Samples returned from the moon and Asteroid Itokawa by NASA's Apollo Missions and JAXA's Hayabusa Mission, respectively, provide a unique record of their interaction with the space environment. Space ...weathering effects result from micrometeorite impact activity and interactions with the solar wind. While the effects of solar wind interactions, ion implantation and solar flare particle track accumulation, have been studied extensively, the rate at which these effects accumulate in samples on airless bodies has not been conclusively determined. Results of numerical modeling and experimental simulations do not converge with observations from natural samples. We measured track densities and rim thicknesses of three olivine grains from Itokawa and multiple olivine and anorthite grains from lunar soils of varying exposure ages. Samples were prepared for analysis using a Leica EM UC6 ultramicrotome and an FEI Quanta 3D dual beam focused ion beam scanning electron microscope (FIB-SEM). Transmission electron microscope (TEM) analyses were performed on the JEOL 2500SE 200kV field emission STEM. The solar wind damaged rims on lunar anorthite grains are amorphous, lack inclusions, and are compositionally similar to the host grain. The rim width increases as a smooth function of exposure age until it levels off at approximately 180 nm after approximately 20 My (Fig. 1). While solar wind ion damage can only accumulate while the grain is in a direct line of sight to the Sun, solar flare particles can penetrate to mm-depths. To assess whether the track density accurately predicts surface exposure, we measured the rim width and track density in olivine and anorthite from the surface of rock 64455, which was never buried and has a surface exposure age of 2 My based on isotopic measurements. The rim width from 64455 (60-70nm) plots within error of the well-defined trend for solar wind amorphized rims in Fig. 1. Measured solar flare track densities are accurately reflecting the surface exposure of the grains. Track densities correlate with the amorphous rim thicknesses. While the space-weathered rims of anorthite grains are amorphous, the space-weathered rims on both Itokawa and lunar olivine grains show solar wind damaged rims that are not amorphous. Instead, the rims are nanocrystalline with high dislocation densities and sparse inclusions of nanophase Fe metal. The rim thicknesses on the olivine grains also correlate with track density. The Itokawa olivine grains have track densities that indicate surface exposures of approximately 10(exp 5) years. Longer exposures (up to approximately 10(exp 7) years) do not amorphize the rims, as evidenced by lunar soil olivines with high track densities (approximately 10(exp 11) cm(exp -2)). From the combined data, shown in Fig. 1, it is clear that olivine is damaged (but not amorphized) more rapidly by the solar wind compared to anorthite. The olivine damaged rim forms quickly (in approximately 10(exp 6) y) and saturates at approximately 120nm with longer exposure time. The anorthite damaged rims form more slowly, amorphize, and grow thicker than the olivine rims. This is in agreement with numerical modeling data which predicts that solar wind damaged rims on anorthite will be thicker than olivine. However, the models predict that both olivine and anorthite rims will amorphize and reach equilibrium widths in less than 10(exp 3) y, in contrast to what is observed for natural samples. Laboratory irradiation experiments, which show rapid formation of fully amorphous and blistered surfaces from simulated solar wind exposures are also in contrast to observations of natural samples. These results suggest that there is a flux dependence on the type and extent of irradiation damage that develops in olivine. This flux dependence suggests that great caution be used in extrapolating between high-flux laboratory experiments and the natural case, as demonstrated by. We constrain the space weathering rate through analysis of returned samples. Provided that the track densities and the solar wind damaged rim widths exhibited by the Itokawa grains are typical of the fine-grained regions of Itokawa, then the space weathering rate is on the order of 10(exp 5) y. Space weathering effects in lunar soils saturate within a few My of exposure while those in Itokawa regolith grains formed in approximately 10(exp 5) y. Olivine and anorthite respond differently to solar wind irradiation. The space weathering effects in olivine are particularly difficult to reconcile with laboratory irradiation studies and numerical models. Additional measurements, experiments, and modeling are required to resolve the discrepancies among the observations and calculations involving solar wind amorphization of different minerals on airless bodies.
