Stable isotope study of the Archaean rocks of the Vredefort impact structure,central Kaapvaal Craton,South Africa

The Vredefort dome in the Kaapvaal Craton was formed as a result of the impact of a large meteorite at 2.02 Ga. The central core of Archaean granitic basement rocks is surrounded by a collar of uplifted and overturned strata of the Witwatersrand Supergroup, exposing a substantial depth section of the Archaean crust. Orthogneisses of the core show little variation in whole-rock δ ¹⁸O value, with the majority being between 8 and 10‰, with a mean of 9.2‰ (n = 35). Quartz and feldspar have per mil differences that are consistent with O-isotope equilibrium at high temperatures, suggesting minimal interaction with fluids during subsequent cooling. These data refute previous suggestions that the Outer Granite Gneiss (OGG) and Inlandsee Leucogranofels (ILG) of the core represent middle and lower crust, respectively. Granulite-facies greenstone remnants from the ILG have δ ¹⁸O values that are on average 1.5‰ higher than the ILG host rocks and are unlikely, therefore, to represent the residuum from the partial melting event that formed the host rock. Witwatersrand Supergroup sedimentary rocks of the collar, which were metamorphosed at greenschist-to amphibolite-facies conditions, generally have lower δ ¹⁸O values than the core rocks with a mean value for metapelites of 7.7‰ (n = 45). Overall, through an ∼20 km thick section of crust, there is a general increase in whole-rock δ ¹⁸O value with increasing depth. This is the reverse of what is normal in the crust, largely because the collar rocks have δ ¹⁸O values that are unusually low in comparison with metamorphosed sedimentary rocks worldwide. The collar rocks have δD values ranging from −35 to −115‰ (average −62‰, n = 29), which are consistent with interaction with water of meteoric origin, having a δD of about −25 to −45‰. We suggest that fluid movement through the collar rocks was enhanced by impact-induced secondary permeability in the dome structure. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Li-Sr-Nd isotope signatures of the plume and cratonic lithospheric mantle beneath the margin of the rifted Tanzanian craton (Labait)

Lithium concentrations and isotopic compositions of olivine and ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd of coexisting clinopyroxene from peridotite xenoliths from the Quaternary Labait volcano, Tanzania, document the influence of rift-related metasomatism on the ancient cratonic mantle. Olivines show negative correlations between Fo content and both δ⁷Li and Li concentrations. Olivines in iron-rich peridotites (Fo_85–87) have high Li concentrations (3.2–4.8 ppm) and heavy δ⁷Li (+5.2 to +6.6). In contrast, olivines in ancient, refractory peridotites have lower Li concentrations (∼2 ppm) and relatively light δ⁷Li (+2.6 to +3.5). This reflects mixing between ancient, refractory cratonic lithosphere and asthenosphere-derived rift magmas. A uniquely fertile, deformed, high-temperature garnet lherzolite, interpreted to be from the base of the lithosphere, has a ⁸⁷Sr/⁸⁶Sr of 0.7029 and ¹⁴³Nd/¹⁴⁴Nd of 0.51286, similar to HIMU oceanic basalts. It provides the best estimate of the Sr–Nd isotope composition of the upwelling mantle (i.e., plume, sensu lato) underlying this portion of the East African Rift, and is slightly less radiogenic compared to previous estimates of the plume that were based on rift basalts. Although elevated δ⁷Li are not exclusive to HIMU source regions, the data collectively indicate that the plume beneath Labait has HIMU characteristics in Sr, Nd and Li isotope composition. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Timing of UHP metamorphism in the Hong’an area,western Dabie Mountains,China: evidence from zircon U–Pb age,trace element and Hf isotope composition

