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INL CRMO XRF Special Report No. 3: INL CRMO XRF Calibration Methods for the Analysis of Ceramics and Brick

This report details the analytical methods used by the Idaho National Laboratory Cultural Resource Management Office to characterize ceramic and brick artifacts using X-ray fluorescence spectrometry. More specifically, this report provides details on instrumentation, analysis times, and matrix-specific calibration protocols for ceramic materials. Calibration curves were developed to adjust raw instrumental output for 13 elements using a suite of reference standards made from historic brick borrowed from the Yale Peabody Museum. Calibration curves were validated by plotting predicted values against published reference values for the calibration set as well as a certified soil reference standard (SRM 2711a).

36 MATERIALS SCIENCE↗

A Deep Search with HST for Late Time Supernova Signatures in the Hosts of XRF 011030 and XRF 020427

X-ray Flashes (XRFs), are, like Gamma-Ray Bursts (GRBs) thought to signal the collapse of massive stars in distant galaxies. Many models posit that the isotropic equivalent energies of XRFs are lower than those for GRBs, such that they are visible hom a reduced range of distances when compared with GRBs. Here we present the results of two epoch Hubble Space Telescope imaging of two XRFs. These images taken approximately 45 and 200 days post bust reveal no evidence for an associated supernova in either case. Supernovae such as SN 1998bw would have been visible out to z approximately 1.5 in each case, while faint supernovae such as SN 2002ap would be visible to z approximately 1. At these distances the bursts would not fit the observed correlations between E(sub p) and E(sub iso) and would have required extremely luminous X-ray afterglows. We conclude that should these XRFs reside at low redshift, it is necessary either that their line of sight is heavily extinguished, or that XRFs, unlike GRBs do not have temporally coincident supernovae.

Patel, Sandeep↗

A Deep Search with the Hubble Space Telescope for Late-Time Supernova Signatures in the Hosts of XRF 011030 and XRF 020427

X-ray flashes (XRFs) are, like gamma-ray bursts (GRBs), thought to signal the collapse of massive stars in distant galaxies. Many models posit that the isotropic equivalent energies of XRFs are lower than those for GRBs, such that they are visible fiom a reduced range of distances when compared with GRBs. Here we present the results of two-epoch Hubble Space Telescope imaging of two XRFs. These images, taken approximately 45 and 200 days postburst, reveal no evidence of an associated supernova in either case. Supernovae such as SN 1998bw would have been visible out to z approximately 1.5 in each case, while fainter supernovae such as SN 2002ap would have been visible to z approximately 1. If the XRFs lie at such large distances, their energies would not fit the observed correlation between the GRB peak energy and isotropic energy release (E(sub p) proportional to E(sub iso)(sup 1/2), in which soft bursts are less energetic. We conclude that, should these XRFs reside at low redshifts (z less than 0.6), either their line of sight is heavily extinguished, they are associated with extremely faint supernovae, or, unlike GRBs, these XRFs do not have temporally coincident supernovae.

Levan, Andrew↗

Rapid AI-based Dissection of Ashes using Raman and XRF Spectroscopy (RADAR-X)

