Origin of Halogens and Nitrogen in Enstatite Chondrites

The EH and EL enstatite chondrites are the most reduced chondrite groups, having formed in nebular regions where the gas may have had high C/O and/or pH₂/pH₂O ratios. Enstatite chondrites (particularly EH) have higher CI- and Mg-normalized abundances of halogens (especially F and Cl) and nitrogen than ordinary chondrites and most groups of carbonaceous chondrites. Even relative to CI chondrites, EH and EL chondrites are enriched in F. We have found that literature values for the halogen abundance ratios in EH and EL chondrites are strongly correlated with the electronegativities of the individual halogens. We suggest that the most reactive halogens were the most efficient at forming compounds (e.g., halides) that were incorporated into EH-chondrite precursor materials. It seems plausible that, under the more-oxidizing conditions pertaining to the other chondrite groups, a larger fraction of the halogens remained in the gas. Nitrogen may have been incorporated into the enstatite chondrites as simple nitrides that did not condense under the more-oxidizing conditions in the regions where other chondrite groups formed. Literature data show that unequilibrated enstatite chondrites have light bulk N (δ ¹⁵N ≈ −20‰) compared to most ordinary (−5 to +20‰) and carbonaceous (+20 to +190‰) chondrites; this may reflect the contribution in enstatite chondrites of nitride condensates with δ¹⁵ N values close to the proposed nebular mean (~−400‰). In contrast, N in carbonaceous chondrites is mainly contained within ¹⁵N-rich organic matter. The major carrier of N in ordinary chondrites is unknown.     

1600 K和20 GP温压条件下的顽火辉石电导率

在温度750～1600 K和压力10～20 GPa条件下,借助于Kawai-5000多面顶砧高温高压设备,就位测量了(Mg_0.9Fe_0.1) SiO₃ 顽火辉石的电导率.实验结果显示,顽火辉石的电导率在高温区以小极化子机制为主,在低温区以质子导电为主,因为实验后的样品中有一定的水含量.另外,X射线衍射实验表明压力（20 GPa）诱发了顽火辉石向林伍德石的相变,这是我们首次在顽火辉石的电导率实验中观测到林伍德石含水相变,而且含水林伍德石的电导率与已有的实验结果相当一致.     

Hydrogen incorporation in enstatite in the system MgO–SiO2–H2O–NaCl

The incorporation of hydrogen in enstatite in a hydrous system containing various amounts of NaCl was investigated at 25 kbar. The hydrogen content in enstatite shows a clear negative correlation to the NaCl-concentration in the system. The most favourable explanation is the reduction of water fugacity due to dilution. Other reasons for the limited hydrogen incorporation at high NaCl levels, such as a significant influence of Na⁺ on the defect chemistry or an exchange between OH^- and Cl⁻in enstatite, appear much less important. A partition coefficient D _Na ^En/Fluid = 0.0013 could be determined, demonstrating that Na is less incompatible in enstatite than H. The new results support the idea that dissolved components have to be considered when the total hydrogen storage capacity in nominally anhydrous minerals is estimated, especially in geological settings with high levels of halogens, such as subduction zones.     

Experimental Studies on Elasticities of Forsterite-Enstatite Composites:Towards an Understanding of the Rules of Mixture

Which rule of mixture is the best for predicting the overall elastic properties of polyphase rocks based on the elastic properties and volume fractions of their constituents? In order to address this question, we sintered forsterite-enstatite polycrystalline aggregates with a varied forsterite volume fraction (0, 0.2, 0.4, 0.5, 0.6, 0.8, and 1.0). Elastic properties (shear, bulk, and Young's moduli) of these synthesized composites were measured as a function of pressure up to 3.0 GPa in a liquid-medium piston-cylinder apparatus using a high-precision ultrasonic interferometric technique. The experimental data can be much better described by the shear-lag model than by the commonly used simple models such as Voigt, Ruess and Hill averages, Hashin-Shtrikman bounds, Ravichandran bounds, Halpin-Tsai equations, and Paul's calculations. We attributed this to the fact that the elastic interaction and stress transfer between phases are neglected in all the models except for the shear-lag model. In particular, t     

A unified model for hydrogen in the Earth and Moon: No one expects the Theia contribution

The Moon is thought to have formed after a planetary embryo, known as Theia, collided with the proto-Earth 4.5 billion years ago. This so-called Giant Impact was the last major event during Earth’s accretion, and its effects on the composition of the Earth and the newly forming Moon would be measureable today. Recent work on lunar samples has revealed that the Moon’s water was not lost as a result of this giant impact. Instead, the Moon appears to contain multiple hydrogen reservoirs with diverse deuterium-to-hydrogen (D/H) ratios. For the first time, we incorporate hydrogen isotopic measurements of lunar samples to help constrain the composition of Theia. We show that the Moon incorporated very low-D/H (δD ≈ -750‰) materials that only could have derived from solar nebula H₂ ingassed into the magma ocean of a large (∼0.4 M_E) planetary embryo that was largely devoid of chondritic water. We infer Theia was a very large body comparable in size to the proto-Earth, and was composed almost entirely of enstatite chondrite-like material. These conclusions limit the type of impact to a “merger” model of similarly-sized bodies, or possibly a “hit-and-run” model, and they rule out models that mix isotopes too effectively.     

