LA-MC-ICPMS Pb-Pb dating of rutile from slowly cooled granulites: Confirmation of the high closure temperature for Pb diffusion in rutile

Rapid Pb-Pb dating of natural rutile crystals by laser ablation multiple-collector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) is investigated as a tool for constraining geological temperature-time histories. LA-MC-ICPMS was used to analyse Pb isotopes in rutile from granulite-facies rocks from the Reynolds Range, Northern Territory, Australia. The resultant ages were compared with previous U-Pb zircon and monazite age determinations and new mica (muscovite, phlogopite, and biotite) Rb-Sr ages from the same metamorphic terrane. Rutile crystals ranging in size from 3.5 to 0.05 mm with ?20 ppm Pb were ablated with a 300-25 μm diameter laser beam. Crystals larger than 0.5 mm yielded sufficiently precise ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb ratios to correct for the presence of common Pb, and individual rutile crystals often exhibited sufficient Pb isotopic heterogeneity to allow isochron calculations to be performed on replicate analyses of a single crystal. The mean of 12 isochron ages is 1544 ± 8 Ma (2 SD), with isochron ages for single crystals having uncertainties as low as ±1.3 Myr (2 SD). The ²⁰⁷Pb-²⁰⁶Pb ages calculated without correction for common Pb are typically <0.5% higher than the common-Pb-corrected isochron ages reflecting the very minor amounts of common Pb present in the rutile. The LA-MC-ICPMS method described samples only the outer 0.1-0.2 mm of the rutile crystals, resulting in a grain size-independent apparent closure temperature (T_c) for Pb diffusion in rutile that is less than the T_c of monazite ?0.1 mm in diameter, but significantly higher than the Rb-Sr system in muscovite (550 °C), phlogopite (435 °C) and biotite (400 °C). Even small rutile crystals are extremely resistant to isotopic resetting. For the established slow cooling rate of ca. 3 °C/Myr, the T_c for Pb diffusion in the analysed rutile is ca. 630 °C. This is in excellent agreement with recent experimental results that indicate that rutile has a higher T_c than previously thought (ca. 600-640 °C for rutile 0.1-0.2 mm diameter cooled at 3 °C/Myr; near 600 °C [Cherniak D.J., 2000. Pb diffusion in rutile. Contrib. Mineral. Petrol. 139, 198-207], versus 400 °C [Mezger, K., Hanson G.N., Bohlen S.R., 1989a. High precision U-Pb ages of metamorphic rutile: applications to the cooling history of high-grade terranes. Earth Planet. Sci. Lett. 96, 106-118.] for 1 °C/Myr), and with current T_c estimates for monazite and other high temperature geochronometers, which have been revised upwards in recent years. The new rutile ages, together with the other geochronological data from the region, support the interpretation that the Reynolds Range underwent prolonged slow cooling on a conductive geotherm, under nearly steady-state conditions. Slow cooling at ca. 3 °C/Myr persisted for at least 40 Myr followed the peak of high-T/low-P metamorphism to granulite-facies conditions, and probably continued at ca. 2-3 °C/Myr for ca. 200 Myr overall.     

Cr diffusion in orthopyroxene: Experimental determination, Mn-Cr thermochronology, and planetary applications

We have determined Cr diffusion coefficients (D) in orthopyroxene parallel to the a-, b-, and c-axial directions as a function temperature at f(O₂) corresponding to those of the wüstite-iron (WI) buffer. Diffusion is found to be significantly anisotropic with D(//c) > D(//b) > D(//a), conforming to an earlier theoretical prediction. Increase of f(O₂) from WI buffer conditions to 4.5 log unit above the buffer at 950 and 1050 °C leads to decrease of D(Cr) by a factor of two to three, possibly suggesting significant contribution from an interstitial diffusion mechanism. We have used the diffusion data to calculate the closure temperatures (T_c) of the Mn-Cr decay system in orthopyroxene as a function of initial temperature (T₀), grain size (a) and cooling rate for spherical and plane sheet geometries. We also present graphical relations that permit retrieval of cooling rates from knowledge of the resetting of Mn-Cr ages in orthopyroxene during cooling, T₀ and a. Application of these relations to the Mn-Cr age data of the cumulate eucrite Serra de Magé yields a T_c of 830-980 °C, and cooling rates of 2-27 °C/Myr at T_c and ∼1-13 °C/Myr at 500 °C. It is shown that the cooling of Serra de Magé to the closure temperature of the Mn-Cr system took place at its original site in the parent body, and thus implies a thickness for the eucrite crust in the commonly accepted HED parent body, Vesta, of greater than 30 km. This thickness of the eucrite crust is compatible only with a model of relatively olivine-poor bulk mineralogy in which olivine constitutes 19.7% of the total asteroidal mass.     

P–T–t evolution of garnet amphibolites in the Wutai–Hengshan area,North China Craton: insights from phase equilibria and geochronology