The Japanese space agency's (JAXA) Hayabusa mission returned the first particulate samples (typically <100micron) from the surface of an asteroid (25143 Itokawa). These precious samples provide ...important insights into early Solar System processes, but their sizes pose tremendous challenges to coordinated analysis using a variety of nano- and micro-beam techniques. The ability to glean maximal information from individual particles has become increasingly important and depends critically on sample preparation. We developed a hybrid technique combining traditional ultramicrotomy with focused ion beam (FIB) techniques, allowing for more thorough in situ investigations of grain surfaces and interiors. Using this method, we increase the number of FIB-prepared sections that can be recovered from a particle with dimensions on the order of tens of microns. These sections can be subsequently analyzed using a variety of analytical techniques. Particle RA-QD02-0211 is a approx. 40×40×20 micron particle from Itokawa containing olivine and Fe sulfides. It was embedded in low viscosity epoxy and partly sectioned to a depth of approx 10 micron; sections are placed on Cu grids with thin amorphous films for transmission electron microscope (TEM) analyses. With the sample surface partly exposed, the epoxy bullet is trimmed to a height of approx. 5mm to accommodate the allowable dimensions for FIB work (FEI Quanta 600 3D dual beam FIB-SEM). Using a diamond trim knife, the epoxy surrounding the grain is removed on 3 sides (to within a few microns of the grain); the depth of material removed extends well below the bottom of the particle. The sample is attached to an SEM pin mount, the epoxy coated with conductive paint, and the entire assembly coated with approx. 40nm of carbon to eliminate sample charging during FIB work. A protective carbon cap is placed according to the plan for the 15 FIB sections. The central 'spine' of the cap runs perpendicular to the front of the sample, and the 'ribs' protruding from either side run parallel. Each rib indicates the location of a planned FIB section, and the spine contains the final two planned sections. We use a cap with a 4 micron-wide spine and 2micron-wide ribs that have ≳3.5 micron of space between them (narrower cuts result in too much re-deposition of material inside the trenches). Using a 30kV, 3nA ion-beam we expose the front surface of the grain and commence milling trenches between sections. Rather than using the typical C-cut to prepare the sample for lift-out, an L-cut is used instead, leaving the sample connected by an interior tab. tab. Sections are lifted out, attached to TEM grids and thinned to electron transparency. TEM analyses show that our hybrid technique preserves both interior and edge features, including surface modifications from exposure to the space environment, such as damaged rims that form in response to solar wind implantation effects and adhering grains. In addition, the FIB sections provide larger areas that are free of fractures and chatter effects in comparison to the microtome thin sections, thus enabling more accurate measurements of solar flare particle track densities that are used to determine the surface exposure age of the particles.
Mineral grains in lunar and asteroidal regolith samples provide a unique record of their interaction with the space environment. Exposure to the solar wind results in implantation effects that are ...preserved in the rims of grains (typically the outermost 100 nm), while impact processes result in the accumulation of vapor-deposited elements, impact melts and adhering grains on particle surfaces. These processes are collectively referred to as space weathering. A critical element in the study of these processes is to determine the rate at which these effects accumulate in the grains during their space exposure. For small particulate samples, one can use the density of solar flare particle tracks to infer the length of time the particle was at the regolith surface (i.e., its exposure age). We have developed a new technique that enables more accurate determination of solar flare particle track densities in mineral grains <50 micron in size that utilizes focused ion beam (FIB) sample preparation combined with transmission electron microscopy (TEM) imaging. We have applied this technique to lunar soil grains from the Apollo 16 site (soil 64501) and most recently to samples from asteroid 25143 Itokawa returned by the Hayabusa mission. Our preliminary results show that the Hayabusa grains have shorter exposure ages compared to typical lunar soil grains. We will use these techniques to re-examine the track density-exposure age calibration from lunar samples reported by Blanford et al. (1975).
