Reconnaissance paleomagnetism of Late Triassic blocks, Kuyul region, Northern Kamchatka Peninsula, Russia

The northernmost Kamchatka Peninsula is located along the northwestern margin of the Bering Sea and consists of complexly deformed accreted terranes. Progressing inland from the northwestern Bering Sea, the Olyutorskiy, Ukelayat and Koryak superterranes (OLY, UKL and KOR) are crossed. These terranes were accreted to the backstop Okhotsk-Chukotsk volcanic-plutonic belt (OChVB) in northernmost Kamchatka. A sedimentary sequence of Albian to Maastrichtian age overlaps the terranes and units of the Koryak superterrane, and constrains their accretion time. A paleomagnetic study of blocks within the Kuyul (KUY) terrane of the Koryak superterrane was completed at two localities (Camp 2: λ=61.83°N, φ=165.83°E and Camp 3: λ=61.67°N, φ=164.75°E). At both localities, paleomagnetic samples were collected from Late Triassic (225–208 Ma) limestone blocks (2–10 m in outcrop height) within a melange zone. Although weak in remanent magnetization, two components of remanent magnetization were observed during stepwise thermal demagnetization at 32 sites. The A component of magnetization was observed between room temperature and approximately 250 °C. This magnetic component is always of downward directed inclination and shows the best grouping at relatively low degrees of unfolding. Using McFadden–Reid inclination-only statistics and averaging all site means, the resulting A component mean is I_opt=60.3°, I₉₅=5.0° and n=36 (sites). The B magnetic component is observed up to 565 °C, at which temperature, most samples have no measurable remanent magnetization, or growth of magnetic minerals has disrupted the thermal demagnetization process. Combining sites with Fisher estimates of kappa (k-value)≥13 and n (sites)≥3, where bedding orientation differs within a block, most of these sites show the best grouping of B component directions at 100% unfolding, and two of the blocks display remanent magnetizations of both upward and downward directed magnetic inclination. Combining sites with Fisher estimates of kappa (k-value)≥13 and n (sites)≥3, the resulting overall B component paleolatitude and associated uncertainty are λ_obs=30.4°N or S, λ₉₅=8.9° and n=19 (sites). When compared with the expected North America paleolatitude of λ_{APWP expected}=57.9°N, our data support a model in which blocks within the Koryak superterrane are allochthonous and far travelled.     

Paleomagnetism of Khatyrka and Maynitsky superterranes, Koryak highlands, far eastern Russia

We have completed a paleomagnetic reconnaissance study of sedimentary and volcanic extrusive rocks collected from two major tectonic zones in northeastern Russia. Paleomagnetic sites were sampled within the fault-bounded structural units of the Khatyrka and Maynitsky superterranes and an overlap sequence of the Khatyrka superterrane. These sampling localities were chosen to allow both within-site and between-site fold tests. Stepwise thermal demagnetization within the temperature range 200–640°C showed a characteristic linear demagnetization path between thermal demagnetization steps of 400°C and 530°C. For thermal steps above 550°C, the magnetic intensity of many samples began to increase rapidly with magnetic directions, which were random between heating steps, suggesting the formation of new magnetic phases in these samples. Paleomagnetic samples collected from basalts and sediments of the Khatyrka superterrane and basalts and gabbros of the Maynitsky superterrane pass fold tests and show significant poleward motion of these superterranes since the formation of their rocks. The observed paleomagnetic paleolatitudes between 24°N or S and 32°N or S can be compared with expected paleolatitudes of 57°N to 79°N. Paleomagnetic results from sites collected from overlapping Senonian rocks pass a fold test at the 99% confidence level and give a pole position not significantly different from that expected from the apparent polar wander path for the Eurasia or North America plates, suggesting that these sedimentary units overlapping the Khatyrka superterrane were deposited along the ancient northeast margin of the Eurasian plate. The declination, in stratigraphie coordinates, shows a maximum clockwise rotation of about 20° when compared with the Eurasian APWP.     

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.     

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.     