Garnet amphibolites can provide valuable insights into geological processes of orogenic belts, but their metamorphic evolution is still poorly constrained. Garnet amphibolites from the Wutai–Hengshan area of the North China Craton mainly consist of garnet, hornblende, plagioclase, quartz, rutile and ilmenite, with or without titanite and epidote. Four samples selected in a south–north profile were studied by the pseudosection approach in order to elucidate the characteristics of their metamorphic evolution, and to better reveal the northwards prograde change in P–T conditions as established previously. For the sample from the lower Wutai Subgroup, garnet exhibits obvious two‐substage growth zoning characteristic of pyrope (X_py) increasing but grossular (X_gr) decreasing outwards in the core, and both X_py and X_gr increasing outwards in the rim. Phase modelling using thermocalc suggests that the garnet cores were formed by chlorite breakdown over 7–9 kbar at 530–600 °C, and rims grew from hornblende and epidote breakdown over 9.5–11.5 kbar at 600–670 °C. The isopleths of the minimum An in plagioclase and maximum X_py in garnet were used to constrain the peak P–T conditions of ~11.5 kbar/670 °C. The modelled peak assemblage garnet + hornblende + epidote+ plagioclase + rutile + quartz matches well the observed one. Plagioclase–hornblende coronae around garnet indicate post‐peak decompression and fluid ingress. For the samples from the south Hengshan Complex, the garnet zoning weaken gradually, reflecting modifications during decompression of the rocks. Using the same approach, the rocks are inferred to have suprasolidus peak conditions, increasing northwards from 11.5 kbar/745 °C, 12.5 kbar/780 °C to 13 kbar/800 °C. Their modelled peak assemblages involve diopside, garnet, hornblende, plagioclase, rutile and quartz, yet diopside is not observed petrographically. The post‐peak decompression is characterized by diopside + garnet + quartz + melt = hornblende + plagioclase, causing the diopside consumption and garnet compositions to be largely modified. Thus, the pesudosection approach is expected to provide better pressure results than conventional thermobarometry, because the later approach cannot be applied with confidence to rocks with multi‐generation assemblages. U–Pb dating of zircon in the Wutai sample records a protolith age of c. 2.50 Ga, and a metamorphic age of c. 1.95 Ga, while zircon in the Hengshan samples records metamorphic ages of c. 1.92 Ga. The c. 1.95 Ga is interpreted to represent the pre‐peak or peak metamorphic stages, and the ages of c. 1.92 Ga are assigned to represent the cooling stages. All rocks in the Wutai–Hengshan area share similar clockwise P–T morphologies. They may represent metamorphic products at different crustal depths in one orogenic event, which included a main thickening stage at c. 1.95 Ga followed by a prolonged uplift and cooling after 1.92 Ga.     

The influence of artificial radiation damage and thermal annealing on helium diffusion kinetics in apatite

Recent work [Shuster D. L., Flowers R. M. and Farley K. A. (2006) The influence of natural radiation damage on helium diffusion kinetics in apatite. Earth Planet. Sci. Lett.249(3-4), 148-161] revealing a correlation between radiogenic ⁴He concentration and He diffusivity in natural apatites suggests that helium migration is retarded by radiation-induced damage to the crystal structure. If so, the He diffusion kinetics of an apatite is an evolving function of time and the effective uranium concentration in a cooling sample, a fact which must be considered when interpreting apatite (U-Th)/He ages. Here we report the results of experiments designed to investigate and quantify this phenomenon by determining He diffusivities in apatites after systematically adding or removing radiation damage.Radiation damage was added to a suite of synthetic and natural apatites by exposure to between 1 and 100 h of neutron irradiation in a nuclear reactor. The samples were then irradiated with a 220 MeV proton beam and the resulting spallogenic ³He used as a diffusant in step-heating diffusion experiments. In every sample, irradiation increased the activation energy (E_a) and the frequency factor (D_o/a²) of diffusion and yielded a higher He closure temperature (T_c) than the starting material. For example, 100 h in the reactor caused the He closure temperature to increase by as much as 36 °C. For a given neutron fluence the magnitude of increase in closure temperature scales negatively with the initial closure temperature. This is consistent with a logarithmic response in which the neutron damage is additive to the initial damage present. In detail, the irradiations introduce correlated increases in E_a and ln(D_o/a²) that lie on the same array as found in natural apatites. This strongly suggests that neutron-induced damage mimics the damage produced by U and Th decay in natural apatites.To investigate the potential consequences of annealing of radiation damage, samples of Durango apatite were heated in vacuum to temperatures up to 550 °C for between 1 and 350 h. After this treatment the samples were step-heated using the remaining natural ⁴He as the diffusant. At temperatures above 290 °C a systematic change in T_c was observed, with values becoming lower with increasing temperature and time. For example, reduction of T_c from the starting value of 71 to ∼52 °C occurred in 1 h at 375 °C or 10 h at 330 °C. The observed variations in T_c are strongly correlated with the fission track length reduction predicted from the initial holding time and temperature. Furthermore, like the neutron irradiated apatites, these samples plot on the same E_a − ln(D_o/a²) array as natural samples, suggesting that damage annealing is simply undoing the consequences of damage accumulation in terms of He diffusivity.Taken together these data provide unequivocal evidence that at these levels, radiation damage acts to retard He diffusion in apatite, and that thermal annealing reverses the process. The data provide support for the previously described radiation damage trapping kinetic model of Shuster et al. (2006) and can be used to define a model which fully accommodates damage production and annealing.     

Mapping lithospheric boundaries using Os isotopes of mantle xenoliths: An example from the North China Craton

The petrology, mineral compositions, whole rock major/trace element concentrations, including highly siderophile elements, and Re-Os isotopes of 99 peridotite xenoliths from the central North China Craton were determined in order to constrain the structure and evolution of the deep lithosphere. Samples from seven Early Cretaceous-Tertiary volcanic centers display distinct geochemical characteristics from north to south. Peridotites from the northern section are generally more fertile (e.g., Al₂O₃ = 0.9-4.0%) than those from the south (e.g., Al₂O₃ = 0.2-2.2%), and have maximum whole-rock Re-depletion Os model ages (T_RD) of ∼1.8 Ga suggesting their coeval formation in the latest Paleoproterozoic. By contrast, peridotites from the south have maximum T_RD model ages that span the Archean-Proterozoic boundary (2.1-2.5 Ga). Peridotites with model ages from both groups are found at Fansi, the southernmost locality in the northern group, which likely marks a lithospheric boundary. The Neoarchean age of the lithospheric mantle in the southern section matches that of the overlying crust and likely reflects the time of amalgamation of the North China Craton via collision between the Eastern and Western blocks. The Late Paleoproterozoic (∼1.8 Ga) lithospheric mantle beneath the northern section is significantly younger than the overlying Archean crust, indicating that the original lithospheric mantle was replaced in this region, either during a major north-south continent-continent collision that occurred during assembly of the Columbia supercontinent at ∼1.8-1.9 Ga, or from extrusion of ∼1.9 Ga lithosphere from the Khondalite Belt beneath the northern Trans-North China Orogen, during the ∼1.85 Ga continental collision between Eastern and Western blocks. Post-Cretaceous heating of the southern section is indicated by high temperatures (>1000 °C) recorded in peridotites from the 4 Ma Hebi suite, which are significantly higher than the temperatures recorded in peridotites from the nearby Early Cretaceous Fushan suite (<720 °C), and likely reflects significant lithospheric thinning after the Early Cretaceous. Combining previous Os isotope results on mantle xenoliths from the eastern North China Craton with our new data, it appears that lithospheric thinning and replacement may have evolved from east to west with time, commencing before the Triassic on the eastern edge of the craton, occurring during the Jurassic-Cretaceous within the interior, and post-dating 125 Ma on the westernmost boundary.     