Occurrence and origin of keilite, (Fe>0.5,Mg<0.5)S, in enstatite chondrite impact-melt rocks and impact-melt breccias

Keilite (Fe_>0.5,Mg_<0.5)S, the iron-dominant cubic analog of niningerite, (Mg_>0.5,Fe_<0.5)S, occurs in enstatite chondrites [Shimizu, M., Yoshida, H., Mandarino, J.A., 2002. The new mineral species keilite, (Fe,Mg)S, the iron-dominant analog of niningerite. Can. Mineral. 40, 1687–1692]. I find that keilite occurs only in enstatite chondrite impact-melt rocks and impact-melt breccias. Based on the phase relations in the system MgS–MnS–CaS–FeS [Skinner, B.J., Luce, F.D., 1971. Solid solutions of the type (Ca,Mg,Mn,Fe)S and their use as geothermometers for the enstatite chondrites. Am. Mineral. 56, 1269–1296], I conclude that keilite formed from niningerite or alabandite (Mn_>0.5,Fe_<0.5)S by reaction with troilite (FeS) at elevated temperatures of well above 500 °C (the lowest equilibration temperature of keilite), but it is likely that the maximum temperatures during melting experienced by keilite-bearing impact-melt rocks and impact-melt breccias were considerably higher, perhaps >1500 °C, as indicted by the occurrence of euhedral enstatite that formed from a melt [McCoy, T.J., Dickinson, T.L., Lofgren, G.E., 1999. Partial melting of the Indarch (EH4) meteorite: a textural, chemical, and phase relations view of melting and melt migration. Meteorit. Planet. Sci. 34, 735–746]. Based on the classifications of the keilite-bearing meteorites as impact-melt rocks and impact-melt breccias and my own textural observations, I conclude that this elevated temperature was reached as a result of impact and not internal heating and melting, followed by fast cooling, thus, quenching in keilite. Enstatite chondrite impact-melt rocks and impact-melt breccias that do not contain keilite may have been more deeply buried after impact and, hence, cooled slowly and were annealed so that FeS exsolved from keilite, concomitant with the formation of niningerite, alabandite or various (Mn,Mg,Fe) mixed sulfides.     

Nanodeformation in enstatite single crystals: Simulation of micrometeoroid impacts by femtosecond pulsed laser experiments

Space weathering by micrometeoroid bombardment is a cosmic phenomenon on atmosphere-free celestial bodies, a process that is expected to particularly overprint planetesimals and cosmic dust in debris discs. We reproduced micrometeoroid impact craters by femtosecond pulsed laser irradiation on oriented enstatite single crystals (En₉₃Fs₇) to investigate the deformation behavior and its orientation dependence. All microcraters show typical bowl shaped morphologies, a glass surface layer with splash like ejecta material and subsurface layering. Although we could reproduce melting and vaporization as typical space weathering effects in the enstatite experiments, there is no formation of agglutinate particles or metallic nanoparticles (npFe⁰). The shock effects in the deformation layer consist of planar structures like microfractures and cleavages, amorphous lamellae, stacking faults and clinoenstatite lamellae. Their activation and/or orientation depends on the shock direction. In special orientations we observe the activation of glide systems along specific low indexed crystallographic planes. Due to the short timescale and the high strain rates, the most prominent effect is the failure of enstatite by microfracturing along non-rational crystallographic planes. Common deformation mechanisms reported in meteorites like the formation of clinoenstatite lamellae via shearing along [001] (100) occur less frequently. Shear is apparently the dominant mechanism in the formation of the above-mentioned effects and causes also their modification by frictional heating. The wide-spread formation of amorphous lamellae is, for example, interpreted to be the result of this shear heating along planar structures. We interpret this unconventional deformation behavior as a consequence of the small spatial and temporal scale of the experiments, resulting in a short-lived spherical shock wave with high deviatoric stresses in contrast to a long pressure pulse and quasi-hydrostatic compression in large scale impacts that produce typical shock features.     

