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Seismological observations in the lunar mantle, in conjunction with experimental knowledge on the elastic wave velocities and density of lunar mantle minerals, provide important constraints on the composition and mineralogy of the lunar mantle. Here we report elastic wave velocities and density of a lunar orthopyroxene (Mg0.84Fe0.13Ca0.03SiO3) up to 5.5 GPa and 1,273 K. The result shows that the bulk and shear moduli of orthopyroxene decrease with increasing iron content. Based on the mineral elasticity data, we modeled the P‐ and S‐wave velocities and density of petrologically suggested lunar upper mantle rock composition. The petrological lunar upper mantle rock model shows consistent seismic wave velocities with those observed in the lunar upper mantle whereas markedly lower density. Our modeling suggests an iron‐rich (Fe/(Mg + Fe) = 0.20) lunar upper mantle to explain P‐ and S‐wave velocities and density of the lunar upper mantle at 40–740 km depth.

This study provides a comprehensive review of the crystal preferred orientation (CPO) of olivine and orthopyroxene in the upper mantle, and of several hydrous minerals in the mantle wedge and at the slab-mantle interface. It discusses the seismic anisotropy of those minerals. Water-induced CPOs of olivine produced by previous experimental studies under high pressure and temperature conditions were found in many natural rocks. It is emphasized that the strong CPOs of hydrous minerals such as serpentine, chlorite, and amphibole, play an important role in interpreting the anomalously strong seismic anisotropy observed in subduction zones.

We present two-feldspar thermometry and diffusion chronometry from sanidine, orthopyroxene and quartz from multiple samples of the Bishop Tuff, California, to constrain the temperature stratification within the pre-eruptive magma body and the timescales of magma mixing prior to its evacuation. Two-feldspar thermometry yields estimates that agree well with previous Fe–Ti oxide thermometry and gives a ~80 °C temperature difference between the earlier- and later-erupted regions of the magma chamber. Using the thermometry results, we model diffusion of Ti in quartz, and Ba and Sr in sanidine as well as Fe–Mg interdiffusion in orthopyroxene to yield timescales for the formation of overgrowth rims on these crystal phases. Diffusion profiles of Ti in quartz and Fe–Mg in orthopyroxene both yield timescales of <150 years for the formation of overgrowth rims. In contrast, both Ba and Sr diffusion in sanidine yield nominal timescales 1–2 orders of magnitude longer than these two methods. The main cause for this discrepancy is inferred to be an incorrect assumption for the initial profile shape for Ba and Sr diffusion modelling (i.e. growth zoning exists). Utilising the divergent diffusion behaviour of Ba and Sr, we place constraints on the initial width of the interface and can refine our initial conditions considerably, bringing Ba and Sr data into alignment, and yielding timescales closer to 500 years, the majority of which are then within uncertainty of timescales modelled from Ti diffusion in quartz. Care must be thus taken when using Ba in sanidine geospeedometry in evolved magmatic systems where no other phases or elements are available for comparative diffusion profiling. Our diffusion modelling reveals piecemeal rejuvenation of the lower parts of the Bishop Tuff magma chamber at least 500 years prior to eruption. Timescales from our mineral profiling imply either that diffusion coefficients currently used are uncertain by 1–2 orders of magnitude, or that the minerals concerned did not experience a common history, despite being extracted from the same single pumice clasts. Introduction of the magma initiating crystallisation of the contrasting rims on sanidine, quartz, orthopyroxene and zircon was prolonged, and may be a marker of other processes that initiated the Bishop Tuff eruption rather than the trigger itself.

Kimberlites are rare diamond-bearing volcanic rocks that originate as melts in the Earth’s mantle. The original composition of kimberlitic melt is poorly constrained because of mantle and crustal contamination, exsolution of volatiles during ascent, and pervasive alteration during and after emplacement. One recent model (Russell et al. in Nature 481(7381):352–356, 2012 . doi: 10.1038/nature10740 ) proposes that kimberlite melts are initially carbonatitic and evolve to kimberlite during ascent through continuous assimilation of orthopyroxene and exsolution of CO 2 . In high-temperature, high-pressure experiments designed to test this model, assimilation of orthopyroxene commences between 2.5 and 3.5 GPa by a reaction in which orthopyroxene reacts with the melt to form olivine, clinopyroxene, and CO 2 . No assimilation occurs at 3.5 GPa and above. We propose that the clinopyroxene produced in this reaction can react with the melt at lower pressure in a second reaction that produces olivine, calcite, and CO 2 , which would explain the absence of clinopyroxene phenocrysts in kimberlites. These experiments do not confirm that assimilation of orthopyroxene for the entirety of kimberlite ascent takes place, but rather two reactions at lower pressures (<3.5 GPa) cause assimilation of orthopyroxene and then clinopyroxene, evolving carbonatitic melts to kimberlite and causing CO 2 exsolution that drives rapid ascent.