The effect of Ca-Tschermaks component on trace element partitioning between clinopyroxene and silicate melt

We have studied the influence of Ca-Tschermaks (Calcium Tschermaks or CaTs) content of clinopyroxene on the partitioning of trace elements between this phase and silicate melt at fixed temperature and pressure. Ion probe analyses of experiments carried out in the system Na₂O–CaO–MgO–Al₂O₃–SiO₂, at 0.1 MPa and 1218°C, produced crystal-melt partition coefficients (D) of 36 trace elements (Li, Cl, Sc, Ti, V, Cr, Fe, Co, Ge, Sr, Y, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta and W), for clinopyroxene compositions between 10 and 32 mol% CaTs. Partition coefficients for 2+ to 5+ cations show, for each charge, a near parabolic dependence of log D on ionic radius of the substituting cation, for partitioning into both the M1 and M2 sites of clinopyroxene. Fitting the results to the elastic strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal-melt partition coefficients from elastic moduli. Nature 372, 452–454] we obtain results for the strain-free partition coefficients of theoretical cations (D₀), with site radius r₀, and for the site's Young's Modulus (E).

In agreement with earlier data our results show that increasing ^ivAl concentration in cpx is matched by increasing D, E_M1, E_M2 and D₀ for tri-, tetra- and pentavalent cations. The degree of fractionation between chemically similar elements (i.e. Ta/Nb, Zr/Hf) also increases. In contrast, D values for mono-, di- and hexavalent cations decrease with increasing ^ivAl in the cpx. The large suite of trace elements used has allowed us to study the effects of cation charge on D₀, r₀ and E. We have found that D₀ and r₀ decrease with increasing cation charge, e.g. r₀=0.66 Å for 4+ cations and 0.59 Å for 5+ cations substituting into M1. Values of E_M1 and E_M2 increase with cation charge as well as with increasing ^ivAl content. The increase in E_M2 is linear and close to the trend set by Hazen and Finger [Hazen, R.M., Finger, L.W., 1979. Bulk modulus-volume relationship for cation–anion polyhedra. J. Geophys. Res. 84 (10) 6723–6728] for oxides. E_M1 values are much higher and do not fit the trend predicted by the Hazen and Finger relationship.     

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.     

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.     

Solubility of silica polymorphs in electrolyte solutions, I. Activity coefficient of aqueous silica from 25° to 250°C, Pitzer''s parameterisation

Within the framework of Pitzer's specific interaction model, interaction parameters for aqueous silica in concentrated electrolyte solutions have been derived from Marshall and co-authors amorphous silica solubility measurements. The values, at 25°C, of the Pitzer interaction parameter (λ_SiO2(aq)−i) determined in this study are the following: 0.092 (i = Na⁺), 0.032 (K⁺), 0.165 (Li⁺), 0.292 (Ca²⁺, Mg²⁺), −0.139 (SO₄²⁻), and −0.009 (NO₃⁻). A set of polynomial equations has been derived which can be used to calculate λ_SiO2(aq)−i for these ions at any temperature up to 250°C. A linear relationship between the aqueous silica-ion interaction parameters (λ_SiO2(aq)−i) and the surface electrostatic field (Z_i/r_e,i) of ions was obtained. This empirical equation can be used to estimate, in first approximation, λ_SiO2(aq)−i if no measurements are available. From this parameterisation, the calculated activity coefficient of aqueous silica is 2.52 at 25°C and 1.45 at 250°C in 5 m NaCl solution. At lower concentrations, e.g. 2 m NaCl, the activity coefficient of silica is 1.45 at 25°C and 1.2 at 250°C. Hence, in practice, it is necessary to take into account the activity coefficient of aqueous silica (λ_SiO2(aq)≠1) in hydrothermal solutions and basinal brines where the ionic strength exceeds 1. A comparison of measured [Marshall, W.L., Chen, C.-T.A., 1982. Amorphous silica solubilities, V. Prediction of solubility behaviour in aqueous mixed electrolyte solutions to 300°C. Geochim. Cosmochim. Acta 46, 289–291.] and computed amorphous silica solubility, using this parameterisation, shows a good agreement. Because the effect of individual ions on silicate and silica polymorph solubilities are additive, the present study has permitted to derive Pitzer interaction parameters that allow a precise computation of γ_SiO2(aq) in the Na---K---Ca---Mg---Cl---SO₄---HCO₃---SiO₂---H₂O system, over a large range of salt concentrations and up to temperatures of 250°C.     