Impact features of enstatite-rich meteorites

Enstatite-rich meteorites include EH and EL chondrites, rare ungrouped enstatite chondrites, aubrites, a few metal-rich meteorites (possibly derived from the mantle of the aubrite parent body), various impact-melt breccias and impact-melt rocks, and a few samples that may be partial-melt residues ultimately derived from enstatite chondrites. Members of these sets of rocks exhibit a wide range of impact features including mineral-lattice deformation, whole-rock brecciation, petrofabrics, opaque veins, rare high-pressure phases, silicate darkening, silicate-rich melt veins and melt pockets, shock-produced diamonds, euhedral enstatite grains, nucleation of enstatite on relict grains and chondrules, low MnO in enstatite, high Mn in troilite and oldhamite, grains of keilite, abundant silica, euhedral graphite, euhedral sinoite, F-rich amphibole and mica, and impact-melt globules and spherules. No single meteorite possesses all of these features, although many possess several. Impacts can also cause bulk REE fractionations due to melting and loss of oldhamite (CaS) – the main REE carrier in enstatite meteorites. The Shallowater aubrite can be modeled as an impact-melt rock derived from a large cratering event on a porous enstatite chondritic asteroid; it may have been shock melted at depth, slowly cooled and then excavated and quenched. Mount Egerton may share a broadly similar shock and thermal history; it could be from the same parent body as Shallowater. Many aubrites contain large pyroxene grains that exhibit weak mosaic extinction, consistent with shock-stage S4; in contrast, small olivine grains in some of these same aubrites have sharp or undulose extinction, consistent with shock stage S1 to S2. Because elemental diffusion is much faster in olivine than pyroxene, it seems likely that these aubrites experienced mild post-shock annealing, perhaps due to relatively shallow burial after an energetic impact event. There are correlations among EH and EL chondrites between petrologic type and the degree of shock, consistent with the hypothesis that collisional heating is mainly responsible for enstatite-chondrite thermal metamorphism. Nevertheless, the apparent shock stages of EL6 and EH6 chondrites tend to be lower than EL3-5 and EH3-5 chondrites, suggesting that the type-6 enstatite chondrites (many of which possess impact-produced features) were shocked and annealed. The relatively young Ar–Ar ages of enstatite chondrites record heating events that occurred long after any ²⁶Al that may have been present initially had decayed away. Impacts remain the only plausible heat source at these late dates. Some enstatite meteorites accreted to other celestial bodies: Hadley Rille (EH) was partly melted when it struck the Moon; Galim (b), also an EH chondrite, was shocked and partly oxidized when it accreted to the LL parent asteroid. EH, EL and aubrite-like clasts also occur in the polymict breccias Kaidun (a carbonaceous chondrite) and Almahata Sitta (an anomalous ureilite). The EH and EL clasts in Kaidun appear unshocked; some clasts in Almahata Sitta may have been extensively shocked on their parent bodies prior to being incorporated into the Almahata Sitta host.     

Water solubility in nominally anhydrous minerals measured by FTIR and 1H MAS NMR: the effect of sample preparation

Samples of enstatite and forsterite were crystallized in the presence of a hydrous fluid at 15 kbar and 1100 °C. Water contents in quenched samples were measured by ¹H MAS NMR and by FTIR. If the samples were prepared in the same way, similar water concentrations were obtained by both methods. There is no evidence that one or the other method would severely over or underestimate water contents in nominally anhydrous minerals. However, measured water contents vary by orders of magnitude depending on sample preparation. The lowest water contents are measured by polarized FTIR spectroscopy on clear, inclusion-free single crystals. These water contents probably reflect the real point defect solubility in the crystals. Polycrystalline material shows much higher total water concentrations, presumably due to hydrous species on grain boundaries, growth defects, and in submicroscopic fluid inclusions. Grinding the sample in air further increases water concentration. This effect is even more pronounced if the sample is ground in water and subsequently dried at 150 °C. Polarized FTIR measurements on clear single crystals of enstatite saturated at 15 kbar and 1100 °C give 199 ± 25 ppm by weight of water. The spectra show sharp and strongly polarized bands. These bands are also present in spectra measured through turbid, polycrystalline aggregates of enstatite. However, in these spectra, they are superimposed on much broader, nearly isotropic bands resulting from hydrous species in grain boundaries, growth defects, and submicroscopic fluid or melt inclusions. Total water contents for these polycrystalline aggregates are between 2000 and 4000 ppm. Water contents measured by FTIR on enstatite powders are 5300 ppm after grinding in air and 12 600 ppm after grinding under water und subsequent drying at 150 °C. Received: 25 June 1999 / Revised, accepted: 4 October 1999