Waste-to-energy (WTE) facilities incinerate ~35 million tons of municipal solid waste annually in the United States. The incineration process reduces the mass and the volume of the waste fraction by over 75 and 95%, respectively. The fraction left after incineration remains as ash residues and is referred to as WTE ash, compromising of bottom and fly ash. In the United States, ~10 million tons of WTE ashes are generated annually and predominantly landfilled because of the lack of secondary end-use pathways. This incurs a significant financial burden (landfilling costs) on U.S. WTE facilities and also results in the loss of materials to the landfill. The primary objective of this research is to understand better the elemental and mineralogical composition of WTE ashes from diverse origins and find composition dependent upcycling pathways for diverting these ashes from landfills. This primary objective was addressed through three research tasks –(Task I) An AI-led Multi-Modal Approach for Compositional Analysis, (Task II) Developing a Dissolution-Based Test for Real Time Analysis, and (Task III) Establishing composition-dependent end uses. The chemical composition of WTE ash is dependent on two factors, i.e., the input waste composition and the operational parameters of a WTE facility (combustion conditions). Amongst these two factors, the input waste composition will likely show spatial and temporal variation. As a result, the chemical composition of WTE ash will also fluctuate. To understand the spatial and temporal variation in WTE ash composition, in Task I, we collected 128 ash samples (62 bottom ash and 66 fly ash samples) from 11 WTE facilities located in 11 U.S. states and characterized them via X-ray Fluorescence, powder X-ray Diffraction, and Raman Spectroscopy. The findings from this extensive characterization work indicated that the key elements in WTE fly ashes are Ca, Cl (greater than 10 wt. %), Si, S, K, Zn ( between 1 and 10 wt. %), Mg, Al, P, Ti, Fe, Cu, Br, and Pb (between 0.1 and 1 wt. %). Similarly, the key elements in WTE bottom ash fraction finer than 45μm are Ca (greater than 10 wt. %), Mg, Al, Si, S, Cl, K, Ti, Fe, Zn (between 1 and 10 wt. %), P, V, Cr, Mn, Cu, Br, and Pb (between 0.1 and 1 wt. %). Here, we note that the dominant fraction of WTE bottom ash is the coarse fraction. The coarse WTE bottom ash fraction (rich in silicon) was not characterized in this study because of excessive grinding requirements and their unsuitability as a supplementary cementitious material due to their coarse nature. The elements in WTE bottom ashes are present as calcite, anhydrite, vaterite, hydroxyapatite, quartz, bassanite, gehlenite, akermanite, hydrocalumite, and portlandite. Similarly, the mineralogical species present in WTE fly ashes are calcium chloride hydroxide, halite, calcite, anhydrite, sylvite, hydrocalumite, vaterite, hannebachite, quartz, and bassanite. Temporal variation in ash composition may also result in significant fluctuations in chemical compositions. Therefore, a WTE facility may need to monitor the ash composition (elemental and mineralogical composition) in real time. In Task I, we evaluated the possibility of using a portable X-ray fluorescence (XRF) spectrometer to monitor the elemental composition in real-time. Specifically, we collected XRF data on identical specimens via a portable XRF spectrometer (low-end) and a lab-based benchtop XRF spectrometer (high-end). The collected data was used to train an A.I. algorithm (portable XRF data as an input and benchtop XRF data as an output) to predict accurate elemental composition using portable XRF data. Finally, we developed a 2-minute photobleaching protocol to monitor the mineralogical characteristics of WTE ashes via Raman spectroscopy. Overall, the activities in Task I improved our understanding of ash composition and developed techniques to monitor elemental and mineralogical composition in near real-time. Based on the findings of Task I, we find that WTE ashes exhibit wide variability in mineralogy. For ICP-based elemental analysis, all the mineralogical species in WTE ashes must be brought into solution. This is traditionally accomplished with acid digestion using a combination of multiple acids. However, acid digestion with multiple acids is time-consuming and often fails to ensure complete digestion of the ash matrix. To address this limitation, in Task II, we developed an alkali-fusion-based digestion protocol using a combination of lithium tetraborate, lithium metaborate, and their combinations as possible alkali fluxes for digesting WTE ashes entirely and rapidly. The validity of the developed method was evaluated on two standard ash specimens, i.e., SRM 1633c coal fly ash and BCR-176R incineration fly ash specimen. The findings suggest that the developed protocol can ensure complete digestion of elements such as Al, Ba, Ca, Cr, Cu, Mg, Mn, P, Sr, V, Zn, Be, K, and rare earth elements. The recent changes in the energy market towards renewables and increased metal recycling have resulted in reduced supplies of supplementary cementitious materials (coal fly ash and slag). Therefore, in Task III, we evaluated the possibility of employing WTE ashes as SCMs. As the chemical composition of WTE ashes varies temporally (on an hourly basis), there was also a need to develop tests that can evaluate the suitability of material to act as supplementary cementitious material rapidly, i.e., in a few minutes. Therefore, in Task II, we also developed a rapid test to assess the suitability of a material to act as an SCM in 5 minutes. This represents a significant advance over the state-of-the-art R 3 test, which takes ~144 hours. This test was initially validated on amorphous aluminosilicates, such as calcined clays, and could be extended to evaluate other industrial by-products, such as WTE ashes. In Task III, we evaluated the possibility of employing WTE ashes for two applications, i.e., as an SCM and a lime substitute for clay stabilization. The findings from Task I indicated that WTE ashes are enriched in chlorine and, therefore, cannot be used directly as an SCM due to corrosion-related risks and altered hydration kinetics. Accordingly, we developed an ash treatment protocol to reduce the solubility of chlorine-containing species in WTE ashes. The developed treatment protocol also immobilized lead in certain mineral forms. As a result of the treatment, WTE ashes can be used as SCMs without any corrosion or heavy metal leaching concerns. The second application examined in this study was clay stabilization. WTE ashes are calcium-rich and can be an adequate lime replacement for clay stabilization. Our findings reveal that the sum of the concentrations of Ca(OH) 2 and CaClOH controls the clay stabilization capability of WTE ashes. In summary, in this work, we evaluated the elemental and mineralogical characteristics of U.S. WTE ashes from diverse origins and developed tests to evaluate the chemical characteristics of these ashes in real time through a portable XRF and a benchtop Raman spectrometer. Based on the chemical characteristics of these ashes, we developed an ash treatment process to enable the use of WTE ashes as an SCM and also evaluated the possibility of employing these ashes for clay stabilization. Overall, the findings from this work enables the diversion of WTE ashes from landfills for multiple end-uses, i.e., as an SCM or a lime substitute for clay stabilization.