Origin of the Alxa Block,western China: New evidence from zircon U–Pb geochronology and Hf isotopes of the Longshoushan Complex

The NW–SE trending Longshoushan is in the southwestern margin of the Alxa Block, which was traditionally considered the westernmost part of the North China Craton (NCC). Precambrian crystalline basement exposed in the Longshoushan area was termed the “Longshoushan Complex”. This complex's formation and metamorphism are significant to understand the geotectonics and early Precambrian crustal evolution of the western NCC. In this study, field geology, petrology, and zircon U–Pb and Lu–Hf isotopes of representative orthogneisses and paragneisses in the Longshoushan Complex were investigated. U–Pb datings reveal three Paleoproterozoic magmatic episodes (ca. 2.33, ca. 2.17 and ca. 2.04 Ga) and two subsequent regional metamorphic events (ca. 1.95–1.90 Ga and ca. 1.85 Ga) for metamorphic granitic rocks in the Longshoushan Complex. U–Pb dating of the detrital magmatic zircons from two paragneisses yields concordant ²⁰⁷Pb/²⁰⁶Pb ages between 2.2 Ga and 2.0 Ga, and a small number of metamorphic zircon rims provide a ca. 1.95 Ga metamorphic age, suggesting that the depositional time of the protolith was between 2.0 and 1.95 Ga and that the sedimentary detritus was most likely derived from the granitic rocks in the Longshoushan Complex itself. Zircon Lu–Hf isotopic analyses indicate that nearly all magmatic zircons from ca. 2.0 Ga to ca. 2.17 Ga orthogneisses have positive εHf(t) values with two-stage Hf model ages (T_DMC) ranging from 2.45 to 2.65 Ga (peak at ca. 2.5 Ga), indicating that these Paleoproterozoic granitic rocks were derived from the reworking of the latest Neoarchean–early Paleoproterozoic juvenile crust. Detrital magmatic zircons from two paragneisses yield scattered ¹⁷⁶Hf/¹⁷⁷Hf ratios, εHf(t) and T_DMC values, further indicating that the sedimentary detritus was not only derived from these plutonic rocks but also from other unreported or denuded Paleoproterozoic igneous rocks. The ca. 2.15 Ga detrital magmatic zircons from one paragneiss have negative εHf(t) values with T_DMC ranging from 2.76 to 3.04 Ga, indicating another important crustal growth period in the Longshoushan region. These data indicate that the Longshoushan Complex experienced Neoarchean–Early Paleoproterozoic crustal growth, approximately ca. 2.3–2.0 Ga experienced multiphase magmatic events, and approximately ca. 1.95–1.90 Ga and ca. 1.85 Ga experienced high-grade metamorphic events. The sequence of tectonothermal events is notably similar to that of the main NCC. Together with the datasets from an adjacent area, we suggest that the western Alxa Block was most likely an integrated component of the NCC from the Neoarchean to the Paleoproterozoic.     

Comparison between grain size and multi-mineral Ar/Ar thermochronology

In the case of volume diffusion, the closure temperature of a mineral is function of, among other factors, the characteristic diffusion dimension, which can be approximated by the grain size of the mineral analysed for grains smaller than or similar in size to the diffusion domains. The theoretical possibility of single mineral grain size thermochronology had been demonstrated empirically in earlier studies, mostly using biotite. In order to examine the potential of this method, it was tested alongside the widely used multi-mineral ⁴⁰Ar/³⁹Ar thermochronology. The sample comes from the granitic McLean pluton, in the south section of the Grenville orogeny. Seven grain size separates of biotite (ranging between 90 and 1000 μm), eight size fractions of amphibole (between 63 and 1000 μm), and three size fractions of K-feldspar (250-600 μm) were extracted and dated by the laser step-heating ⁴⁰Ar/³⁹Ar method. The total gas ages obtained behave as theoretically predicted, with increasing ages for increasing grain sizes, including for K-feldspar, but with the exception of the smallest and the largest grains for biotite and amphibole. The calculated cooling rates are ca. 0.7 °C/Ma for K-feldspar, ca. 2.5 °C/Ma for biotite, and ca. 11 °C/Ma for amphibole, corresponding very well to a monotonic cooling of the McLean pluton. A quick initial thermal re-equilibration with the cooler host-rocks is followed by a much slower cooling on a thermal path parallel to that of the Frontenac Terrain situated immediately to the southeast. The validity of the single mineral grain size thermochronology is demonstrated by comparison with the thermal evolution of the adjacent units and with the cooling history derived from a multi-mineral thermochronology, suggesting that it can be routinely used. The application of this method can be hampered by insufficiently low analytical uncertainties.     

Cooling rates of basaltic hyaloclastites and pillow lava glasses from the HSDP2 drill core

