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Novel Applications of Focused Ion Beam Technique for Planetary Sample Analyses

We are using innovative FIB techniques to prepare samples of planetary materials for different types of coordinated analyses using ion microprobes, synchrotron beamlines, and specialized transmission electron microscopy (TEM) techniques. In these cases, the FIB sample preparation is the critical step in enabling these specialized analyses. We discuss several examples below utilizing the FEI Quanta3D instrument at the NASA Johnson Space Center. Trace element analyses utilizing synchrotron x-ray fluorescence. The trace element content of mineral grains in comet dust provides important clues on their formation and processing in the early solar system. We preformed coordinated analyses of a comet dust particle that had been prepared using ultramicrotomy for TEM analysis. Following the TEM analyses, we extracted a 70 nm thick section from a region of the carbon (C) film of the TEM grid, for additional analyses. A carbon ring ~2-3 μm thick was deposited on top of the C film using the FIB. The C film on the outer rim of the ring was milled away using various patterns to uniformly release the stresses on the film, preventing rupture and collapse, and was attached to the micromanipulator needle. We then isolated the ring completely and transferred the section to a silicon sample holder for analysis using the HXN (hard X-ray nanoprobe) beamline at NSLSII at Brookhaven National Lab. Coordinated Analyses of Presolar Grains. Rare sub-m presolar grains that originate in evolved stars and supernovae, occur in primitive astromaterials and are identified by their exotic isotopic compositions. Coordinated analyses of these grains using NanoSIMS, TEM, and other techniques on the same grain is enabled by innovative FIB sample preparation. In order to obtain subsequent isotopic analyses of Mg and Fe, contributions from surrounding grains were minimized. We precisely deposited a protective cap of Pt on top of the grain to preserve the grain of interest and then milled away about 5 μm diameter of the surrounding material. Following the isotopic analyses, the spindle was extracted and thinned to electron transparency for TEM microstructural analyses. In situ heating TEM experiments on lunar samples. We extracted a FIB thin section from Apollo 17 lunar rock 76015. To avoid ion-beam damage, e-beam deposition was used to deposit the first 500 nm of the C strap, followed by ion beam-assisted deposition of ~3 μm carbon. We performed an ex situ lift-out of the section and placed the section on one of the elements of a microelectromechanical systems (MEMS) - specialized heating substrate and attached the section to the substrate by depositing small C straps with the FIB. The heating chips utilize silicon nitride windows to support the samples and provide uniform heating while enabling TEM imaging. The heating chip was loaded into a Hitachi “Blaze” heating holder and analyzed using a Hitachi HF5000 at the University of Arizona.

Rahman, Z.↗

Ground Calibration of the Astro-H (Hitomi) Soft X-Ray Spectrometer

The Astro-H (Hitomi) Soft X-ray Spectrometer (SXS) was a pioneering imaging x-ray spectrometer with 5 eV energy resolution at 6 keV. The instrument used a microcalorimeter array at the focus of a high-throughput soft x-ray telescope to enable high-resolution non-dispersive spectroscopy in the soft x-ray waveband (0.3-12 keV). We present the suite of ground calibration measurements acquired from 2012-2015, including characterization of the detector system, anti-coincidence detector, optical blocking filters, and filter-wheel filters. The calibration of the 36-pixel silicon thermistor microcalorimeter array includes parameterizations of the energy gain scale and line spread function for each event grade over a range of instrument operating conditions, as well as quantum efficiency measurements. The x-ray transmission of the set of five Al/polyimide thin-film optical blocking filters mounted inside the SXS dewar has been modeled based on measurements at synchrotron beamlines, including with high spectral resolution at the C, N, O, and Al K-edges. In addition, we present the x-ray transmission of the dewar gate valve and of the filters mounted on the SXS filter wheel (external to the dewar), including beryllium, polyimide, and neutral density filters.