Crystal chemical algorithms were used to estimate the chemical composition of selected mineral phases observed with the CheMin X-ray diffractometer onboard the NASA Curiosity rover in Gale crater, Mars. The sampled materials include two wind-blown soils, Rocknest and Gobabeb, six mudstones in the Yellowknife Bay formation (John Klein and Cumberland) and the Murray formation (Confidence Hills, Mojave2, and Telegraph Peak), as well as five sandstones, Windjana and the samples of the unaltered Stimson formation (Big Sky and Okoruso) and the altered Stimson formation (Greenhorn and Lubango). The major mineral phases observed with the CheMin instrument in the Gale crater include plagioclase, sanidine, P21/c and C2/c clinopyroxene, orthopyroxene, olivine, spinel, and alunite-jarosite group minerals. The plagioclase analyzed with CheMin has an overall estimated average of An40(11) with a range of An30(8) to An63(6). The soil samples, Rocknest and Gobabeb, have an average of An56(8) while the Murray, Yellowknife Bay, unaltered Stimson, and altered Stimson formations have averages of An38(2), An37(5), An45(7), and An35(6), respectively. Alkali feldspar, specifically sanidine, average composition is Or74(17) with fully disordered Al/Si. Sanidine is most abundant in the Wind-jana sample (∼26 wt% of the crystalline material) and is fully disordered with a composition of Or87(5). The P21/c clinopyroxene pigeonite observed in Gale crater has a broad compositional range {[Mg0.95(12)-1.54(17)Fe0.18(17)-1.03(9)Ca0.00-0.28(6)]Σ2Si2O6} with an overall average of Mg1.18(19)Fe0.72(7)Ca0.10(9)Si2O6. The soils have the lowest Mg and highest Fe compositions [Mg0.95(5)Fe1.02(7)Ca0.03(4)Si2O6] of all of the Gale samples. Of the remaining samples, those of the Stimson formation exhibit the highest Mg and lowest Fe [average = Mg1.45(7)Fe0.35(13)Ca0.19(6)Si2O6]. Augite, C2/c clinopyroxene, is detected in just three samples, the soil samples [average = Mg0.92(5)Ca0.72(2)Fe0.36(5)Si2O6] and Windjana (Mg1.03(7)Ca0.75(4)Fe0.21(9)Si2O6). Orthopyroxene was not detected in the soil samples and has an overall average composition of Mg0.79(6)Fe1.20(6)Ca0.01(2)Si2O6 and a range of [Mg0.69(7)-0.86(20)Fe1.14(20)-1.31(7)Ca0.00-0.04(4)]Σ2Si2O6, with Big Sky exhibiting the lowest Mg content [Mg0.69(7)Fe1.31(7)Si2O6] and Okoruso exhibiting the highest [Mg0.86(20)Fe1.14(20)Si2O6]. Appreciable olivine was observed in only three of the Gale crater samples, the soils and Windjana. Assuming no Mn or Ca, the olivine has an average composition of Mg1.19(12)Fe0.81(12)SiO4 with a range of 1.08(3) to 1.45(7) Mg apfu. The soil samples [average = Mg1.11(4)Fe0.89SiO4] are significantly less magnesian than Windjana [Mg1.35(7)Fe0.65(7)SiO4]. We assume magnetite (Fe3O4) is cation-deficient (Fe3-x∎xO4) in Gale crater samples [average = Fe2.83(5)∎0.14O4; range 2.75(5) to 2.90(5) Fe apfu], but we also report other plausible cation substitutions such as Al, Mg, and Cr that would yield equivalent unit-cell parameters. Assuming cation-deficient magnetite, the Murray formation [average = Fe2.77(2)∎0.23O4] is noticeably more cation-deficient than the other Gale samples analyzed by CheMin. Note that despite the presence of Ti-rich magnetite in martian meteorites, the unit-cell parameters of Gale magnetite do not permit significant Ti substitution. Abundant jarosite is found in only one sample, Mojave2; its estimated composition is (K0.51(12)Na0.49)(Fe2.68(7)Al0.32)(SO4)2(OH)6. In addition to providing composition and abundances of the crystalline phases, we calculate the lower limit of the abundance of X-ray amorphous material and the composition thereof for each of the samples analyzed with CheMin. Each of the CheMin samples had a significant proportion of amorphous SiO2, except Windjana that has 3.6 wt% SiO2. Excluding Windjana, the amorphous materials have an SiO2 range of 24.1 to 75.9 wt% and an average of 47.6 wt%. Windjana has the highest FeOT (total Fe content calculated as FeO) at 43.1 wt%, but most of the CheMin samples also contain appreciable Fe, with an average of 16.8 wt%. With the exception of the altered Stimson formation samples, Greenhorn and Lubango, the majority of the observed SO3 is concentrated in the amorphous component (average = 11.6 wt%). Furthermore, we provide average amorphous-component compositions for the soils and the Mount Sharp group formations, as well as the limiting element for each CheMin sample.

