (¹⁷⁶Hf/¹⁷⁷Hf = 0.2823 ± 11, epsilon-Hf > + 6). These data provide supporting evidence for the depleted mantle Hf-isotope evolution curve in a time period where juvenile igneous rocks are scarce on a global scale. They also identify a hitherto unknown event of mafic underplating in the region, and provide new and important limits on the crustal evolution of the SW part of the Fennoscandian Shield. This juvenile geochemical component in the deep crust may have contributed to the 1.0–0.92 Ga anorogenic magmatism in the region, which includes both A-type granite and a large anorthosite–mangerite–charnockite–granite intrusive complex. The gneisses of the Vråvatn complex were intruded by a granitic pluton with mafic enclaves and hybrid facies (the Vrådal granite) in that period. LAM-ICPMS U–Pb data from zircons from granitic and hybrid facies of the pluton indicates an intrusive age of 966 ± 4 Ma, and give a hint of ca. 1.46 Ga inheritance. The initial Hf isotopic composition of this granite (¹⁷⁶Hf/¹⁷⁷Hf = 0.28219 ± 13, epsilon-Hf = − 5 to + 6) overlaps with mixtures of pre-1.7 Ga crustal rocks and juvenile Sveconorwegian crust, lithospheric mantle and/or global depleted mantle. Contributions from ca. 1.2 Ga crustal underplate must be considered when modelling the petrogenesis of late Sveconorwegian anorogenic magmatism in the region.