detectors↗

Reflectivity Around the Gold L-Edges of X-Ray Reflector of the Soft X-Ray Telescope Onboard ASTRO-H

We report the atomic scattering factor in the 11.215.4 keV for the ASTRO-H Soft X-ray Telescope (SXT) obtained in the ground based measurements. The large effective area of the SXT covers above 10 keV. In fact, the flight data show the spectra of the celestical objects in the hard X-ray band. In order to model the area, the reflectivity measurements in the 11.2-15.4 keV band with the energy pitch of 0.4-0.7 eV were made in the synchrotron beamline Spring-8 BL01B1. We obtained atomic scattering factors f1 and f2 by the curve fitting to the reflectivities of our witness sample. The edges associated with the golds L-I, II, and III transitions are identified, of which the depths are found to be roughly 60 percent shallower than those expected from the Henke's atomic scattering factor.

X-rays↗

Olivine Dissolution and Formation of Secondary phases in Ultramafic Soils

Introduction: Olivine has been proposed as an indicator for the duration of water-rock interaction within Martian rocks and sediments [1-3]. The use of olivine as a mineralogical indicator for past aqueous alteration on Mars requires interpretation of a complex combination of factors including pH, temperature, and composition [5,6]. Here, we examine the persistence of natural olivine within terrestrial ultramafic soils (Fe/Mg-rich, Al-poor) developing under different climatic conditions and the incipient dissolution of emplaced forsterite (Fo) and fayalite (Fa) surfaces to investigate environmental effects on incipient olivine dissolution, olivine persistence in soils, and formation of secondary phases. Methods: Field Sites. We examined olivine weathering and secondary material formation in ultramafic soils at 6 sites in the Klamath Mountains (KM) of northern California with a mean annual temperature of ~12.8℃ and precipitation of ~55.7-95.4 cm/year [7], and soil pH of ~6.5-7.3; 4 sites in the Tablelands (TB) of Newfoundland, Canada with a mean annual temperature of <3.9℃ and precipitation of ~120.0 cm/year [8], and soil pH of ~7.7; and at 3 sites at Pickhandle Gulch (PG), Nevada with a mean annual temperature of ~14.4℃ and precipitation of ~14.1 cm/year [7], and soil pH of ~8.5. Sampling sites span an age range of ~12.1-50+ kya in the Klamath Mountains [9,10] and ~13-30 kya in the Tablelands [11]. Pickhandle Gulch sites are undated. Parent Material and Soil Analyses. Polished thin sections of bulk soil prepared by Wagner Petrographic, Inc were carbon-coated and analyzed on a JEOL 2100 SEM in back-scattered electron mode in the EMIL lab at UNLV and at the 13-ID-E synchrotron beamline at Argonne National Laboratory using µXRF, µXRD, and XAS. Soil and parent material samples were powdered in a Fritsch pulverisette and analyzed by XRD and soil by VNIR. Soil preparation is further described in [12]. Disk Preparation, Burial, and Collection. Fo disks were cut from a column prepared via hot-pressing and Fa disks by sintering synthetic fayalite powder, see [13] for detail. Disks were polished to a 0.25-micron level with diamond grit. Disks were buried in 3 KM soils, 4 TB soils, and 3 PG soils, collected after exactly 365 days, and washed gently with 100% reagent grade ethanol to remove potential adhered soil material. Weathered disks and soil samples were stored in a -20℃ freezer until analysis. Unaltered control disks prepared identically to the buried disks were stored at -20℃ for the duration of the experiment. Disk Analyses. One Fo and Fa disk from each climate zone was analyzed on a variable pressure Zeiss Supra 40VP SEM at Northern Arizona University. A separate Fo and Fa disk from each climate zone was analyzed by XPS using a Physical Electronics VersaProbe II at the Penn State Univ. Materials Characterization Lab after a Na-dodecyl sulfate wash and ozonation to remove carbon contamination as in [14]. VNIR measurements were conducted at Johnson Space Center using an ASD FieldSpec3 under ambient lab conditions on a separate Fo and Fa disk from each climate zone. One separate Fo and Fa control sample was analyzed for each technique for comparison with weathered samples. XPS uncertainty was determined from 5 repeat measurements on controls. Results: Bedrock and Soil Results Olivine is present in the parent material in the KM and TB. Olivine is found in ~12.1 ka KM soils but is absent from all older soils, while persisting into the oldest (>20 ka) TB soil (Figure 1). In both locations, olivine is found as cores surrounded by a serpentine rind (Figure 2). VNIR spectra from the analyzed soils possess strong OH-associated spectral features at ~2.33 µm indicating the presence of Mg-rich phyllosilicates as well as ferric-oxide features at ~0.92 µm in the KM (Figure 3). Primary crystalline silicate grains mostly incorporate Fe2+, while poorly crystalline weathering rinds are best fit by ferric oxide XAS standards (Figure 4). µXRF also shows that Fe and Ni concentrate in weathering rinds and Cr remains within interior silicate grains (Figure 4). Buried Sample Results All Fo surfaces exhibited formation of dissolution features including shallow pitting not observed on controls. Dissolution features were most visually widespread on the KM disk (Figure 5). Leaching of Mg from KM and TB Fo disks was evident from <1.6 Mg/Si ratios measured by XPS (Figure 6). Fe-rich precipitates in SEM (Figure 5) and Fe presence in XPS scans (Figure 6) indicate Fe deposition onto KM and TB Fo disk surfaces. The appearance of a spectral feature at 0.55 µm in the VNIR spectra from the TB Fo suggests this Fe is ferric (Figure 7). The PG Fo appears least altered, with minimal formation of dissolution features in SEM (Figure 5), a Mg/Si ratio inconsistent with leaching (~2) (Figure 6), and VNIR spectra almost identical to the control sample. Analysis of Fa surfaces is ongoing. The higher temperatures and more acidic pH in the KM soils likely drive the faster dissolution of the Fo disks described above. While the TB soils experience greater precipitation than in the KM, the cooler temperatures and more basic soil pH facilitate observable but more limited alteration. The dry climate and basic soil pH at PG lead to minimal dissolution of the PG disk surfaces.