The Hayabusa mission to asteroid 25143 Itokawa successfully returned the first direct samples of the regolith from the surface of an asteroid. The Hayabusa samples thus present a special opportunity ...to directly investigate the evolution of asteroidal surfaces, from the development of the regolith to the study of the more complex effects of space weathering. Here we describe the mineralogy, microstructure and composition of three Hayabusa mission particles using transmission electron microscope (TEM) techniques
The discovery of Ni-, Cu-, and Zn-bearing Fe-sulfides from comet 81P/Wild 2 represents the strongest evidence, in the Stardust collection, of grains that formed in an aqueous environment. Crystalline ...sulfide assemblages from Wild 2 and the hydrothermally altered CI chondrite Orgueil were investigated. Structural and compositional characterizations of the sulfide grains from both collections reveal similarities. The Stardust samples include a cubanite (CuFe₂S₃) grain, a pyrrhotite (Fe,Ni)₁₋ₓS/pentlandite (Fe,Ni)₉S₈ assemblage, and a pyrrhotite/sphalerite (Fe,Zn)S assemblage. Similarly, the CI-chondrite sulfides include individual cubanite and pyrrhotite grains, cubanite/pyrrhotite assemblages, pyrrhotite/pentlandite assemblages, as well as possible sphalerite inclusions within pyrrhotite grains. The cubanite is the low temperature orthorhombic form, which constrains temperature to a maximum of 210°C. The Stardust and Orgueil pyrrhotites are the 4C monoclinic polytype, which is not stable above ~250°C. The combinations of cubanite and pyrrhotite, as well as pyrrhotite and pentlandite, signify even lower temperatures. The crystal structures, compositions, and petrographic relationships of these sulfides constrain formation and alteration conditions. Taken together, these constraints attest to low-temperature hydrothermal processing. The hydrothermal conditions under which cubanite forms were investigated through thermodynamic modeling and experimental synthesis. A thermodynamic model for cubanite was developed to constrain its formation environment. Cubanite was synthesized under hydrothermal conditions consistent with those predicted for the CI-chondrite parent body. The similarity between Stardust and CI-chondrite sulfides suggest similar fluid conditions may have existed on the comet at some point in its history. The presence of cubanite in the Stardust collection has implications for large scale issues such as: heat sources in the comet-forming region; aqueous activity on cometary bodies; and the extent and mechanisms of radial mixing of material in the early nebula. The Wild 2 sulfides are most likely the products of low-temperature aqueous alteration and provide evidence of radial mixing of material from the inner solar system to the comet-forming region and possible secondary aqueous processing on the cometary body.
Eucrites are among the oldest and best studied asteroidal basalts (1). They represent magmatism that occurred on their parent asteroid, likely 4-Vesta, starting at ~ 4563 Ma and continuing for ...approx. 30 Myr. Two hypotheses are debated for the genesis of eucrites, a magma ocean model (2), and a mantle partial melting model. In general, volatiles (H, C, F, Cl) have been ignored for eucrites and 4-Vesta, but solubility of wt% levels of H2O are possible at Vestan interior PT conditions. Targeted measurements on samples could aid our understanding considerably. Recent studies have found evidence of volatile elements in eucrites, but quantifying the abundance of volatiles remains problematic (6). Volatile elements have a disproportionately large effect on melt properties and phase stability, relative to their low abundance. The source of volatile elements can be elucidated by examining the hydrogen isotope ratio (D/H), as different H reservoirs have drastically different H isotope compositions. Recent studies of apatite in eucrites have shown that the D/H of 4-Vesta matches that of Earth and carbonaceous chondrites, however, the D/H of apatites may not represent the D/H of a primitive 4-Vesta melt due to the possibility of degassing prior to the crystallization of apatite. Therefore, the D/H of early crystallizing phases must be measured to determine if the D/H of 4-Vesta is equal to that of the Earth and carbonaceous chondrites.
Focused ion beam (FIB) sectioning has revolutionized preparation of meteorite samples for characterization by analytical transmission electron microscopy (TEM) and other techniques. Although FIB is ...not "non-destructive" in the purest sense, each extracted section amounts to no more than nanograms (approximately 500 cubic microns) removed intact from locations precisely controlled by SEM imaging and analysis. Physical alteration of surrounding material by ion damage, fracture or sputter contamination effects is localized to within a few micrometers around the lift-out point. This leaves adjacent material intact for coordinate geochemical analysis by SIMS, microdrill extraction/TIMS and other techniques. After lift out, FIB sections can be quantitatively analyzed by electron microprobe prior to final thinning, synchrotron x-ray techniques, and by the full range of state-of-the-art analytical field-emission scanning transmission electron microscope (FE-STEM) techniques once thinning is complete. Multiple meteorite studies supported by FIB/FE-STEM are currently underway at NASA-JSC, including coordinated analysis of refractory phase assemblages in CAIs and fine-grained matrices in carbonaceous chondrites. FIB sectioning of CAIs has uncovered epitaxial and other overgrowth relations between corundum-hibonite-spinel consistent with hibonite preceding corundum and/or spinel in non-equilibrium condensation sequences at combinations of higher gas pressures, dust-gas enrichments or significant nebular transport. For all of these cases, the ability of FIB to allow for coordination with spatially-associated isotopic data by SIMS provides immense value for constraining the formation scenarios of the particular CAI assemblage. For carbonaceous chondrites matrix material, FIB has allowed us to obtain intact continuous sections of the immediate outer surface of Murchison (CM2) after it has been experimentally ion processed to simulate solar wind space weathering. The surface amorphization and loss of OH produced by the irradiation provides important clues regarding space weathering on primitive asteroids such as the OSIRIS-Rex target 101955 Bennu.