The Hong’an area (western Dabie Mountains) is the westernmost terrane in the Qinling-Dabie-Sulu orogen that preserves UHP eclogites. The ages of the UHP metamorphism have not been well constrained, and thus hinder our understanding of the tectonic evolution of this area. LA-ICPMS U–Pb age, trace element and Hf isotope compositions of zircons of a granitic gneiss and an eclogite from the Xinxian UHP unit in the Hong’an area were analyzed to constrain the age of the UHP metamorphism. Most zircons are unzoned or show sector zoning. They have low trace element concentrations, without significant negative Eu anomalies. These metamorphic zircons can be further subdivided into two groups according to their U–Pb ages, and trace element and Lu–Hf isotope compositions. One group with an average age of 239 ± 2 Ma show relatively high and variable HREE contents (527 ≥ Lu_N ≥ 14) and ¹⁷⁶Lu/¹⁷⁷Hf ratios (0.00008–0.000931), indicating their growth prior to a great deal of garnet growth in the late stage of continental subduction. The other group yields an average age of 227 ± 2 Ma, and shows consistent low HREE contents and ¹⁷⁶Lu/¹⁷⁷Hf ratios, suggesting their growth with concurrent garnet crystallization and/or recrystallization. These two groups of age are taken as recording the time of prograde HP to UHP and retrograde UHP–HP stages, respectively. A few cores have high Th/U ratios, high trace element contents, and a clear negative Eu anomaly. These features support a magmatic origin of these zircon cores. The upper intercept ages of 771 ± 86 and 752 ± 70 Ma for the granitic gneiss and eclogite, respectively, indicate that their protoliths probably formed as a bimodal suite in rifting zones in the northern margin of the Yangtze Block. Young Hf model ages (T _DM1) of magmatic cores indicate juvenile (mantle-derived) materials were involved in their protolith formation. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Influence of temperature,composition, silica activity and oxygen fugacity on the H<Subscript>2</Subscript>O storage capacity of olivine at 8 GPa

Olivine crystals were grown in the presence of a hydrous silicate fluid during multi-anvil experiments at 8 GPa and 1,000–1,600°C. Experiments were conducted both in a simple system (FeO–MgO–SiO₂–H₂O) and in a more complex system containing additional elements (CaO–Na₂O–Al₂O₃–Cr₂O₃–TiO₂–FeO–MgO–SiO₂–H₂O). Silica activity was buffered by the presence of either pyroxene (high a _SiO2) or ferropericlase (low a _SiO2), and was buffered by the presence of Ni + NiO or Fe + FeO, or constrained by the presence of Fe₂O₃. Raman spectroscopy was used to identify pyroxene polymorphs in the run products. Clinoenstatite was present in the 1,000°C experiment, and enstatite in experiments at 1,400–1,520°C. The H₂O content of olivine was measured using secondary ion mass spectroscopy, and infrared spectroscopy was used to investigate the nature of hydrous defects. The H₂O storage capacity of olivine decreases with increasing temperature at 8 GPa. In contrast to previous experimental results at ≤2 GPa, no significant effect of varying oxygen fugacity is evident, but H₂O storage capacity is enhanced under conditions of low silica activity. No significant growth of low wavenumber (<3,400 cm⁻¹) peaks, generally associated with high at low pressure, was observed in the FTIR spectra of olivine from the high experiments. Our experiments show that previous high pressure H₂O storage capacity measurements for olivine synthesized under more oxidizing conditions than the Earth’s mantle are not likely to be compromised by the of the experiments. However, the considerable effect of temperature on H₂O storage capacity in olivine must be taken into account to avoid overestimation of the bulk upper mantle H₂O storage capacity.     

THERIA_G: a software program to numerically model prograde garnet growth

We present the software program THERIA_G, which allows for numerical simulation of garnet growth in a given volume of rock along any pressure–temperature–time (P–T–t) path. THERIA_G assumes thermodynamic equilibrium between the garnet rim and the rock matrix during growth and accounts for component fractionation associated with garnet formation as well as for intracrystalline diffusion within garnet. In addition, THERIA_G keeps track of changes in the equilibrium phase relations, which occur during garnet growth along the specified P–T–t trajectory. This is accomplished by the combination of two major modules: a Gibbs free energy minimization routine is used to calculate equilibrium phase relations including the volume and composition of successive garnet growth increments as P and T and the effective bulk rock composition change. With the second module intragranular multi-component diffusion is modelled for spherical garnet geometry. THERIA_G allows to simulate the formation of an entire garnet population, the nucleation and growth history of which is specified via the garnet crystal size frequency distribution. Garnet growth simulations with THERIA_G produce compositional profiles for the garnet porphyroblasts of each size class of a population and full information on equilibrium phase assemblages for any point along the specified P–T–t trajectory. The results of garnet growth simulation can be used to infer the P–T–t path of metamorphism from the chemical zoning of garnet porphyroblasts. With a hypothetical example of garnet growth in a pelitic rock we demonstrate that it is essential for the interpretation of the chemical zoning of garnet to account for the combined effects of the thermodynamic conditions of garnet growth, the nucleation history and intracrystalline diffusion. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