A D Feldman↗

UV/VUV radiometric calibrations at SURF II

Since 1981 more than 150 instrument calibrations have been performed on the radiometric instrumentation calibration beamline at the Synchrotron Ultraviolet Radiation Facility (SURF II) at the National Institute of Standards and Technology (NIST) in Gaithersburg, Maryland. This 300 MeV electron storage ring operates routinely at electron currents greater than 250 mA. The spectrometer calibration beamline provides a continuum of radiation from 4 nm through the visual spectral region in the form of an intense beam with total angular divergence of 1.2 mrad. The probable uncertainty for the flux ranges from about 5 percent at 4 nm to less than 2 percent above 20 nm. The new system will radiometrically trace to SURF II, and thus is expected to reduce the calibration uncertainty for diodes in this region by a factor of five to the 1-2 percent level.

Furst, Mitchell L.↗

Searching for the Best Protein Crystals: Synchrotron Based Measurements of Protein Crystal Quality

We are developing X-ray diffraction methods to quantitatively evaluate the quality of protein crystals. The ultimate use for these crystal quality will be to optimize crystal growth and freezing conditions to obtain the best diffraction data. We have combined super fine-phi slicing with highly monochromatic, low divergence synchrotron radiation and the ADSC Quantum 4 CCD detector at the Stanford Synchrotron Radiation laboratory beamline 1.5 to accurately measure crystal mosaicity. Comparisons of microgravity versus earth-grown insulin crystals using these methods will be presented.

