A 4,565-My-old andesite from an extinct chondritic protoplanet.

The age of iron meteorites implies that accretion of protoplanets began during the first millions of years of the solar system. Due to the heat generated by 26Al decay, many early protoplanets were fully differentiated with an igneous crust produced during the cooling of a magma ocean and the segregation at depth of a metallic core. The formation and nature of the primordial crust generated during the early stages of melting is poorly understood, due in part to the scarcity of available samples. The newly discovered meteorite Erg Chech 002 (EC 002) originates from one such primitive igneous crust and has an andesite bulk composition. It derives from the partial melting of a noncarbonaceous chondritic reservoir, with no depletion in alkalis relative to the Sun's photosphere and at a high degree of melting of around 25%. Moreover, EC 002 is, to date, the oldest known piece of an igneous crust with a 26Al-26Mg crystallization age of 4,565.0 million years (My). Partial melting took place at 1,220 °C up to several hundred kyr before, implying an accretion of the EC 002 parent body ca. 4,566 My ago. Protoplanets covered by andesitic crusts were probably frequent. However, no asteroid shares the spectral features of EC 002, indicating that almost all of these bodies have disappeared, either because they went on to form the building blocks of larger bodies or planets or were simply destroyed.

High-spatial-resolution measurements of iron isotopes in pyrites by secondary ion mass spectrometry using the new Hyperion-II radio-frequency plasma source.

RATIONALE: Iron isotopic signatures in pyrites are considered as a good proxy for reconstructing paleoenvironmental and local redox conditions. However, the investigation of micro-pyrites less than 20 µm in size has been limited by the available analytical techniques. The development of a new brighter radio-frequency plasma ion source (Hyperion-II source) enhances the spatial resolution by increasing the beam density 10 times compared with the Duoplasmatron source. METHODS: Here we present high-spatial-resolution measurements of iron isotopes in pyrites using a 3 nA-3 µm primary 16 O- beam on two Cameca IMS 1280-HR2 ion microprobe instruments equipped with Hyperion sources at CRPG-IPNT (France) and at SwissSIMS (Switzerland). We tested analytical effects, such as topography and crystal orientation, that could induce analytical biases perceptible through variations of the instrumental mass fractionation (IMF). RESULTS: The δ56 Fe reproducibility for the Balmat pyrite standard is ±0.25‰ (2 standard deviations) and the typical individual internal error is ±0.10‰ (2 standard errors). The sensitivity on 56 Fe+ was 1.2 × 107 cps/nA/ppm or better. Tests on Balmat pyrites revealed that neither the crystal orientation nor channeling effects seem to significantly influence the IMF. Different pyrite standards (Balmat and SpainCR) were used to test the accuracy of the measurements. Indium mounts must be carefully prepared with a sample topography less than 2 µm, which was checked using an interferometric microscope. Such a topography is negligible for introducing change in the IMF. This new source increases the spatial resolution while maintaining the high precision of analyses and the overall stability of the measurements compared with the previous Duoplasmatron source. CONCLUSIONS: A reliable method was developed for performing accurate and high-resolution measurements of micrometric pyrites. The investigation of sedimentary micro-pyrites will improve our understanding of the processes and environmental conditions during pyrite precipitation, including the contribution of primary (microbial activities or abiotic reactions) and secondary (diagenesis and/or hydrothermal fluid circulation) signatures.

Early oxidation of the martian crust triggered by impacts.

Despite the abundant geomorphological evidence for surface liquid water on Mars during the Noachian epoch (>3.7 billion years ago), attaining a warm climate to sustain liquid water on Mars at the period of the faint young Sun is a long-standing question. Here, we show that melts of ancient mafic clasts from a martian regolith meteorite, NWA 7533, experienced substantial Fe-Ti oxide fractionation. This implies early, impact-induced, oxidation events that increased by five to six orders of magnitude the oxygen fugacity of impact melts from remelting of the crust. Oxygen isotopic compositions of sequentially crystallized phases from the clasts show that progressive oxidation was due to interaction with an 17O-rich water reservoir. Such an early oxidation of the crust by impacts in the presence of water may have supplied greenhouse gas H2 that caused an increase in surface temperature in a CO2-thick atmosphere.

Rapid condensation of the first Solar System solids.

