The origin of amorphous rims on lunar plagioclase grains: Solar wind damage or vapor condensates

A distinctive feature of micron sized plagioclase grains from mature lunar soils is a thin (20 to 100 nm) amorphous rim surrounding the grains. These rims were originally described from high voltage electron microscope observations of lunar plagioclase grains by Dran et al., who observed rims up to 100 nm thick on plagioclase grains from Apollo 11 and 12 soils. These rims are believed to be the product of solar wind damage. The amorphous rims were studied on micron sized plagioclase grains from a mature Apollo 16 soil using a JEOL 200FX transmission electron microscope equipped with an energy dispersive x ray spectrometer. It was found that the amorphous rims are compositionally distinct from the interior plagioclase and it is proposed that a major component of vapor condensates is present in the rims

Transmission electron microscopy of an interplanetary dust particle with links to CI chondrites

The majority of hydrated interplanetary dust particles (IDPs) have compositions that resemble CI and CM chondrites, however, their mineralogies are most similar to the fine grained material in certain altered type-3 carbonaceous and ordinary chondrites. During the transmission electron microscope studies of hydrated IDPs, a unique particle was discovered whose mineralogy is very similar to that reported from CI chondrites. W7013F5 is the first IDP whose mineralogy and chemistry approximates that of CI chondrites. The similarity in mineralogy and mineral chemistry suggests that W7013F5 was altered under conditions similar to those that existed on the CI parent bodies

Impact glasses from the less than 20-micrometer fraction of Apollo 17 soils 72501 and 78221

The chemical compositions of microscopic glasses produced during meteoroid impacts on the lunar surface provide information regarding the various fractionation processes that accompany these events. To learn more about these fractionation processes, we studied the compositions of submicrometer glass spheres from two Apollo 17 sampling sites using electron microscopy. The majority of the analyzed glasses show evidence for varying degrees of impact-induced chemical fractionation. Among these are HASP glasses (high-Al, Si-poor), which are believed to represent the refractory residuum left after the loss of volatile elements (e.g., Si, Fe, Na) from the precursor material. In addition to HASP-type glasses, we also observed a group of volatile-rich, Al-poor (VRAP) glasses that represent condensates of vaporized volatile constituents, and are complementary to the HASP compositions. High-Ti glasses were also found during the course of this study, and are documented here for the first time

Differential Effects of Buffer pH On Ca\u3csup\u3e2+\u3c/sup\u3e-Induced ROS Emission with Inhibited Mitochondrial Complexes I and III

Excessive mitochondrial reactive oxygen species (ROS) emission is a critical component in the etiology of ischemic injury. Complex I and complex III of the electron transport chain are considered the primary sources of ROS emission during cardiac ischemia and reperfusion (IR) injury. Several factors modulate ischemic ROS emission, such as an increase in extra-matrix Ca2+, a decrease in extra-matrix pH, and a change in substrate utilization. Here we examined the combined effects of these factors on ROS emission from respiratory complexes I and III under conditions of simulated IR injury. Guinea pig heart mitochondria were suspended in experimental buffer at a given pH and incubated with or without CaCl2. Mitochondria were then treated with either pyruvate, a complex I substrate, followed by rotenone, a complex I inhibitor, or succinate, a complex II substrate, followed by antimycin A, a complex III inhibitor. H2O2 release rate and matrix volume were compared with and without adding CaCl2 and at pH 7.15, 6.9, or 6.5 with pyruvate + rotenone or succinate + antimycin A to simulate conditions that may occur during in vivo cardiac IR injury. We found a large increase in H2O2 release with high [CaCl2] and pyruvate + rotenone at pH 6.9, but not at pHs 7.15 or 6.5. Large increases in H2O2 release rate also occurred at each pH with high [CaCl2] and succinate + antimycin A, with the highest levels observed at pH 7.15. The increases in H2O2 release were associated with significant mitochondrial swelling, and both H2O2 release and swelling were abolished by cyclosporine A, a desensitizer of the mitochondrial permeability transition pore (mPTP). These results indicate that ROS production by complex I and by complex III is differently affected by buffer pH and Ca2+ loading with mPTP opening. The study suggests that changes in the levels of cytosolic Ca2+ and pH during IR alter the relative amounts of ROS produced at mitochondrial respiratory complex I and complex III