Borgstahl, Gloria↗

Formation of Insoluble Organic Material from the Ultraviolet Irradiation of Laboratory Ice Photolysis Residues

We present preliminary results from the study of ice photolysis residues which were exposed to ultraviolet (UV)/extreme UV (EUV) photon radiation. The residues were produced from the simultaneous deposition and UV irradiation of ice mixtures of astrophysical interest (H2O, CH3OH, CO, NH3, without/with N2 and/or O2, and without/with small quantities of aromatic compounds) at 15–20 K using an H2 lamp, which emits 10.2-eV (121.6 nm) Lyman-α photons and a continuum at 7.5–8 eV (155–165 nm). After warm-up to room temperature and subsequent sublimation of volatile compounds, the refractory materials (residues) recovered at room temperature were analyzed with infrared (IR) microscopy and then further irradiated with UV/EUV photons at a synchrotron facility, on a beamline providing a broad-band photon beam in the 4–45-eV range with a ~1016 photons s-1 flux.2 The residues were UV/EUV irradiated with increasing photon doses ranging from ~1018 to ~1021 photons, i.e., covering 4 orders of magnitude and relevant to those experienced by ice-coated grains in the protosolar nebula.1. After UV/EUV irradiation, residues were analyzed with IR microscopy and the data compared to those before irradiation to identify changes in chemical composition as a function of the photon dose. UV/EUV-irradiated residues were also analyzed with other techniques such as nanoscale secondary-ion mass spectrometry (nanoSIMS) to the study the changes in isotopic composition, and scanning transmission electron microscopy to look at variations in structure and C bonding distribution. Results will be compared with data from extraterrestrial materials, in particular, meteoritic insoluble organic material (IOM) and interplanetary dust particles (IDPs).

Ices↗

Efficiency measurements of reflection gratings in the 100-300-A band

Zero-order and first-order efficiencies of plane diffraction grazings over the 100-300-A band have been measured using the NRL beamline facility at the National Synchrotron Light Source. Measurements were taken at grating angles of 5, 10, and 15 deg, and the incident radiation was polarized primarily in the transverse magnetic mode. Four (three laminar, one blazed) of the gratings were ion etched in high quality quartz blanks, overcoated with 200 A of gold. A fifth (blazed) grating was ruled in gold. The line densities are 1000, 2000, and 3600 grooves/mm for those with laminar profiles. Both blazed gratings have a blaze angle of 8 deg and line densities of 3600 grooves/mm. Measured first-order efficiencies up to 15 percent were obtained for the laminar gratings and up to 8 percent was obtained for the ion-etched blazed grating. Much lower efficiencies (not greater than 2 percent) were measured for the ruled grating. A computer program was written to calculate grating efficiencies using a full electromagnetic model. Measured efficiencies of the ion-etched gratings agree well with predicted values, but the measured first-order efficiency of the ruled grating is much lower than predicted.

Meekins, John F.↗

Trace Element Abundance Measurements on Cosmic Dust Particles

The X-Ray Microprobe on beamline X-26A at the National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory was used to determine the abundances of elements from Cr through Sr in individual interplanetary dust particles (IDPs) collected from the Earth's stratosphere and the Scanning Transmission X-ray Microscope (STXM) on beamline X-1A at the NSLS was used to determine the carbon abundances and spatial distributions in IDPs. In addition, modeling was performed in an attempt to associate particular types of IDPs with specific types of parent bodies, and thus to infer the chemistry, mineralogy, and structural properties of those parent bodies.