Petrology of sapphirine granulite and associated sodic gneisses from the Indian Head Range, Newfoundland

Migmatitic granulites from the Indian Head Range (IHR) are dominated by granoblastic, Opx-bearing (quartz) dioritic gneiss with subordinate garnet+orthopyroxene+biotite+albite (±quartz±microcline±cordierite±sillimanite) gneiss and comparatively biotite-rich, sapphirine+cordierite+orthopyroxene+albite (±microcline±sillimanite±corundum) gneiss. The latter contains at least two generations of sapphirine and cordierite, one apparently predating migmatization, the other associated with or following this event. Mineral thermobarometers yield temperatures up to 800 °C at 8 kbar. The IHR granulites have very high δ¹⁸O values (+10.8 to +14.5) which most likely indicate a sedimentary precursor. Their REE and HFSE contents resemble the trace element signature of post-Archean Australian shale (PAAS). Lithological analogues from other Grenvillian inliers in western Newfoundland have similar oxygen isotopic and immobile-element signatures. They too are interpreted as metasedimentary rocks. The IHR rocks, however, have unusually sodic compositions (e.g., Na₂O/CaO and Na₂O/K₂O=2.1–22.5 and 0.93–13.8, respectively) and contain albite or sodic oligoclase despite their high metamorphic grade. The geochemical data indicate that these rocks were albitized prior to high-grade metamorphism. No counterpart of this event is recorded in granulites from the other inliers, indicating that the IHR may be highly allochthonous with respect to these other Grenvillian terranes.     

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.     

D–H evidence for the timing of kaolinization in Northeast Bavaria, Germany

The δD_SMOW values of sedimentary kaolins from the western border of the Bohemian Massif, northeast Bavaria, that did not suffer a deep burial (less than 1000 m) nor a hydrothermal overprint, change systematically from Late Triassic (−50‰) to Mid-Jurassic and Late Cretaceous (−56‰ to −66‰) to Upper Oligocene–Mid-Miocene (−77‰ to −90‰). All analyzed clays are far from hydrogen isotope equilibrium with present-day meteoric waters. Combined oxygen and hydrogen isotope data of selected samples indicate low temperatures of formation (<30°C) and no evidence for preferential D/H exchange with younger waters. The hydrogen isotopic evolution of kaolins is interpreted as reflecting a systematic isotopic change of paleo-meteoric waters in that region. This can be related mainly to the northward drift of stable Europe after the break-up of Gondwana. Increasing continentality, surface uplift and global cooling are additional factors responsible for decreasing δD_SMOW values since the Mid-Cretaceous.

Kaolinite hydrogen isotope ratios of two large residual economic deposits (Tirschenreuth: δD_SMOW=−80‰ to −76‰; Hirschau–Schaittenbach: δD_SMOW=−70‰ to −63‰) can be used in combination with additional geological evidence to constrain the timing of weathering in these areas. A late Early Cretaceous kaolinization age is suggested for the Early Triassic sandstone-hosted deposits near Hirschau–Schnaittenbach, whereas a Late Oligocene to Mid-Miocene age is indicated for the Carboniferous granite-hosted Tirschenreuth deposits.     

Crustal contamination of mafic magmas: evidence from a petrological, geochemical and Sr–Nd–Os–O isotopic study of the Proterozoic Isortoq dike swarm, South Greenland

The mid-Proterozoic Isortoq dike swarm in the Gardar Province, South Greenland, comprises a variety of alkaline rocks ranging from gabbroic to syenitic in composition. Major magmatic mineral phases are olivine, clinopyroxene, Fe–Ti oxides, amphibole, plagioclase and alkali feldspar. Quartz occurs in some samples as a late magmatic phase. Liquidus temperatures of olivine-bearing samples range between 1120 and 1145 °C and solidus temperatures are 850–930 °C. Calculated silica activities are highly variable between 0.53 and unity. Oxygen fugacities vary from −3 to +1 log units relative to the fayalite–magnetite–quartz buffer.

