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.     

Quantitative textural analysis of packings of elongate crystals

The spatial distribution of grains in a solidifying igneous rock controls the physical properties of the crystal mush, and in turn is controlled by the rate of crystal growth and accumulation. A predominant non-spherical habit for igneous minerals brings into question the use of spherical particles in reference packings used for quantification of spatial distribution. Furthermore, variations of crystal clustering/ordering with length scale require spatial statistics which take into account the distribution of particles beyond nearest neighbours. Using random close packings of spherocylinders, we demonstrate the importance of aspect ratio for the aggregation index (usually known as R) and show that packings of spherical particles have more structure than packings of rods. The spatial distribution functions demonstrate that the plagioclase grains in the colonnade from the Holyoke basalt are clustered on a length scale of 0.5 mm. Understanding the controls on grain spatial distribution in igneous rocks will depend on the application of these techniques to well-understood environments.     

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.     

Chemical and boron-isotope variations in tourmalines from an S-type granite and its source rocks: the Erongo granite and tourmalinites in the Damara Belt,Namibia

Tourmaline is widespread in metapelites and pegmatites from the Neoproterozoic Damara Belt, which form the basement and potential source rocks of the Cretaceous Erongo granite. This study traces the B-isotope variations in tourmalines from the basement, from the Erongo granite and from its hydrothermal stage. Tourmalines from the basement are alkali-deficient schorl-dravites, with B-isotope ratios typical for continental crust (δ¹¹B average −8.4‰ ± 1.4, n = 11; one sample at −13‰, n = 2). Virtually all tourmaline in the Erongo granite occurs in distinctive tourmaline-quartz orbicules. This “main-stage” tourmaline is alkali-deficient schorl (20–30% X-site vacancy, Fe/(Fe + Mg) 0.8–1), with uniform B-isotope compositions (δ¹¹B −8.7‰ ± 1.5, n = 49) that are indistinguishable from the basement average, suggesting that boron was derived from anatexis of the local basement rocks with no significant shift in isotopic composition. Secondary, hydrothermal tourmaline in the granite has a bimodal B-isotope distribution with one peak at about −9‰, like the main-stage tourmaline, and a second at −2‰. We propose that the tourmaline-rich orbicules formed late in the crystallization history from an immiscible Na–B–Fe-rich hydrous melt. The massive precipitation of orbicular tourmaline nearly exhausted the melt in boron and the shift of δ¹¹B to −2‰ in secondary tourmaline can be explained by Rayleigh fractionation after about 90% B-depletion in the residual fluid. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

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.     

Basaltic explosive volcanism: Constraints from deposits and models

Basaltic pyroclastic volcanism takes place over a range of scales and styles, from weak discrete Strombolian explosions (～10²–10³ kg s^?1) to Plinian eruptions of moderate intensity (10⁷–10⁸ kg s^?1). Recent well-documented historical eruptions from Etna, Kīlauea and Stromboli typify this diversity. Etna is Europe's largest and most voluminously productive volcano with an extraordinary level and diversity of Strombolian to subplinian activity since 1990. Kīlauea, the reference volcano for Hawaiian fountaining, has four recent eruptions with high fountaining (>400 m) activity in 1959, 1960, 1969 (–1974) and 1983–1986 (–2008); other summit (1971, 1974, 1982) and flank eruptions have been characterized by low fountaining activity. Stromboli is the type location for mildly explosive Strombolian eruptions, and from 1999 to 2008 these persisted at a rate of ca. 9 per hour, briefly interrupted in 2003 and 2007 by vigorous paroxysmal eruptions. Several properties of basaltic pyroclastic deposits described here, such as bed geometry, grain size, clast morphology and vesicularity, and crystal content are keys to understand the dynamics of the parent eruptions.The lack of clear correlations between eruption rate and style, as well as observed rapid fluctuations in eruptive behavior, point to the likelihood of eruption style being moderated by differences in the fluid dynamics of magma and gas ascent and the mechanism by which the erupting magma fragments. In all cases, the erupting magma consists of a mixture of melt and gaseous bubbles. The depth and rate of degassing, melt rheology, bubble rise and coalescence rates, and extent of syn-eruptive microlite growth define complex feedbacks that permit reversible shifts between fragmentation mechanisms and in eruption style and intensity. However, many basaltic explosive eruptions end after an irreversible shift to open-system outgassing and microlite crystallization in melt within the conduit.Clearer understanding of the factors promoting this diversity of basaltic pyroclastic eruptions is of fundamental importance in order to improve understanding of the range of behaviors of these volcanoes and assess hazards of future explosive events at basaltic volcanoes. The three volcanoes used for this review are the sites of large and growing volcano-tourism operations and there is a public need both for better knowledge of the volcanoes’ behavior and improved forecasting of the likely course of future eruptions.     