Flynn, George↗

First Protein Crystallization Experiments on The International Space Station: Sweet Success in Space With Thaumatin

We determined the room temperature 1.2 A structure of thaumatin using a crystal grown in the first protein crystallization experiment conducted aboard the International Space Station (ISS). The crystals were grown in the Enhanced Gaseous Nitrogen Dewar (EGN) developed by Alexander McPherson and co-workers. EGN transports frozen solutions contained in tygon tubing in a liquid nitrogen Dewar to ISS where the tubes then thaw. Batch, free interface diffusion (FID), or vapor diffusion crystallization occurs after thawing. EGN was flown to the ISS on STS-106 on September 8, 2000. This was a "risk mitigation" flight that tested EGN performance and the process of conducting experiments on ISS. We focused on how to map a hanging drop crystallization recipe to the EGN FID method. Thaumatin was chosen as the test system. Three series of crystallization recipes were set-up. Each series tested different volume ratios of protein-rich solution to precipitant-rich solution. The series differed from each other by fixing either the protein concentration or the amount of protein in the solutions. Upon return of the samples to Earth on October 24 by STS-92, bubbles that spanned the diameter of the tubing were observed in all tubes. Such bubbles interrupt liquid-liquid diffusion and force vapor diffusion equilibration to occur instead. Nonetheless, crystals grew in 9 of 30 tubes. Many large crystals were grown, the largest being 2.0 x 1.1 x 1.0 cubic mm. The largest crystal was used to collect data at room temperature on beamline 7-1 of the Stanford Synchrotron Radiation Source to a maximum resolution of 1.2 A. The structure was refined anisotropically using SHELX with a data to parameter ratio of 4.5 to give an R(sub factor) of 15.8% (R(sub free) = 18.2%) for ail reflections without generated hydrogens. This refinement is proceeding. Comparisons of this 1.2 A microgravity structure to previous reports of the thaumatin structure at 1.75 A and to ground control crystals will be presented.

Kundrot, Craig E.↗

Effect of a Synchrotron X-ray Microtomography Imaging Experiment on the Amino Acid Content of a CM Chondrite

X-ray microcomputed tomography and synchrotron X-ray microcomputed tomography (μCT) are becoming popular tools for the reconnaissance imaging of chondrites. However, there are occasional concerns that the use of μCT may be detrimental to organic components of a chondrite. Soluble organic compounds represent ~2–10% of the total solvent extractable carbon in CI and CM carbonaceous chondrites and amino acids are among the most abundant compounds in the soluble organic fraction. We irradiated two samples of the Murchison CM2 carbonaceous chondrite under conditions slightly harsher (increased beam exposure time) than those typically used for x-ray μCT imaging experiments to determine if detectable changes in the amino acid abundance and distribution relative to a nonexposed control sample occurred. After subjecting two meteorite portions to ionizing radiation dosages of 1.1 kiloGray (kGy) and 1.2 kGy with 48.6 and 46.6 keV monochromatic X-rays, respectively, we analyzed the amino acid content of each sample. Within analytical errors, we found no differences in the amino acid abundances or enantiomeric ratios when comparing the control samples (nonexposed Murchison) and the irradiated samples. We show with calculations that any sample heating due to x-ray exposure is negligible. We conclude that a monochromatic synchrotron X-ray μCT experiment at beamline 13-BM-D of the Advanced Photon Source, which imparts ~1 kGy doses, has no detectable effect on the amino acid content of a carbonaceous chondrite. These results are important for the initial reconnaissance of returned samples from the OSIRIS-REx and Hayabusa 2 asteroid sample return missions.

Jon M. Friedrich↗

Beamline Electrostatic Levitator (BESL) for in-situ High Energy K-Ray Diffraction Studies of Levitated Solids and Liquids at High Temperature

Determinations of the phase formation sequence, the crystal structures and the thermodynamic properties of materials at high temperatures are difficult because of contamination from the sample container and environment. Containerless processing techniques, such as electrostatic (ESL), electromagnetic (EML), aerodynamic, and acoustic levitation, are most suitable these studies. An adaptation of ESL for in-situ structural studies of a wide range of materials, including metals, semiconductors, insulators using high energy (125 keV) synchrotron x-rays is described here. This beamline ESL (BESL) allows the in-situ determination of the atomic structures of equilibrium solid and liquid phases, including undercooled liquids, as well as real-time studies of solid-solid and liquid-solid phase transformations. The use of image plate (MAR345) or GE-Angio detectors enables fast (30 ms - 1s) acquisition of complete diffraction patterns over a wide q-range (4 - 140/mm). The wide temperature range (300 - 2500 K), containerless processing under high vacuum (10(exp -7) - 10(exp -8) torr), and fast data acquisition, make BESL particularly suitable for phase diagram studies of high temperature materials. An additional, critically important, feature of BESL is the ability to also make simultaneous measurement of a host of thermo-physical properties, including the specific heat, enthalpy of transformation, solidus and liquidus temperatures, density, viscosity, and surface tension; all on the same sample and simultaneous with the structural measurements.