The rocks have MgO contents <6 wt.% with Mg# between 53 and 17. Primitive mantle-normalized trace element patterns show a relative enrichment of LIL elements with Ba peaks and Nb troughs. Clinopyroxenes show a general enrichment in REE relative to chondritic values with variable slightly positive to prominent negative Eu anomalies. Two of the dikes were dated with Sm–Nd three-point isochrons at 1190±44 and 1187±87 Ma, respectively. Initial ⁸⁷Sr/⁸⁶Sr ratios of mafic mineral separates range from 0.70289 to 0.70432 and initial _Nd values vary from +0.3 to −10.7. Whole-rock initial ¹⁸⁷Os/¹⁸⁸Os ratios are highly variable including very radiogenic values of up to 7.967. δ¹⁸O_v-smow values of separated clinopyroxene and amphibole range from +5.2‰ to +6.2‰ and fall within the range of typical mantle-derived rocks, although mixing with a lower crustal component is permitted by the data. Using energy-constrained assimilation-fractional crystallization (EC-AFC) modeling equations, the Sr–Nd isotope data of the more radiogenic samples can successfully be modeled by addition of up to 10% lower crustal granulite-facies Archean gneisses as contaminants. The Os isotopic data also suggest the involvement of old radiogenic crust. In accordance with seismic data, we conclude that a wedge of Archean crust extends from West Greenland further to the south below the present erosion level.     

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.     

Sr–Nd–Pb isotopic compositions of the Kovdor phoscorite–carbonatite complex, Kola Peninsula, NW Russia

The Sr, Nd and Pb isotopic compositions for the Kovdor phoscorite–carbonatite complex (PCC), Kola Peninsula, NW Russia, have been determined to characterize the mantle sources involved and to evaluate the relative contributions of a plume and subcontinental lithospheric mantle in the formation of the complex. The Kovdor PCC is a part of the Kovdor ultramafic–alkaline–carbonatite massif, and consists of six intrusions. The initial isotopic ratios of the analyzed samples, calculated at 380 Ma, display limited variations: ε_Nd, + 2.0 to + 4.7; ⁸⁷Sr/⁸⁶Sr, 0.70319 to 0.70361 (ε_Sr, − 12.2 to − 6.2); ²⁰⁶Pb/²⁰⁴Pb, 18.38 to 18.74; ²⁰⁷Pb/²⁰⁴Pb, 15.45 to 15.50; ²⁰⁸Pb/²⁰⁴Pb, 37.98 to 39.28. The Nd and Sr isotope data of the Kovdor PCC generally fit the patterns of the other phoscorites and carbonatites from the Kola Alkaline Province (KAP), but some data are slightly shifted from the mixing line defined as the Kola Carbonatite Line, having more radiogenic ⁸⁷Sr/⁸⁶Sr ratios. However, the less radiogenic Nd isotopic compositions and negative Δ7/4 values of Pb isotopes of the analyzed samples exclude crustal contamination, but imply the involvement of a metasomatized lithospheric mantle source. Isotopic variations indicate mixing of at least three distinct mantle components: FOZO-like primitive plume component, EMI-like enriched component and DMM-like depleted component. The isotopic nature of the EMI- and DMM-like mantle component observed in the Kovdor samples is considered to be inherited from metasomatized subcontinental lithospheric mantle. This supports the previous models invoking plume–lithosphere interaction to explain the origin of the Devonian alkaline carbonatite magmatism in the KAP.     

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.     

Mineral inclusions and geochemical characteristics of microdiamonds from the DO27, A154, A21, A418, DO18, DD17 and Ranch Lake kimberlites at Lac de Gras, Slave Craton, Canada

A mineral inclusion, carbon isotope, nitrogen content, nitrogen aggregation state and morphological study of 576 microdiamonds from the DO27, A154, A21, A418, DO18, DD17 and Ranch Lake kimberlites at Lac de Gras, Slave Craton, was conducted. Mineral inclusion data show the diamonds are largely eclogitic (64%), followed by peridotitic (25%) and ultradeep (11%). The paragenetic abundances are similar to macrodiamonds from the DO27 kimberlite (Davies, R.M., Griffin, W.L., O'Reilly, S.Y., 1999. Diamonds from the deep: pipe DO27, Slave craton, Canada. In: Gurney, J.J., Gurney, J.L., Pascoe, M.D., Richardson, S.H. (Eds.), The J. B. Dawson Vol., Proc. 7th Internat. Kimberlite Conf., Red Roof Designs, Cape Town, pp. 148–155) but differ to diamonds from nearby kimberlites at Ekati (e.g., Lithos (2004); Tappert, R., Stachel, T., Harris, J.W., Brey, G.P., 2004. Mineral Inclusions in Diamonds from the Panda Kimberlite, S. P., Canada. 8th International Kimberlite Conference, extended abstracts) and Snap Lake to the south (Dokl. Earth Sci. 380 (7) (2001) 806), that are dominated by peridotitic stones.