Oxidation of pyrite during extraction of carbonate associated sulfate

The sulfur isotopic composition of carbonate associated sulfate (CAS) has been used to investigate the geochemistry of ancient seawater sulfate. However, few studies have quantified the reliability of δ³⁴S of CAS as a seawater sulfate proxy, especially with respect to later diagenetic overprinting. Pyrite, which typically has depleted δ³⁴S values due to authigenic fractionation associated with bacterial sulfate reduction, is a common constituent of marine sedimentary rocks. The oxidation of pyrite, whether during diagenesis or sample preparation, could thus adversely influence the sulfur isotopic composition of CAS. Here, we report the results of CAS extractions using HCl and acetic acid with samples spiked with varying amounts of pyrite. The results show a very strong linear relationship between the abundance of fine-grained pyrite added to the sample and the resultant abundance and δ³⁴S value of CAS. This data represents the first unequivocal evidence that pyrite is oxidized during the CAS extraction process. Our mixing models indicate that in samples with much less than 1 wt.% pyrite and relatively high δ³⁴S_pyrite values, the isotopic offset imparted by oxidation of pyrite should be much less than ? 4‰. A wealth of literature exists on the oxidation of pyrite by Fe³⁺ and we believe this mechanism drives the oxidation of pyrite during CAS extraction, during which the oxygen used to form sulfate is taken from H₂O, not O₂. Consequently, extracting CAS under anaerobic conditions would only slow, but not halt, the oxidation of pyrite. Future studies of CAS should attempt to quantify pyrite abundance and isotopic composition.     

Application of precise 142Nd/144Nd analysis of small samples to inclusions in diamonds (Finsch,South Africa) and Hadean Zircons (Jack Hills,Western Australia)

¹⁴⁶Sm–¹⁴²Nd and ¹⁴⁷Sm–¹⁴³Nd systematics were investigated in garnet inclusions in diamonds from Finsch (S. Africa) and Hadean zircons from Jack Hills (W. Australia) to assess the potential of these systems as recorders of early Earth evolution. The study of Finsch inclusions was conducted on a composite sample of 50 peridotitic pyropes with a Nd model age of 3.3 Ga. Analysis of the Jack Hills zircons was performed on 790 grains with ion microprobe ²⁰⁷Pb/²⁰⁶Pb spot ages from 3.95 to 4.19 Ga. Finsch pyropes yield 100 × ?¹⁴²Nd = ? 6 ± 12 ppm, ?¹⁴³Nd = ? 32.5, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.1150. These results do not confirm previous claims for a 30 ppm ¹⁴²Nd excess in South African cratonic mantle. The lack of a ¹⁴²Nd anomaly in these inclusions suggests that isotopic heterogeneities created by early mantle differentiation were remixed at a very fine scale prior to isolation of the South African lithosphere. Alternatively, this result may indicate that only a fraction of the mantle experienced depletion during the first 400 Myr of its history. Analysis of the Jack Hills zircon composite yielded 100 × ?¹⁴²Nd = 8 ± 10 ppm, ?¹⁴³Nd = 45 ± 1, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.5891. Back-calculation of this present-day ?¹⁴³Nd yields an unrealistic estimate for the initial ?¹⁴³Nd of ? 160 ?-units, clearly indicating post-crystallization disturbance of the ¹⁴⁷Sm–¹⁴³Nd system. Examination of ^146,147Sm–^142,143Nd data reveals that the Nd budget of the Jack Hills sample is dominated by non-radiogenic Nd, possibly contained in recrystallized zircon rims or secondary subsurface minerals. This secondary material is characterized by highly discordant U–Pb ages. Although the mass fraction of altered zircon is unlikely to exceed 5–10% of total sample, its high LREE content precludes a reliable evaluation of ¹⁴⁶Sm–¹⁴²Nd systematics in Jack Hills zircons.