Cooling rates have been determined for basaltic glasses from different depths of the submarine section of the drill core recovered in the 1999 phase of Hawaii Scientific Drilling Project (HSDP2). The glasses include degassed blocky hyaloclastite clasts and undegassed pillow rims. The degassed glassy clasts were generated in subaerial or shallow submarine environments, during explosive interactions between lava and seawater, before eventual deposition under water. The volatile contents of the glassy pillow rims are consistent with eruption and quenching in water several hundred metres deep. The cooling rates have been calculated from the calorimetric properties of the glass across the glass transition. The heat capacity (c_p) of each sample was measured during several cycles of heating from room temperature to temperatures above their glass transition using a differential scanning calorimeter (DSC). Their compositions did not change during the thermal treatment, a prerequisite for successful c_p measurements, although the glasses with higher H₂O contents became more opaque and their mid-IR spectra changed. Each c_p-T path exhibits the now classic features of the glass transition; glassy and liquid states separated by a hysteresis marking the transition. After experiencing the same experimental thermal history the glass transition occurs at lower temperatures in glasses with higher H₂O contents. Except for one sample, the c_p-T path measured on initial heating also releases energy stored during the natural quench, which is not recovered during subsequent experimental cooling. The energy stored in the HSDP2 glasses is much less than that observed in hyperquenched natural and synthetic glasses. Even so, the Tool-Narayanaswamy enthalpy relaxation geospeedometer, usually used to determine the cooling rates in volcanic glasses, is unable to deal with this energy release. For those samples that exhibit this feature an alternative method, developed for hyperquenched glasses, is applied. This uses the energy released to calculate T_f, from which the cooling rate is calculated. The degassed blocky hyaloclastite clasts exhibit cooling rates 0.1-72.2 K s⁻¹, while the undegassed pillow rims span 0.2-46.4 K s⁻¹. The fastest cooling rates are consistent with the cooling of lava bodies in seawater. The wide variation for both types of glass could reflect quenching at different distances from the basalt-seawater interface. However, for the degassed hyaloclastite clasts the range could indicate that the clasts were generated by different processes operating during the explosive interaction between lava and seawater in the littoral zone. In the undegassed pillow lavas, glassy rims may have been reheated, giving rise to more complex, slower, thermal histories, as a result of latent heat released during the crystallisation of pillow interiors, or flow replenishment. Both types of glass may also have experienced reheating from succeeding flows or deposits. Compared to deep-sea limu o Pele hyaloclastite fragments, whose hyperquench rates indicate simultaneous cooling and fragmentation, the shallow blocky hyaloclastite clasts may have formed during post-cooling brittle fragmentation.     

Diffusion of Ar in muscovite

Hydrothermal treatment of closely sized muscovite aggregates in a piston-cylinder apparatus induced ⁴⁰Ar^∗ loss that is revealed in ⁴⁰Ar/³⁹Ar step heating spectra. Age spectra and Arrhenius data, however, differ from that expected from a single diffusion length scale. A numerical model of episodic loss assuming the presence of multiple diffusion domains yields excellent fits between synthetic and actual degassing spectra. We used this model to isolate ⁴⁰Ar^∗ loss from the grains that remained intact during hydrothermal treatment at 10 kbar permitting calculation of diffusion coefficients in the temperature range 730-600 °C. Diffusion data generated in this manner yield an activation energy (E) of 63 ± 7 kcal/mol and frequency factor (D_o) of 2.3  cm²/s. Experiments at 20 kbar yield diffusivities lower by about an order of magnitude and correspond to an activation volume of ∼14 cm³/mol. Together, these parameters predict substantially greater retentivity of Ar in muscovite than previously assumed and correspond to a closure temperature (T_c) of 425 °C for a 100 μm radius grain cooling at 10 °C/Ma at 10 kbar (T_c = 405 °C at 5 kbar. Age and log (r/r_o) spectra for the run products show strong correlations indicating that muscovites can retain Ar diffusion boundaries and mechanisms that define their natural retentivity during vacuum step heating. This may permit the application of high resolution, continuous ⁴⁰Ar/³⁹Ar thermochronology to low grade, regionally metamorphosed terranes.     

Crustal response to continental collisions between the Tibet, Indian, South China and North China Blocks: geochronological constraints from the Songpan-Garzê Orogenic Belt, western China

We report SHRIMP U–Th–Pb monazite, conventional U–Pb titanite, Sm–Nd garnet and Rb–Sr muscovite and biotite ages for metamorphic rocks from the Danba Domal Metamorphic Terrane in the eastern Songpan‐Garzê Orogenic Belt (eastern Tibet Plateau). These ages are used to determine the timing of polyphase metamorphic events and the subsequent cooling history. The oldest U–Th–Pb monazite and Sm–Nd garnet ages constrain an early Barrovian metamorphism (M1) in the interval c. 204–190 Ma, coincident with extensive Indosinian granitic magmatism throughout the Songpan‐Garzê Orogenic Belt. A second, higher‐grade sillimanite‐grade metamorphic event (M2), recorded only in the northern part of the Danba terrane, was dated at c. 168–158 Ma by a combination of U–Th–Pb monazite and titanite and Sm–Nd garnet ages. It is suggested that M1 was a thermal event that affected the entire orogenic belt while M2 may represent a local thermal perturbation. Rb–Sr muscovite ages range from c. 138–100 Ma, whereas Rb–Sr biotite ages cluster at c. 34–24 Ma. These ages document regional cooling at rates of c. 2–3 °C Myr^?1 following the M1 peak for most of the terrane. However, those parts of the terrane affected by the higher‐temperature M2 event (e.g. the migmatite zone) experienced initially more rapid (c. 8 °C Myr^?1) cooling after peak M2 before joining the regional slow cooling path defined by the rest of the terrane at c. 138 Ma. Regional slow cooling between c. 138 and c. 30 Ma is thought to be the result of post‐tectonic isostatic uplift after extensive crustal thickening caused by collision of the South and North China Blocks. The clustering of biotite Rb–Sr ages marks the onset of rapid uplift across the entire terrane commencing at c. 30–20 Ma. This cooling history is shared with many other regions of the Tibet Plateau, suggesting that uplift of the Tibet Plateau (including the Songpan‐Garzê Orogenic Belt) occurred predominantly in the last c. 30 Myr as a response to the continuing northwards collision of India with Eurasia.     