An experimental study of the grain-scale processes of peridotite melting: implications for major and trace element distribution during equilibrium and disequilibrium melting

The grain-scale processes of peridotite melting were examined at 1,340°C and 1.5 GPa using reaction couples formed by juxtaposing pre-synthesized clinopyroxenite against pre-synthesized orthopyroxenite or harzburgite in graphite and platinum-lined molybdenum capsules. Reaction between the clinopyroxene and orthopyroxene-rich aggregates produces a melt-enriched, orthopyroxene-free, olivine + clinopyroxene reactive boundary layer. Major and trace element abundance in clinopyroxene vary systematically across the reactive boundary layer with compositional trends similar to the published clinopyroxene core-to-rim compositional variations in the bulk lherzolite partial melting studies conducted at similar P–T conditions. The growth of the reactive boundary layer takes place at the expense of the orthopyroxenite or harzburgite and is consistent with grain-scale processes that involve dissolution, precipitation, reprecipitation, and diffusive exchange between the interstitial melt and surrounding crystals. An important consequence of dissolution–reprecipitation during crystal-melt interaction is the dramatic decrease in diffusive reequilibration time between coexisting minerals and melt. This effect is especially important for high charged, slow diffusing cations during peridotite melting and melt-rock reaction. Apparent clinopyroxene-melt partition coefficients for REE, Sr, Y, Ti, and Zr, measured from reprecipitated clinopyroxene and coexisting melt in the reactive boundary layer, approach their equilibrium values reported in the literature. Disequilibrium melting models based on volume diffusion in solid limited mechanism are likely to significantly underestimate the rates at which major and trace elements in residual minerals reequilibrate with their surrounding melt. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Controls on porphyroblast size along a regional metamorphic field gradient

Garnet-bearing schists from the Waterville Formation of south-central Maine provide an opportunity to examine the factors governing porphyroblast size over a range of metamorphic grade. Three-dimensional sizes and locations for all garnet porphyroblasts were determined for three samples along the metamorphic field gradient spanning lowest garnet through sillimanite grade, using high-resolution X-ray computed tomography. Comparison of crystal size distributions to previous data sets obtained by stereological methods for the same samples reveals significant differences in mode, mean, and shape of the distributions. Quantitative textural analysis shows that the garnets in each rock crystallized in a diffusion-controlled nucleation and growth regime. In contrast to the typical observation of a correlation between porphyroblast size and position along a metamorphic field gradient, porphyroblast size of the lowest-grade specimen is intermediate between the high- and middle-grade specimens’ sizes. Mean porphyroblast size does not correlate with peak temperatures from garnet-biotite Fe-Mg exchange thermometry, nor is post-crystallization annealing (Ostwald Ripening) required to produce the observed textures, as was previously proposed for these rocks. Robust pseudosection calculations fail to reproduce the observed garnet core compositions for two specimens, suggesting that these calc-pelites experienced metasomatism. For each of these two specimens, Monte Carlo calculations suggest potential pre-metasomatism bulk compositions that replicate garnet core compositions. Pseudosection analyses allow the estimation of the critical temperatures for garnet growth: ∼481, ∼477, and ∼485°C for the lowest-garnet-zone, middle-garnet-zone, and sillimanite-zone specimens, respectively. Porphyroblast size appears to be determined in this case by a combination of the heating rate during garnet crystallization, the critical temperature for the garnet-forming reaction and the kinetics of nucleation. Numerical simulations of thermally accelerated, diffusion-controlled nucleation, and growth for the three samples closely match measured crystal size distributions. These observations and simulations suggest that previous hypotheses linking the garnet size primarily to the temperature at the onset of porphyroblast nucleation can only partially explain the observed textures. Also important in determining porphyroblast size are the heating rate and the distribution of favorable nucleation sites.     