Amino acids, the building blocks of proteins, have been found to be indigenous in most of the carbonaceous chondrite groups. The abundances of amino acids, as well as their structural, enantiomeric ...and isotopic compositions differ significantly among meteorites of different groups and petrologic types. This suggests that there is a link between parent-body conditions, mineralogy and the synthesis and preservation of amino acids (and likely other organic molecules). However, elucidating specific causes for the observed differences in amino acid composition has proven extremely challenging because samples analyzed for amino acids are typically much larger ((is) approximately 100 mg powders) than the scale at which meteorite heterogeneity is observed (sub mm-scale differences, (is) approximately 1-mg or smaller samples). Thus, the effects of differences in mineralogy on amino acid abundances could not be easily discerned. Recent advances in the sensitivity of instrumentation have made possible the analysis of smaller samples for amino acids, enabling a new approach to investigate the link between mineralogical con-text and amino acid compositions/abundances in meteorites. Through coordinated mineral separation, mineral characterization and highly sensitive amino acid analyses, we have performed preliminary investigations into the relationship between meteorite mineralogy and amino acid composition. By linking amino acid data to mineralogy, we have started to identify amino acid-bearing mineral phases in different carbonaceous meteorites. The methodology and results of analyses performed on the Murchison meteorite are presented here.
The CI chondrites are primitive meteorites with bulk compositions matching the solar photosphere for all but the lightest elements. They have been extensively aqueously altered, and are composed ...primarily of fine-grained phyllosilicate matrix material which is host to carbonates, sulfates, sulfides, and minor amounts of olivine and pyroxene. The alteration, while extensive, is heterogeneous. For example, CI-chondrite cubanite and carbonate grains differ on mm to sub-mm scales, demonstrating multiple aqueous episodes. CI-chondrite variability is also evidenced by degree of brecciation, abundance and size of coarse-grained phyllosilicates, olivine and pyroxene abundance, as well as Ni-content and size of sulfide grains. Our previous work revealed Orgueil sulfide grains with variable Ni-contents, metal:S ratios, crystal structures and textures. We continue to explore the variability of CI-chondrite pyrrhotite (Po, (FeNi)1-xS) and pentlandite (Pn, (Fe,Ni)9S8) grains. We investigate the microstructure of sulfides within and among CI-chondrite meteorites in order to place constraints on the conditions under which they formed.
Pulmonary arterial hypertension (PAH) is a degenerative arteriopathy that leads to right ventricular (RV) failure. BRD4 (bromodomain-containing protein 4), a member of the BET (bromodomain and ...extra-terminal motif) family, has been identified as a critical epigenetic driver for cardiovascular diseases.
To explore the therapeutic potential in PAH of RVX208, a clinically available BET inhibitor.
Microvascular endothelial cells, smooth muscle cells isolated from distal pulmonary arteries of patients with PAH, rats with Sugen5416 + hypoxia- or monocrotaline + shunt-induced PAH, and rats with RV pressure overload induced by pulmonary artery banding were treated with RVX208 in three independent laboratories.
BRD4 is upregulated in the remodeled pulmonary vasculature of patients with PAH, where it regulates FoxM1 and PLK1, proteins implicated in the DNA damage response. RVX208 normalized the hyperproliferative, apoptosis-resistant, and inflammatory phenotype of microvascular endothelial cells and smooth muscle cells isolated from patients with PAH. Oral treatment with RVX208 reversed vascular remodeling and improved pulmonary hemodynamics in two independent trials in Sugen5416 + hypoxia-PAH and in monocrotaline + shunt-PAH. RVX208 could be combined safely with contemporary PAH standard of care. RVX208 treatment also supported the pressure-loaded RV in pulmonary artery banding rats.
RVX208, a clinically available BET inhibitor, modulates proproliferative, prosurvival, and proinflammatory pathways, potentially through interactions with FoxM1 and PLK1. This reversed the PAH phenotype in isolated PAH microvascular endothelial cells and smooth muscle cells
, and in diverse PAH rat models. RVX208 also supported the pressure-loaded RV
. Together, these data support the establishment of a clinical trial with RVX208 in patients with PAH.