A review of the pressure–temperature–time evolution of the Limpopo Belt: Constraints for a tectonic model

Published literature argues that the Limpopo Belt can be subdivided into three zones, each with a distinctive geological character and tectono-metamorphic fingerprint. There are currently two contrasting schools of thought regarding the tectono-metamorphic evolution of the CZ. One camp argues that geochronological, structural and prograde pressure–temperature (P–T) evidence collectively indicate that the CZ underwent tectono-metamorphism at ca. 2.0 Ga which followed a clockwise P–T evolution during a transpressive orogeny that was initiated by the collision of the Kaapvaal and Zimbabwe cratons. Deformation and metamorphism consistent with this scenario are observed in the southern part of the NMZ but are curiously absent from the whole of the SMZ. The opposing view argues that the peak metamorphism associated with the collision of the Kaapvaal and Zimbabwe cratons occurred at ca. 2.6 Ga and the later metamorphic event is an overprint associated with reactivation along Archean shear zones. Post-peak-metamorphic conditions, which at present cannot be convincingly related to either a ca. 2.6 or 2.0 Ga event in the CZ reveal contrasting retrograde paths implying either near-isothermal decompression and isobaric cooling associated with a ‘pop-up’ style of exhumation or steady decompression–cooling linked to exhumation controlled by erosion. Recent data argue that the prograde evolution of the ca. 2.0 Ga event is characterised by isobaric heating prior to decompression–cooling. Contrasting P–T paths indicate that either different units exist within the CZ that underwent different P–T evolutions or that some P–T work is erroneous due to the application of equilibrium thermobarometry to mineral assemblages that are not in equilibrium. The morphology of the P–T path(s) for the ca. 2.6–2.52 Ga event are also a matter of dispute. Some workers have postulated an anticlockwise P–T evolution during this period whilst others regard this metamorphic event as following a clockwise evolution. Granitoid magmatism is broadly contemporaneous in all three zones at ca. 2.7–2.5 suggesting a possible causal geodynamic link. P–T contrasts between and within the respective zones prevent, at present, the construction of a coherent and inter-related tectonic model that can account for all of the available evidence. Detailed and fully-integrated petrological and geochronological studies are required to produce reliable P–T–t paths that may resolve some of these pertinent issues.     

Ancient graphite in the Eoarchean quartz-pyroxene rocks from Akilia in southern West Greenland I: Petrographic and spectroscopic characterization

Because all known Eoarchean (>3.65 Ga) volcano-sedimentary terranes are locked in granitoid gneiss complexes that have experienced high degrees of metamorphism and deformation, the origin and mode of preservation of carbonaceous material in the oldest metasedimentary rocks remain a subject of vigorous debate. To determine the biogenicity of carbon in graphite in such rocks, carbonaceous material must be demonstrably indigenous and its composition should be consistent with thermally altered biogenic carbon as well as inconsistent with abiogenic carbon. Here we report the petrological and spectroscopic characteristics of carbonaceous material, typically associated with individual apatite grains, but also with various other minerals including calcite, in a >3.83 Ga granulite-facies ferruginous quartz-pyroxene unit (Qp rock) from the island of Akilia in southern West Greenland. In thin sections of the fine-grained parts of Akilia Qp rock sample G91-26, mapped apatites were found to be associated with graphite in about 20% of the occurrences. Raman spectra of this carbonaceous material had strong G-band and small D-band absorptions indicative of crystalline graphite. Three apatite-associated graphites were found to contain curled graphite structures, identified by an anomalously intense second-order D-band (or 2D-band) Raman mode. These structures are similar to graphite whiskers or cones documented to form at high temperatures. Raman spectra of apatite-associated graphite were consistent with formation at temperatures calculated to be between 635 and 830 °C, which are consistent with granulite-facies metamorphic conditions. Three graphite targets extracted by focused ion beam (FIB) methods contained thin graphite coatings on apatite grains rather than inclusions sensu stricto as inferred from transmitted light microscopy and Raman spectroscopy. TEM analyses of graphite in these FIB sections showed a (0 0 0 2) interplanar spacing between 3.41 and 3.64 Å for apatite-associated graphite, which is larger than the spacing of pure graphite (3.35 Å) and may be caused by the presence of non-carbon heteroatoms in interlayer sites. Samples analyzed by synchrotron-based scanning transmission X-ray microscopy (STXM) also confirmed the presence of crystalline graphite, but abundances of N and O heteroatoms were below detection limit for this method. Graphite in the Akilia Qp rock was also found to occur in complex polyphase mineral assemblages of hornblende ± calcite ± sulfides ± magnetite that point to high-temperature precipitation from carbon-bearing fluids. These complex mineral assemblages may represent another generation of graphitization that could have occurred during the amphibolite-facies metamorphic event at 2.7 Ga. Several observations point to graphitization from high-temperature fluid-deposition for some of the Akilia graphite and our results do not exclude a biogenic source of carbon in graphite associated with apatite, but ambiguities remain for the origin of this carbon.     

U–Pb systematics of the McClure Mountain syenite: thermochronological constraints on the age of the 40Ar/39Ar standard MMhb

Recent advances in U–Pb geochronology allow unprecedented levels of precision in the determination of geological ages. However, increased precision has also illuminated the importance of understanding subtle sources of open-system behavior such as Pb-loss, inheritance, intermediate daughter product disequilibria, and the accuracy of the model assumptions for initial Pb. Deconvolution of these effects allows a much richer understanding of the power and limitations of U–Pb geochronology and thermochronology. In this study, we report high-precision ID-TIMS U–Pb data from zircon, baddelleyite, titanite and apatite from the McClure Mountain syenite, from which the ⁴⁰Ar/³⁹Ar hornblende standard MMhb is derived. We find that excess ²⁰⁶Pb in zircon due to inclusions of high-Th minerals and elevated Th/U in titanite and apatite jeopardize the utility of the ²³⁸U–²⁰⁶Pb system in this rock. Strongly air-abraded zircons give dates that are younger than chemical-abraded zircons, which yield a statistically robust ²⁰⁷Pb/²³⁵U date of 523.98±0.12 Ma that is interpreted as the crystallization age. We explore the best method of Pb_c correction in titanite and apatite by analyzing the U–Pb isotopes of K-feldspar and using 2-D and 3-D regression methods—the latter of which yields the best results in each case. However, the calculated compositions of Pb_c for titanite, apatite and K-feldspar are different, implying that using a single Pb_c correction for multiple U–Pb thermochronometers may be inaccurate. The U–Pb thermochronological results are used to predict a closure time for Ar in hornblende of 522.98±1.00 Ma. Widely cited K–Ar and ⁴⁰Ar/³⁹Ar dates overlap with the U–Pb date, and relatively large errors make it impossible to verify whether U–Pb dates are systematically ≤1% older than K–Ar and ⁴⁰Ar/³⁹Ar dates.     