Eclogitic diamonds with variable inclusion compositions and temperatures of formation (1040–1300 °C) crystallised at variable lithospheric depths sometimes in changing chemical environments. A large range to very ¹³C-depleted C-isotope compositions (δ¹³C=−35.8‰ to −2.2‰) and an NMORB bulk composition, calculated from trace elements in garnet and clinopyroxene inclusions, are consistent with an origin from subducted oceanic crust and sediments. Carbon isotopes in the peridotitic diamonds have mantle compositions (δ¹³C mode −4.0‰). Mineral inclusion compositions are largely harzburgitic. Variable temperatures of formation (garnet T_Ni=800–1300 °C) suggest the peridotitic diamonds originate from the shallow ultra-depleted and deeper less depleted layers of the central Slave lithosphere. Carbon isotopes (δ¹³C av.=−5.1‰) and mineral inclusions in the ultradeep diamonds suggest they formed in peridotitic mantle (670 km). The diamonds may have been entrained in a plume and subcreted to the base of the central Slave lithosphere.

Poorly aggregated nitrogen (IaA without platelets) in a large number of eclogitic (67%) and peridotitic (32%) diamonds, with similar nitrogen contents, indicates the diamonds were stored in the mantle at low temperatures (1060–<1100 °C) following crystallisation in the Archean. Type IaA diamonds have largely cubo-octahedral growth forms, and Type II and Type IaAB diamonds, with higher nitrogen aggregation states, mostly have octahedral morphologies. However, no correlation between these groups and their mineral inclusion compositions, C-isotopes, and N-contents rules out the possibility of unique source origins and suggests eclogitic and peridotitic diamonds experienced variable mantle thermal states. Variation in mineral inclusion chemistries in single diamonds, possible overgrowths of ¹³C-depleted eclogitic diamond on diamonds with peridotitic and ultradeep inclusions, and Type I ultradeep diamond with low N-aggregation is consistent with diamond growth over time in changing chemical environments.     

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 Al–silicate-bearing trondhjemitic migmatites from NE Sardinia, Italy

The migmatites from Punta Sirenella (NE Sardinia) are layered rocks containing 3–5 vol.% of centimeter-sized stromatic leucosomes which are mainly trondhjemitic and only rarely granitic in composition. They underwent three deformation phases, from D₁ to D₃. The D₁ deformation shows a top to the NW shear component followed by a top to the NE/SE component along the XZ plane of the S₂ schistosity. Migmatization started early, during the compressional and crustal thickening stage of Variscan orogeny and was still in progress during the following extensional stage of unroofing and exhumation.

The trondhjemitic leucosomes, mainly consisting of quartz, plagioclase, biotite ± garnet ± kyanite ± fibrolite, retrograde muscovite and rare K-feldspar, are locally bordered by millimeter-sized biotite-rich melanosomes. The rare granitic leucosomes differ from trondhjemitic ones only in the increase in modal content of K-feldspar, up to 25%. Partial melting started in the kyanite field at about 700–720 °C and 0.8–0.9 GPa, and was followed by re-equilibration at 650–670 °C and 0.4–0.6 GPa, producing fibrolite–biotite intergrowth and coarse-grained muscovite.

The leucosomes have higher SiO₂, CaO, Na₂O, Sr and lower Al₂O₃, Fe₂O₃, MgO, TiO₂, K₂O, P₂O₅, Rb, Ba, Cr, V, Zr, Nb, Zn and REE content with respect to proximal hosts and pelitic metagreywackes. Sporadic anomalous high content of calcium and ferromagnesian elements in some leucosomes is due to entrainment of significant amounts of restitic plagioclase, biotite and accessory phases. The rare granitic leucosomes reveal peritectic K-feldspar produced by muscovite-dehydration melting. Most leucosomes show low REE content, moderately fractionated REE patterns and marked positive Eu anomaly. Proximal hosts and pelitic metagraywackes are characterized by higher REE content, more fractionated REE patterns and slightly negative Eu anomaly.

The trondhjemitic leucosomes were generated by H₂O-fluxed melting at 700 °C of a greywacke to pelitic–greywacke metasedimentary source-rock. The disequilibrium melting process is the most reliable melting model for Punta Sirenella leucosomes.     

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.