Gangopadhyay, A. K.↗

Performance Report: A timeline for the synchrotron calibration of AXAF

Presented herein are the known elements of the timeline for synchrotron reflectance calibrations of HRMA witness samples (Section 2). In Section 3, lists of measurements to be done on each witness flat are developed. The elements are then arranged into timelines for the three beamlines we expect to employ in covering the full 50-12,000 eV energy range (Section 4). Although the required AXAF operational range is only 0.1-10 keV, we must calibrate the extent to which radiation just outside this band may contaminate our in-band response. In Section 5, we describe the working relationships which exist with each of the beamlines, and estimate the time available for AXAF measurements on each. From the timelines and the available time, we calculate the number of flats which could be measured in full detail over the duration of the program for each beamline. A suggestion is made regarding a minimum required baselines of witness flats from each element coating run or qualification run to be used in the calibration. We intend that this suggestion open discussion of the issue of witness flat deployment.

Tananbaum, H. D.↗

Effect of Tube-Based X-Ray Microtomography Imaging on the Amino Acid and Amine Content of the Murchison CM2 Chondrite

X-ray and synchrotron X-ray micro-computed tomography (micro-CT) are increasingly being used for three dimensional reconnaissance imaging of chondrites and returned extraterrestrial material prior to detailed chemical and mineralogical analyses. Although micro-CT imaging is generally considered to be a non-destructive technique since silicate and metallic minerals in chondrites are not affected by X-ray exposures at the intensities and wavelengths typically used, there are concerns that the use of micro-CT could be detrimental to the organics in carbonaceous chondrites. We recently conducted a synchrotron micro-CT experiment on a powdered sample of the Murchison CM2 carbonaceous chondrite exposed to a monochromatic high energy (approximately 48 kiloelectronvolts) total X-ray radiation dose of approximately 1 kilogray (kGy) using the Advanced Photon Source beamline 13-BMD (13-Bending Magnet-D Beamline) at Argonne National Laboratory and found that there were no detectable changes in the amino acid abundances or enantiomeric compositions in the chondrite after exposure relative to a Murchison control sample that was not exposed. However, lower energy bremsstrahlung X-rays could interact more with amino acids and other lower molecular weight amines in meteorites. To test for this possibility, three separate micro-CT imaging experiments of the Murchison meteorite using the GE Phoenix v/tome/x s 240 kilovolt microfocus high resolution tungsten target X-ray tube instrument at the American Museum of Natural History (AMNH) were conducted and the amino acid abundances and enantiomeric compositions were determined. We also investigated the abundances of the C1-C5 amines in Murchison which were not analyzed in the first study.

Microtomography Imaging↗

Radiation Beamline Testbeds for the Simulation of Planetary and Spacecraft Environments for Human and Robotic Mission Risk Assessment