Destruction of ancient lower crust through magma underplating beneath Jiaodong Peninsula, North China Craton: U-Pb and Hf isotopic evidence from granulite xenoliths

Zircons from granulite xenoliths entrained in a Late Cretaceous mafic dike in the Jiaodong Peninsula, North China Craton (NCC), show three distinct U-Pb age populations. Part of the old zircon grains yield discordant data that project to ages of about 2.4 to 2.5 Ga, a few grains indicate growth at about 2.0 Ga and a third group yield Cretaceous ages with peaks at 120 and 90 Ma. The oldest zircons give Hf T_DM model ages of 2.6-2.8 Ga. These results demonstrate the existence of original Archean lower crust in the Jiaodong region. Zircons of 2.0 Ga have similar Hf T_DM model ages as the Neoarchean-Paleoproterozoic grains, suggesting that these zircons were products of metamorphic recrystallization due to thermal event without juvenile input. Early Cretaceous zircons yield εHf(t) values of − 21 to − 12 and Late Cretaceous zircons large variable εHf(t) from + 4 to − 50. These data suggest that magmatic underplating occurred in the Neoarchean to Earliest Proterozoic lower crust of the NCC, both in the Early and Late Cretaceous. It is suggested that the Mesozoic magma underplating, which also provided the heat source for the voluminous Mesozoic magmatism in the NCC, significantly modified the composition of the Archean to Paleoproterozoic lower crust of the NCC.     

Paleoproterozoic gabbronoritic and granitic magmatism in the northern margin of the North China craton: Evidence of crust–mantle interaction

Paleoproterozoic Xuwujia gabbronorites in the northern margin of the North China craton occur as dykes, sills and small plutons intruded into khondalite (aluminous paragneisses, sedimentary protoliths deposited at ca. 2.0–1.95 Ga), and as numerous entrained bodies and fragments of variable scales in the Liangcheng granitoids (ca. 1.93–1.89 Ga). These gabbronoritic dykes are present at all locations where ca. 1.93–1.92 Ga ultra-high-temperature metamorphism is recorded in the khondalite. A gabbronorite sample from the Hongmiaozi dyke gives zircon ²⁰⁷Pb/²⁰⁶Pb mean ages of 1954 ± 6 Ma (core domains) and 1925 ± 8 Ma (rim domains). These ages, as well as previously reported ages, constrain the age of mafic magmatism to be at ca. 1.96–1.92 Ga (∼1.93 Ga). One sample from the Xigou gabbro intruded by the Liangcheng granitoids gives a zircon ²⁰⁷Pb/²⁰⁶Pb mean age of 1857 ± 4 Ma, which is interpreted as the age of a metamorphic overprint. The Xuwujia gabbronorites comprise mainly gabbronorite compositions, as well as some norite, olivine gabbronorite, monzonorite, quartz gabbronorite, and quartz monzonorite. Chemically, they are tholeiitic and can be divided into two groups: a high-Mg group (6.2–22.9 wt.% MgO) and a relatively low-Mg group (2.2–5.7 wt.% MgO). The high-Mg group shows negative Eu-anomalies (Eu/Eu* = 0.53–0.72), slight light rare earth element enrichment (La/Yb_N = 0.56–1.53), and small negative anomalies in high field-strength elements. The ?Nd (t = 1.93 Ga) values vary from +0.3 to +2.4. The low-Mg group shows varied Eu-anomalies (Eu/Eu* = 0.48–1.05), and is enriched in light rare earth elements (La/Yb_N = 1.51–11.98). The majority shows negative anomalies in high field-strength elements (e.g., Th, Nb, Zr, and Ti). Initial ?Nd (at 1.93 Ga) values for low-Mg gabbronorites vary from −5.0 to 0. The Xuwujia gabbronorites possibly experienced assimilation of crust, and fractional crystallization of initially olivine and hypersthene (the high-Mg group), and then olivine, clinopyroxene, and plagioclase (the low-Mg group). The slightly younger Liangcheng granitoids consist of garnet-bearing granite, granodiorite and quartz-rich granitic compositions. They are intermediate to felsic calc-alkaline rocks, thought to be derived from surrounding metasedimentary crust. Xigou gabbro could represent early cumulates. The granitoids have relatively high-Mg numbers (up to 54), and show some chemical affinities with the gabbronorites, which could have resulted from incorporation of gabbronoritic melts. The occurrence and chemical variations of the Xuwujia gabbronorites and Liangcheng granitoids can be interpreted to have resulted from crust–mantle interaction, with mingling and partial mixing of mantle (gabbronoritic) and crustal (granitic) melts. The Xuwujia gabbronorites originated from a mantle region with high potential temperatures (∼1550 °C), possibly associated with a plume or more likely a ridge-subduction-related mantle upwelling event. They could have had extremely high primary intrusion temperatures (up to 1400 °C). Emplacement of these magmas was likely responsible for the extensive crustal anatexis (Liangcheng granitoids) and the local ultra-high-temperature metamorphism. These sequences may have followed ca. 1.95 Ga continent–continent (arc?) juxtaposition and were themselves followed by significant regional uplift and exhumation in the northern margin of the North China craton.     