Absorption Efficiencies of Forsterite. I: DDA Explorations in Grain Shape and Size

We compute the absorption efficiency (Qabs) of forsterite using the discrete dipole approximation (DDA) in order to identify and describe what characteristics of crystal grain shape and size are important to the shape, peak location, and relative strength of spectral features in the 8-40 {\mu}m wavelength range. Using the DDSCAT code, we compute Qabs for non-spherical polyhedral grain shapes with a_eff = 0.1 {\mu}m. The shape characteristics identified are: 1) elongation/reduction along one of three crystallographic axes; 2) asymmetry, such that all three crystallographic axes are of different lengths; and 3) the presence of crystalline faces that are not parallel to a specific crystallographic axis, e.g., non-rectangular prisms and (di)pyramids. Elongation/reduction dominates the locations and shapes of spectral features near 10, 11, 16, 23.5, 27, and 33.5 {\mu}m, while asymmetry and tips are secondary shape effects. Increasing grain sizes (0.1-1.0 {\mu}m) shifts the 10, 11 {\mu}m features systematically towards longer wavelengths and relative to the 11 {\mu}m feature increases the strengths and slightly broadens the longer wavelength features. Seven spectral shape classes are established for crystallographic a-, b-, and c-axes and include columnar and platelet shapes plus non-elongated or equant grain shapes. The spectral shape classes and the effects of grain size have practical application in identifying or excluding columnar, platelet or equant forsterite grain shapes in astrophysical environs. Identification of the shape characteristics of forsterite from 8-40 {\mu}m spectra provides a potential means to probe the temperatures at which forsterite formed.Comment: 55 pages, 15 figure

Microstructure, Chemistry, and Origin of Grain Rims on ilmenite from the Lunar Soil Finest Fraction

Analytical transmission electron microscope (TEM) observations reveal that ilmenite grains sampled from the sub-10 micron size fraction of Apollo 11 (10084) and Apollo 16 (61221, 67701) soils have rims 10-300 nm thick that are chemically and microstructurally distinct from the host ilmenite. The rims have a thin outer sublayer 10-50 nm thick that contains the ilmenite-incompatible elements Si, Al, Ca and S. This overlies a relatively thicker (50-250 nm) inner sublayer of nanocrystalline Ti-oxide precipitates in a matrix of single-crystal ilmenite that is structurally continuous with the underlying host grain. Microstructural information, as well as data from x-ray spectrometry (EDS) and electron energy loss spectrometry (EELS) analysis of the inner sublayer, suggest that both the inner and outer sublayer assemblages are reduced and that the inner layer is depleted in Fe relative to the underlying ilmenite. The chemistry of the outer sublayer suggests that it is a surface deposit of sputtered or impact-vaporized components from the bulk lunar soil. The inner sublayer is part of the original host grain that has been physically and chemically processed, but not amorphized, by solar ion irradiation and possibly some subsolidus heating. The fact that the deposited outer sublayer is consistently much thinner than the radiation-altered inner sublayer indicates that only a minor fraction of the total rim volume is a product of vapor or sputter deposition. This finding is in contrast to recent descriptions of thick deposited layers on one-third of regolith silicate grains and indicates that ilmenite and silicate rims as a group are different in the fraction of deposited material that they contain

A quantitative empirical directing group scale for selectivity in iridium-catalysed hydrogen isotope exchange reactions

A palette of commonly used directing groups, including various pharmaceutically relevant nitrogen-containing heterocycles, are quantitatively ranked based on the results of intermolecular hydrogen isotope exchange competition reactions using two iridium complexes: [Ir(COD)(IMes)(PPh3)][BArF24] and [IrCl(COD)(IMes)]. The directing group power scales that have been constructed from these data reveal a wide range of reactivity covering four orders of magnitude. Intramolecular competition experiments have demonstrated that the obtained reactivity scale provides accurate predictions of regioselectivity within molecules with multiple competing directing groups. This work contributes to our understanding and control of regioselectivity in metal-catalysed C-H activation reactions