Mineral inclusions in diamonds from the Kelsey Lake Mine, Colorado, USA: Depleted Archean mantle beneath the Proterozoic Yavapai province

Thirty-four silicate and oxide inclusions large enough for in situ WDS electron microprobe analysis were exposed by grinding/polishing of 19 diamonds from the Kelsey Lake Mine in the Colorado-Wyoming State Line Kimberlite district. Eighteen olivines, seven Cr-pyropes, four Mg-chromites, and one orthopyroxene in 15 stones belong to the peridotite (P) suite and three garnets and one omphacite in three stones belong to the eclogite (E) suite. The fact that this suite is dominated by the peridotite population is in stark contrast to the other diamond suites studied in the State Line district (Sloan, George Creek), which are overwhelmingly eclogitic. Kelsey Lake olivine inclusions are magnesian (17 of 18 grains in 9 stones are in the range Fo 92.7-93.1), typical of harzburgitic P-suite stones worldwide, but unlike the more Fe-rich (lherzolitic) Sloan olivine suite. Mg-chromites (wt% MgO = 12.8-13.8; wt% Cr₂O₃ = 61.4-66.6) are in the lower MgO range of diamond inclusion chromites worldwide. Seven harzburgitic Cr-pyropes in five stones have moderately low calcium contents (wt% CaO = 3.3-4.3) but are very Cr-rich (wt% Cr₂O₃ = 9.7-16.7). A few stones have been analyzed by SIMS for carbon isotope composition and nitrogen abundance. One peridotitic stone is apparently homogeneous in carbon isotope composition (δ¹³C_PDB = −6.2‰) but with variable nitrogen abundance (1296-2550 ppm). Carbon isotopes in eclogitic stones range from “normal” for the upper mantle (δ¹³C_PDB = −5.5‰) to somewhat low (δ¹³C_PDB = −10.2‰), with little internal variation in individual stones (maximum difference is 3.6‰). Nitrogen contents (2-779 ppm) are lower than in the peridotitic stone, and are lower in cores than in rims. As, worldwide, harzburgite-suite diamonds have been shown to have formed in Archean time, we suggest that the Kelsey Lake diamond population was derived from a block of Archean lithosphere that, at the time of kimberlite eruption, existed beneath the Proterozoic Yavapai province. The mixed diamond inclusion populations from the State Line kimberlites appear to support models in which volumes of Wyoming Craton Archean mantle survive buried beneath Proterozoic continental crust. Such material may be mixed with eclogitic/lherzolitic regimes emplaced beneath or intermingled with the Archean rocks by Proterozoic subduction.     

Evidence for crustal degassing of CF4 and SF6 in Mojave Desert groundwaters

Dissolved tetrafluoromethane (CF₄) and sulfur hexafluoride (SF₆) concentrations were measured in groundwater samples from the Eastern Morongo Basin (EMB) and Mojave River Basin (MRB) located in the southern Mojave Desert, California. Both CF₄ and SF₆ are supersaturated with respect to equilibrium with the preindustrial atmosphere at the recharge temperatures and elevations of the Mojave Desert. These observations provide the first in situ evidence for a flux of CF₄ from the lithosphere. A gradual basin-wide enhancement in dissolved CF₄ and SF₆ concentrations with groundwater age is consistent with release of these gases during weathering of the surrounding granitic alluvium. Dissolved CF₄ and SF₆ concentrations in these groundwaters also contain a deeper crustal component associated with a lithospheric flux entering the EMB and MRB through the underlying basement. The crustal flux of CF₄, but not of SF₆, is enhanced in the vicinity of local active fault systems due to release of crustal fluids during episodic fracture events driven by local tectonic activity. When fluxes of CF₄ and SF₆ into Mojave Desert groundwaters are extrapolated to the global scale they are consistent, within large uncertainties, with the fluxes required to sustain the preindustrial atmospheric abundances of CF₄ and SF₆.