Growth rate of the preserved continental crust: II. Constraints from Hf and O isotopes in detrital zircons from Greater Russian Rivers

Detrital zircons from the Ob, Yenisey, Lena, Amur, Volga, Dnieper, Don and Pechora rivers have been analyzed for U-Th-Pb, O and Lu-Hf isotopes to constrain the growth rate of the preserved continental crust in Greater Russia. Four major periods of zircon crystallization, 0.1-0.55, 0.95-1.3, 1.45-2.0 and 2.5-2.9 Ga, were resolved from a compilation of 1366 zircon U/Pb ages. The Archean zircons have δ¹⁸O values lying between 4.53‰ and 7.33‰, whereas Proterozoic and Phanerozoic zircons have a larger range of δ¹⁸O values in each of the recognized U/Pb time intervals with maximum δ¹⁸O values up to 12‰. We interpret the zircons with δ¹⁸O between 4.5‰ and 6.5‰ to have been derived from a magmatic precursor that contains little or no sedimentary component. The variable δ¹⁸O values of the zircons were used to constrain the ¹⁷⁶Lu/¹⁷⁷Hf ratios of the crustal source region of the zircons, which, in turn, were used to calculate Hf model ages (T_DM^V). The crustal incubation time, the time difference between primitive crust formation (dated by T_DM^V) and crustal melting (dated by zircon U/Pb age), varies between 300 to 1000 Myr for the majority of analyzed zircon grains, but can be up to 2500 Myr. The average T_DM^V Hf model age weighted by the fraction of zircons in the river load is 2.12 Ga, which is in reasonable agreement with the area-weighted average of 2.25 Ga. The T_DM^V Hf model age crustal growth curve for zircons with mantle-like δ¹⁸O values (4.5-6.5‰), weighted by area, shows that growth of the Great Russian continental crust started at 4.2 Ga, and that there are two principal periods of crustal growth, 3.6-3.3 Ga and 0.8-0.6 Ga, which are separated by an interval of low but more or less continuous growth. An alternative interpretation, in which the average ¹⁷⁶Lu/¹⁷⁷Hf ratio (0.0115) of the continental crust is used for the Paleoproterozoic zircons from the Lena River, lowers the average T_DM^V age of these grains by about 500 Myr and delays the onset of significant crustal growth to 3.5 Ga.The two principal growth periods recognized in Greater Russia differ from those identified from the Gondwana and the Mississippi river basin, which show peaks at 1.7-1.9 and 2.9-3.1 Ga (Hawkesworth and Kemp, 2006a) and 1.6-2.2 and 2.9-3.4 Ga (Wang et al., 2009), respectively. The older 3.6-3.3 Ga or 3.5-3.3 Ga peak for Greater Russia is slightly older than the older Gondwana-Mississippi peaks, whereas the younger 0.8-0.6 Ga peak is distinctly younger than the youngest peak in either Gondwana or the Mississippi river basin. This suggests that the two major peaks of crustal growth identified in Gondwana and the Mississippi river basin may not be global periods of enhanced continental growth and that the major periods of crustal growth may differ from continent to continent.     

Tracing Nile sediment sources by Sr and Nd isotope signatures (Uganda, Ethiopia, Sudan)

Strontium and neodymium isotopes, measured on diverse mud and sand fractions of sediment in transit along all major Nile branches, identify detritus sourced from Precambrian basements, Mesozoic strata, and Tertiary volcanic rocks exposed along the shoulders of the East African rift and in Ethiopian highlands. Sr and Nd isotopic ratios reflect the weighted average of detrital components generated in different catchments, allowing us to discriminate provenance, calculate sediment budgets, and investigate grain-size and hydraulic-sorting effects.⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd range, respectively, from as high as 0.722 and as low as 0.5108 for sediment derived from Archean gneisses in northern Uganda, to 0.705 and 0.5127 for sediment derived from Neoproterozoic Ethiopian and Eritrean basements. ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd, ranging 0.705-0.709 and 0.5124-0.5130 for Blue Nile tributaries, are 0.704-0.705 and 0.5127-0.5128 for largely volcaniclastic sediments of River Tekeze-Atbara, and 0.705-0.706 and 0.5126-0.5127 for main Nile sediments upstream Lake Nasser.Model mantle derivation ages (t_DM), oldest in Uganda where sediment is principally derived from the Congo Craton (3.4-3.0 Ga for Victoria and Albert Nile), progressively decrease northward across the Saharan Metacraton, from 2.6 Ga (Bahr el Jebel in South Sudan), to 2.4-2.2 Ga (Bahr ez Zeraf across the Sudd), and finally 1.6-1.3 Ga (White Nile upstream Khartoum). Instead, t_DM ages of Sobat mud increase from 0.9 to 1.5 Ga across the Machar marshes. T_DM ages are younger for sediments shed by Ethiopian (1.2-0.7 Ga) and Eritrean basements (1.5-1.2 Ga), and youngest for sediments shed from Ethiopian flood basalts (0.3-0.2 Ga).Integrated geochemical, mineralogical, and settling-equivalence analyses suggest influence on the Nd isotopic signal by volcanic lithic grains and titanite rather than by LREE-rich monazite or allanite. Because contributions by ultradense minerals is subordinate, intrasample variability of Sr and Nd ratios is minor. In Blue Nile, Atbara and main Nile sediments of mixed provenance, however, the Nd ratio tends to be higher and t_DM ages lower in largely volcaniclastic mud than in mixed volcaniclastic/metamorphiclastic sand.The complete geochemical database presented here, coupled with high-resolution bulk-petrography and heavy-mineral data, provides a key to reconstructing erosion patterns and detrital fluxes across the whole Nile basin, and to investigate and understand how sources of sediment have changed in the historical and pre-historical past in relation to shifting climatic zones across arid northern Africa.     

The thermal history of equilibrated ordinary chondrites and the relationship between textural maturity and temperature