The magmatic systems that give rise to voluminous crystal-poor rhyolite magma bodies can be considered to operate on two contrasting timescales: Those governed by longer-term processes by which a magma acquires its chemical and isotopic characteristics (e.g., fractional crystallisation and assimilation), and those operating at shorter timescales during the physical accumulation of the melt-dominant magma body that finally erupts. We explore the compositional and textural relationships between amphibole and orthopyroxene crystals from the 25.4 ka, 530 km 3 (magma) Oruanui eruption products (Taupo volcano, New Zealand) to investigate how processes related to the physical assembly of the pre-eruptive magma body are represented in the crystal record. Over 90 % of orthopyroxenes from the volumetrically dominant high-SiO 2 (>74 wt%) rhyolite pumices record textural evidence for a significant disequilibrium event (partial dissolution ± resorption of cores and interiors) prior to the growth of 40–500 μm thick rim zones. This dissolution/regrowth history of orthopyroxene is recorded in the chemistry of co-crystallising amphiboles as a prominent inflection in the concentrations of Mn and Zn, two elements notably enriched in orthopyroxene relative to amphibole. Textural and chemical features, linked with in situ thermobarometric estimates, indicate that a major decompression event preceded the formation of the melt-dominant body. The decompression event is inferred to represent the extraction of large volumes of melt plus crystals from the Oruanui crystal mush/source zone at pressures of 140–300 MPa (~6–12 km depth). Orthopyroxene underwent partial dissolution during ascent before reestablishing in the melt-dominant magma body at pressures of 90–140 MPa (~3.5–6 km). We model Fe–Mg diffusion across the core-rim boundaries along the crystallographic a or b -axes to constrain the timing of this decompression event, which marked establishment of the melt-dominant magma body. Maximum modelled ages indicate that this event did not begin until ~1,600 years before eruption, consistent with constraints from zircon model-age spectra. Once extraction began, it underwent runaway acceleration with a peak extraction age of ~230 years, followed by an apparent period of stasis of ~60 years prior to eruption. The rapidity of the extraction and accumulation processes implies the involvement of a dynamic driving force which, in the rifted continental arc setting of the Taupo Volcanic Zone, seems likely to be represented by magma-assisted extensional tectonic processes.

We have measured the dependence of the Fe–Mg interdiffusion coefficient, D Fe-Mg , on the ferrosilite component in orthopyroxene, which so far has not been experimentally calibrated. Diffusion couples, consisting of approximately 1 µm thin-films were deposited by pulsed laser ablation on orthopyroxene crystals of En 91 Fs 9 composition. Diffusion experiments were carried out at atmospheric pressure in vertical gas mixing furnaces (CO-CO 2 ) at temperatures between 950 and 1100 °C at constant f O 2  = 10 –7 Pa. Using a focused ion beam-scanning electron microscope (FIB-SEM), FIB-foils were cut from diffusion couples before and after annealing. Diffusion profiles were extracted by using combined backscattered electron (BSE) imaging and energy dispersive X-ray (EDXS) mapping on FIB-foils which allowed to resolve concentration gradients within 20 nm. The microstructure of the diffusion experiments was investigated using transmission electron microscopy (TEM). Using this method, we obtained the first experimentally determined data on the dependence of D Fe-Mg on the ferrosilite content in orthopyroxene at different temperatures, appearing to increase with increasing a temperature. For the temperature range (950 – 1100 °C), log f O 2  = -7 Pa, along [001] in the composition Fs9, the log D Fe-Mg yields the following Arrhenius equation: D F e - M g [ m 2 / s ] = 3.8 · 10 - 9 exp [ - 261.07 ± 24 [ k J / m o l ] / ( R / T [ K ] ) ] The effect of X Fe on D Fe-Mg, given by D ( X Fe ) = D ( X Fe = 0.09 ) · 10 m ( X Fe - 0.09 ) , can be calculated by the following parameterization where m follows a linear regression of m on temperature: m = - 2.711 · 10 4 / T ( K ) + 23.5408 By considering the D Fe-Mg dependence on X Fe , the timescales of natural processes obtained from modelling the compositional zoning of natural crystal may considerably differ from previously estimated timescales.