The Center for Radiation Engineering and Science for Space Exploration (CRESSE) at Prairie View A&M University, Prairie View, Texas, USA, is establishing an integrated, multi-disciplinary research program on the scientific and engineering challenges faced by NASA and the international space community caused by space radiation. CRESSE focuses on space radiation research directly applicable to astronaut health and safety during future long term, deep space missions, including Martian, lunar, and other planetary body missions beyond low earth orbit. The research approach will consist of experimental and theoretical radiation modeling studies utilizing particle accelerator facilities including: 1. NASA Space Radiation Laboratory (NSRL) at Brookhaven National Laboratory; 2. Proton Synchrotron at Loma Linda University Medical Center; and 3. Los Alamos Neutron Science Center (LANSCE) at Los Alamos National Laboratory. Specifically, CRESSE investigators are designing, developing, and building experimental test beds that simulate the lunar and Martian radiation environments for experiments focused on risk assessment for astronauts and instrumentation. The testbeds have been designated the Bioastronautics Experimental Research Testbeds for Environmental Radiation Nostrum Investigations and Education (BERT and ERNIE). The designs of BERT and ERNIE will allow for a high degree of flexibility and adaptability to modify experimental configurations to simulate planetary surface environments, planetary habitats, and spacecraft interiors. In the nominal configuration, BERT and ERIE will consist of a set of experimental zones that will simulate the planetary atmosphere (Solid CO2 in the case of the Martian surface.), the planetary surface, and sub-surface regions. These experimental zones can be used for dosimetry, shielding, biological, and electronic effects radiation studies in support of space exploration missions. BERT and ERNIE are designed to be compatible with the experimental areas associated with the above facilities. CRESSE has broad expertise in space radiation in the areas of space radiation environment modeling, Monte-Carlo radiation transport modeling, space radiation instrumentation and dosimetry, radiation effects on electronics, and multi-functional composite shielding materials. The BERT and ERNIE testbeds will be utilized in individual and collaborative research incorporating this expertise. The research goal is to maximize the technical readiness level (TRL) of radiation instrumentation for human and robotic missions, optimizing the return value of CRESSE for NASA exploration and international co-operative missions. Outcomes and knowledge from research utilizing BERT and ERNIE will be applied to a variety of scientific and engineering disciplines vital for safe and reliable execution of future space exploration missions, which can be negatively impacted by the space radiation environment. The testbeds will be central to a variety of university educational activities and educational goals of NASA. Specifically, BERT and ERNIE will enhance educational opportunities in science, technology, engineering and mathematics (STEM) disciplines for engineering and science students at PVAMU, a historically black college/university. Preliminary data on prototype testbed configurations, including simulated lunar regolith (JSC-1A stimulant based on Apollo 11 samples), regolith/polyethylene composites, and dry ice, will be presented to demonstrate the usefulness of BERT and ERNIE in radiation beam line experiments.

Wilkins, Richard↗

Diversity in C-Xanes Spectra Obtained from Carbonaceous Solid Inclusions from Monahans Halite

Monahans meteorite (H5) contains fluid inclusion- bearing halite (NaCl) crystals [1]. Microthermometry and Raman spectroscopy showed that the fluid in the inclusions is an aqueous brine and they were trapped near 25degC [1]. Their continued presence in the halite grains requires that their incorporation into the H chondrite asteroid was post metamorphism [2]. Abundant solid inclusions are also present in the halites. The solid inclusions include abundant and widely variable organics [2]. Analyses by Raman microprobe, SEM/EDX, synchrotron X-ray diffraction and TEM reveal that these grains include macromolecular carbon similar in structure to CV3 chondrite matrix carbon, aliphatic carbon compounds, olivine (Fo99−59), high- and low-Ca pyroxene, feldspars, magnetite, sulfides, lepidocrocite, carbonates, diamond, apatite and possibly the zeolite phillipsite [3]. Here we report organic analyses of these carbonaceous residues in Monahans halite using C-, N-, and O- X-ray absorption near edge structure (XANES). Samples and Methods: Approximately 100 nm-thick sections were extracted with a focused ion beam (FIB) at JSC from solid inclusions from Monahans halite. The sections were analyzed using the scanning transmission X-ray microscope (STXM) on beamline 5.3.2.2 at the Advanced Light Source, Lawrence Berkeley National Laboratory for XANES spectroscopy. Results and Discussion: C-XANES spectra of the solid inclusions show micrometer-scale heterogeneity, indicating that the macromolecular carbon in the inclusions have complex chemical variations. C-XANES features include 284.7 eV assigned to aromatic C=C, 288.4-288.8 eV assigned to carboxyl, and 290.6 eV assigned to carbonate. The carbonyl features obtained by CXANES might have been caused by the FIB used in sample preparation. No specific N-XANES features are observed. The CXANES spectra obtained from several areas in the FIB sections include type 1&2 chondritic IOM like, type 3 chondritic IOM like, and none of the above. The natures of the macromolecular carbon in the solid inclusions observed by C-XANES are consistent with the previous studies showing that the carbonaceous solid inclusions have not originated from Monahans parent body [1-3], and have various origins, including various chondritic meteorite parent bodies as well as other unknown source(s).