The compositions and textures of phases in eleven equilibrated ordinary chondrites from the H, L, and LL groups spanning petrographic types 4-6 were studied and used to constrain the thermal histories of their parent bodies. Based on Fe-Mg exchange between olivine and spinel, average equilibration temperatures for type 4-6 chondrites encompass a small range, 586-777 °C, relative to what is commonly assumed for peak temperatures (600-950 °C). The maximum temperatures recorded by individual chondrites, which are minima relative to peak metamorphic temperatures, increase subtly but systematically with metamorphic type and are tightly clustered for H4-6 (733-754 °C) and LL4-6 (670-777 °C). For the Ls, Ausson (L5) records a higher maximum olivine-spinel temperature (761 °C) than does the L4 chondrite Saratov (673 °C) or the L6 chondrite Glatton (712 °C). Our data combined with olivine-spinel equilibration temperatures calculated for other equilibrated ordinary chondrites using mineral compositions from the literature demonstrate that, in general, type 4 chondrites within each chemical group record temperatures lower than or equal to those of types 5-6 chondrites.For H chondrites, the olivine-spinel closure temperature is a function of spinel grain size, such that larger grains, abundant in types 5-6 chondrites, record temperatures of ∼740 °C or more while smaller grains, rare in types 5-6 but abundant in type 4 chondrites, record lower temperatures. Olivine-spinel temperatures in the type 6 chondrites Guareña and Glatton are consistent with rapid (50-100 °C/Myr) cooling from high temperatures in the ordinary chondrite parent bodies. With one exception (∼500 °C/Myr), olivine-spinel data for St.-Séverin (LL6) are consistent with similar cooling rates. Cooling rates of order 100 °C/Myr at ∼750 °C for type 6 chondrites are considerably higher than previously determined cooling rates for lower temperatures (?550 °C) based on metallography, fission tracks, and geochronology. For H chondrites, current thermal models of an “onion shell” parent body are inconsistent with a small range of peak temperatures based on olivine-spinel and two pyroxene thermometry combined with a wide dispersion of cooling rates at low temperatures. Equilibrated chondrites may have sampled regions near a major transition in physical properties such as near the base of a regolith pile.     

P–T evolution and tectonic significance of lawsonite-bearing schists from the eastern segment of the southwestern Tianshan,China

Robust quantification of pressure (P)–temperature (T) paths for subduction-related HP/UHP metamorphic rocks is fundamental in recognizing spatial changes in both the depth of detachment from the down-going plate and the thermal evolution of convergent margin sutures in orogenic belts. Although the Chinese southwestern (SW) Tianshan is a well-known example of an accretionary metamorphic belt in which HP/UHP metabasites occur in voluminous host metasedimentary schists, information about the P–T evolution of these rocks in the eastern segment is limited, precluding a full understanding of the development of the belt as a whole. In this study at Kekesu in the eastern segment of the SW Tianshan, we use microstructural evidence and phase equilibrium modelling to quantify the peak and retrograde P–T conditions from two lawsonite-bearing micaschists and an enclosed garnet–epidote blueschist; for two of the samples we also constrain the late prograde P–T path. In the two micaschist samples, relics of prograde lawsonite are preserved in quartz inclusions in garnet, whereas in the metabasite, polymineralic aggregates included in garnet are interpreted as pseudomorphs after lawsonite. For garnet micaschist TK21, which is mainly composed of garnet, phengite/paragonite, albite, chlorite, quartz and relict lawsonite, with accessary rutile, titanite and ilmenite, the maximum P–T conditions for the peak stage are 18.0–19.0 kbar at 480–485°C. During initial exhumation, the retrograde P–T path passed through metamorphic conditions of 15.0–17.0 kbar at 460–500°C. For garnet–glaucophane micaschist TK33, which is mainly composed of garnet, glaucophane, phengite/paragonite, albite, chlorite, quartz, relict lawsonite and minor epidote, with accessary titanite, apatite, ilmenite and zircon, the maximum P conditions for the peak stage are >24.0 kbar at 400–500°C. During exhumation, the P–T path passed through metamorphic conditions of 17.5–18.5 kbar at 485–495°C and 14.0–17.5 kbar at 460–500°C. For garnet–epidote blueschist TK37, which is mainly composed of garnet, glaucophane, epidote, phengite, chlorite, albite and quartz, with accessary titanite, apatite, ilmenite, zircon and calcite, the prograde evolution passed through metamorphic conditions of ~20.0 kbar at ~445°C to P_max conditions of ~21.5 kbar at 450–460°C and T_max conditions of 19.5–21.0 kbar at 490–520°C. During exhumation, the rock passed through metamorphic conditions of 17.5–19.0 kbar at 475–500°C, before recording P–T conditions of <17.5 kbar at <500°C. These results demonstrate that maximum recorded pressures for individual samples vary by as much as 6 kbar in the eastern segment of the SW Tianshan, which may suggest exhumation from different depths in the subduction channel. Furthermore, the three samples record similar P–T paths from ~17.0 to 15.0 kbar, which suggests they were juxtaposed at a similar depth along the subduction interface. We compare our new results with published information from eclogites in the same area before considering the wider implications of these data for the orogenic development of the belt as a whole.     

Numerical modeling of thermal structure, circulation of H2O, and magmatism–metamorphism in subduction zones: Implications for evolution of arcs

Numerical models on thermal structure, convective flow of solid, generation and transportation of H₂O-rich fluid in subduction zones are consolidated to have a comprehensive view of the subduction zone processes: heat balance, circulation of H₂O magmatism–metamorphism, growth of arcs and continental margins. A large scale convection model with steady subduction of a cold old slab (130 Myr old) predicts rapid ( 100 Myr) cooling of subduction zones, resulting in cessation of magmatism. The model also predicts that the mantle temperature beneath arcs and continental margins is greatly affected by the effective temperature of the subducting slab, i.e., the age of the subducting slab. If subduction of a young hot slab, including ridge subduction, occurs every 60 to 120 Myr as is suggested for eastern Asia, the average temperature beneath arcs is increased by about 300 °C, which may explain the long-lasting magmatism in eastern Asia. Associated with subduction of young slabs and ridges, thermal structure and circulation of H₂O are greatly modified to cause a transition from (1) normal arc magmatism, (2) forearc mantle melting, to (3) slab melting to produce a significant amount (100 km³) of granitic melts, associated with both high-P/T and low-P/T type metamorphism. The last stage of (3) can result in formation of a granitic batholith belt and a paired metamorphic belts. Synthesis of the numerical models and observations suggest that episodic subduction of young slabs and ridges can explain heat source for generating a large amount of granitic magmas of batholiths, synchronous formation of batholith and regional metamorphic belts, and P–T conditions of the paired metamorphism. Even the high-P/T metamorphism requires an elevated geothermal structure in the forearc region, associated with ridge subduction. Although the emplacement of the batholiths and the regional metamorphic belts, and the mass balance in subduction zones are not well constrained at present, the episodic event associated with ridge subduction is thought to be essential for net growth of arcs and continental margins, as well as for the long-term heat balance in subduction zones.