Chondritic meteorites are composed of primitive components formed during the evolution of the Solar protoplanetary disk. The oldest of these components formed by condensation, yet little is known about their formation mechanism because of secondary heating processes that erased their primordial signature. Amoeboid Olivine Aggregates (AOAs) have never been melted and underwent minimal thermal annealing, implying they might have retained the conditions under which they condensed. We performed a multiisotope (O, Si, Mg) characterization of AOAs to constrain the conditions under which they condensed and the information they bear on the structure and evolution of the Solar protoplanetary disk. High-precision silicon isotopic measurements of 7 AOAs from weakly metamorphosed carbonaceous chondrites show large, mass-dependent, light Si isotope enrichments (-9‰ < δ30Si < -1‰). Based on physical modeling of condensation within the protoplanetary disk, we attribute these isotopic compositions to the rapid condensation of AOAs over timescales of days to weeks. The same AOAs show slightly positive δ25Mg that suggest that Mg isotopic homogenization occurred during thermal annealing without affecting Si isotopes. Such short condensation times for AOAs are inconsistent with disk transport timescales, indicating that AOAs, and likely other high-temperature condensates, formed during brief localized high-temperature events.

High-precision in situ silicon isotopic analyses by multi-collector secondary ion mass spectrometry in olivine and low-calcium pyroxene.

RATIONALE: High-precision determination of silicon isotopes can be achieved by in situ multi-collector secondary ion mass spectrometry (MS-SIMS). The accuracy of the analyses is, however, sensitive to ion yields and instrumental mass fractionations (IMFs) induced by the analytical procedure. These effects vary from one instrument to another, with the analytical settings, and with the composition and nature of the sample. Because ion yields and IMF effects are not predictable and rely on empirical calibrations, high-accuracy analyses require suitable sets of standards. METHODS: Here, we document calibrations of ion yields and matrix effects in a set of 23 olivine standards and 3 low-Ca pyroxene for silicon isotopic measurements in both polarities using Cameca IMS 1270 E7 and IMS 1280 HR2 ion probes set with the cesium (Cs) or radiofrequency (RF) source. RESULTS: Silicon ion yields show (i) strong variations with the chemical composition, and (ii) an opposite behavior between the secondary positive and negative polarities. The magnitude of IMF along the fayalite-forsterite (olivine) series shows a complex behavior, increasing overall by ≈7‰ (secondary positive) and ≈15‰ (secondary negative) with increasing olivine Mg#. A drastic change in olivine IMF occurs at Mg# ≈ 70 in both polarities. The magnitude of IMF for low-Ca pyroxene from Mg# = 70-100 is almost constant in both polarities, i.e. ≈0.1‰ in secondary positive and ≈0.15‰ in secondary negative. The analytical uncertainties on individual analyses were ± 0.05-0.15‰ (2 S.E.) with both sources, and the external errors for each standard material were ≈ ±0.05-0.5‰ (2 S.E.) with the Cs source and ≈ ±0.03-0.15‰ (2 S.E.) with the RF source. CONCLUSIONS: The IMF effect of Si isotopes in silicates shows complex behaviors that vary with the chemistry and the settings of the instrument. We developed a suitable set of standards in order to perform high-accuracy in situ measurements of Si isotopes in olivine and low-Ca pyroxene characterized by varying chemical compositions by MC-SIMS.

Excess water storage induced by viscous strain localization during high-pressure shear experiment.

Strain localization in viscously deformed rocks commonly results in fine-grained shear zones where massive fluid circulation is regularly observed. Recently attributed to strain-induced pumping, this phenomenon may have major implications for the distribution of ores deposits and rock rheology. However, although grain size reduction and/or creep cavitation have been proposed as important processes, the source mechanism of fluid concentration remains unresolved, particularly at high pressure. Here we use secondary ion mass spectrometry to document the H2O content of fine-grained olivine across an experimental shear zone, which developed with grain size reduction during a H2O-saturated shear experiment at 1.2 GPa and 900 °C. Through data interpolation, the olivine matrix reveals high fluid concentrations where shear strain is localized. These concentrations far exceed the predicted amount of H2O that grain boundaries can contain, excluding grain size reduction as a unique source of water storage. Instead, we show that H2O increases per unit of grain boundary across the shear zone, suggesting that cavitation and "healing" processes compete with each other to produce a larger pore volume with increasing strain rate. This provides an alternative process for fluids to be collected where strain rate is the highest in deep shear zones.

Homogeneous distribution of 26Al in the solar system from the Mg isotopic composition of chondrules.

The timing of the formation of the first solids in the solar system remains poorly constrained. Micrometer-scale, high-precision magnesium (Mg) isotopic analyses demonstrate that Earth, refractory inclusions, and chondrules from primitive meteorites formed from a reservoir in which short-lived aluminum-26 (26Al) and Mg isotopes were homogeneously distributed at +/-10%. This level of homogeneity validates the use of 26Al as a precise chronometer for early solar system events. High-precision chondrule 26Al isochrons show that several distinct chondrule melting events took place from approximately 1.2 million years (My) to approximately 4 My after the first solids condensed from the solar nebula, with peaks between approximately 1.5 and approximately 3 My, and that chondrule precursors formed as early as 0.87(-0.16)(+0.19) My after.