Kebukawa, Y.↗

Killing of Bacillus Megaterium Spores by X-Rays at the Phosphorus K-Edge

This study continues a progression of experiments on the radiation-induced killing of bacterial spores that began at the Argonne National Laboratory in 1957. A series of aliquots of Bacillus megaterium spores were prepared onto polycarbonate filters and irradiated with photons of 2159 eV compared to 2140 eV energy on the 2-IDB beamline at the Advanced Photon Source. Flux density was approximately 10 photons/sec/mm . The phosphorous K-edge absorption spectrum in these spores was determined to peak at 2159 eV, wheras 2140 eV was determined to be outside that absorption spectrum. Spores on filters were irradiated at ambient conditions, and were either immediately plated for colony formation after irradiation, or were held for postirradiation exposure to oxygen prior to plating. Slopes of survival curves from the four conditions of irradiation, i.e., two photon energies each comparing immediate plating vs postirradiation holding, were used for quantitative determination of differences in rates of spore killing over a range of radiation doses. It was found that spores irradiated at the phosphorus K-edge were killed 20% more efficiently than when irradiated with 2140eV photons, and this was true for both immediate plating and postirradiation holding in air. Postirradiation holding in air increased killing efficiency by about 12% for both photon energies compared to plating immediately after irradiation. The increase of killing efficiency with postirradiation holding is less than expected from earlier experiments using relatively low-flux X-rays, and raises the possibility of dose-mitigation by radical-radical recombination in the case of high-flux X-rays from the synchrotron.

Richmond, Robert C.↗

Killing of Bacillus Megaterium Spores by X-rays at the Phosphorus K-edge

This study continues a progression of experiments on the radiation-induced killing of bacterial spores that began at the Argonne National Laboratory in 1957. A series of aliquots of Bacillus megaterium spores were prepared onto polycarbonate filters and irradiated with photons of 2159 eV compared to 2140 eV energy on the 2-IDB beamline at the Advanced Photon Source. Flux density was approximately 10(exp 18) photons/sec/sq mm. The phosphorous K-edge absorption spectrum in these spores was determined to peak at 2159 eV, wheras 2140 eV was determined to be outside that absorption spectrum. Spores on filters were irradiated at ambient conditions, and were either immediately plated for colony formation after irradiation, or were held for postirradiation exposure to oxygen prior to plating. Slopes of survival curves from the four conditions of irradiation, i.e., two photon energies each comparing immediate plating vs postirradiation holding, were used for quantitative determination of differences in rates of spore killing over a range of radiation doses. It was found that spores irradiated at the phosphorus K-edge were killed 20% more efficiently than when irradiated with 2140 eV photons, and this was true for both immediate plating and postirradiation holding in air. Postirradiation holding in air increased killing efficiency by about 12% for both photon energies compared to plating immediately after irradiation. The increase of killing efficiency with postirradiation holding is less than expected from earlier experiments using relatively low-flux X-rays, and raises the possibility of dose-mitigation by radical-radical recombination in the case of high-flux X-rays from the synchrotron.

Richmond, Robert C.↗