We performed first-principles calculations on the energy, and NMR and polarized infrared (IR) spectra for anhydrous and hydrous aluminous orthoenstatite (OEn) models to help clarify the incorporation mechanisms of Al and OH defects in OEn. Our calculations revealed that proton pairs in M2 vacancies ((2H) M2 ) adjacent to a tetrahedral Al (Al IV ) are energetically more favorable than those remote from Al, and may contribute to the observed correlated 1 H NMR peaks near 3.7 and 8.0 ppm, and IR bands near 3550–3570 and 3066 cm −1 (A4 band) for aluminous OEn. Coupled substitutions of Al VI (octahedral Al) + H for 2Mg were found to adopt multiple configurations, and may contribute to the observed IR bands near 3520, 3475 and 3320 cm −1 . Coupled substitution of Al IV  + H for 1Si may contribute to the observed IR band near 3380–3400 cm −1 . 4H in SiB vacancies ((4H) SiB ) adjacent to an Al VI were found to be energetically more favorable than those remote from Al, and may be the origin for an IR band observed near 3600–3620 cm −1 . These results allow the incorporation mechanisms of water in synthetic and natural aluminous orthopyroxenes to be deciphered from the available NMR and IR data, and suggest that both (2H) M2 defects associated with Al and simultaneous coupled substitutions of Al + H for 2Mg and 1Si contribute to the observed correlation between Al and water incorporation, and the nearly unity Al IV /Al VI ratio. (4H) SiB defects associated with Al may also be present in some synthetic OEn and mantle-derived orthopyroxene.

The thermal properties of major minerals play a key role in understanding the internal dynamic mechanism and thermal evolution of the Earth and rocky planets. In this study, we first investigated the effect of Fe on the thermal conductivity (κ) and the thermal diffusivity (D) of orthopyroxene at 1–3 GPa and 293–873 K by the transient plane source method. The κ and D both decrease with increasing temperature and decreasing pressure. With increasing Fe content, the two parameters both quickly decrease from the beginning and then slack off. We further modeled the thermal evolution of S‐type asteroids, which strongly depends on the composition model and the dimension of the planet. Combining the present data with surface heat flow and heat production, the lunar's geotherm until 1,400 km is constructed. The core‐mantle boundary temperature of the Moon is refined from 1,883 to 1,754 K. Plain Language Summary The thermal state and the thermal evolution of rocky planets are strongly influenced by the thermal properties of the major constituent minerals. Orthopyroxene is one of such minerals for rocky planets (e.g., S‐type asteroids and moon). The Fe content can potentially affect the thermal properties of orthopyroxene. However, there are no relevant studies up to now. In this study, we systematically measured the thermal conductivity and the thermal diffusivity of pyroxene with variable Fe content at high temperature and high pressure. Our research shows that the thermal conductivity and the thermal diffusivity of orthopyroxene decrease with increasing Fe content. Adopting the results of this study, we simulate the thermal evolution of S‐type asteroids with different compositions and dimensions and construct the lunar's geotherm until the core‐mantle boundary. Key Points Both the thermal conductivity and the thermal diffusivity of orthopyroxene decrease with temperature and increase with pressure The thermal conductivity and the thermal diffusivity of orthopyroxene quickly decrease with iron content The thermal evolutions of S‐type asteroids are first simulated and the thermal structure of the lunar interior until the CMB is constrained

We performed 1 H and 29 Si NMR and infrared measurements, and first-principles calculations to clarify the nature of OH defects in MgSiO 3 orthoenstatite. An orthoenstatite sample synthesized at 7 GPa and 1200 °C from a composition of MgSiO 3  + 0.1 wt% H 2 O yielded two 1 H MAS NMR peaks near 5.9 and 7.6 ppm that are correlated in 2D NMR spectra, and two infrared bands near 3361 and 3066 cm − 1 that correspond to the previously reported A3 and A4 bands. The first-principles calculations confirmed that they are due to a pair of protons in a Mg (M2) vacancy. The previously reported A1 and A2 infrared bands near 3687 and 3592 cm − 1 for orthoenstatite synthesized at low silica activities were confirmed to arise from four protons in a SiB vacancy. The latter is predicted to give two additional OH stretching bands associated with two strongly hydrogen-bonded O3b-H bonds with frequencies below the spectral range reported thus far. The previously reported infrared absorption coefficients were thus revised to account for the undetected bands. 1 H NMR may be used to quantitatively detect all four protons (expected at 1–12 ppm). Other mantle minerals should also be examined for potentially overlooked OH defects with strong hydrogen bonding.