36 MATERIALS SCIENCE↗

Digital Equivalent Data System for XRF Labeling of Objects

A digital equivalent data system (DEDS) is a system for identifying objects by means of the x-ray fluorescence (XRF) spectra of labeling elements that are encased in or deposited on the objects. As such, a DEDS is a revolutionary new major subsystem of an XRF system. A DEDS embodies the means for converting the spectral data output of an XRF scanner to an ASCII alphanumeric or barcode label that can be used to identify (or verify the assumed or apparent identity of) an XRF-scanned object. A typical XRF spectrum of interest contains peaks at photon energies associated with specific elements on the Periodic Table (see figure). The height of each spectral peak above the local background spectral intensity is proportional to the relative abundance of the corresponding element. Alphanumeric values are assigned to the relative abundances of the elements. Hence, if an object contained labeling elements in suitably chosen proportions, an alphanumeric representation of the object could be extracted from its XRF spectrum. The mixture of labeling elements and for reading the XRF spectrum would be compatible with one of the labeling conventions now used for bar codes and binary matrix patterns (essentially, two-dimensional bar codes that resemble checkerboards). A further benefit of such compatibility is that it would enable the conversion of the XRF spectral output to a bar or matrix-coded label, if needed. In short, a process previously used only for material composition analysis has been reapplied to the world of identification. This new level of verification is now being used for "authentication."

Schramm, Harry F.↗

XRF-XFS-XAS-Auto v1.0 - Beta release

This software allows to analyze XRF maps, XFS spectra and XAS spectra collected at the Advanced Light Source's Beamline 10.3.2. Features include: 1) XRF maps: - process XRF maps, all elemental maps are saved as bmp automatically and labeled with the incident energy used, the scale bar is also labeled and can be controlled. - XRF elemental correlation plots, save the correlation plots automatically - Extract single or multiple transects in XRF maps on one or several regions of interest, each transect profile is numbered and saved in a corresponding folder, along with the corresponding maps showing transect location. 2) XFS spectra - save in log10 scale the XFS spectra, either a single or multiple files all at once. The files are saved as .bmp. - XFS spectra are labeled according to tabulated fluorescence emission lines. 3) XAS spectra - allows to plot individual scalers in the raw data. - allows calibration of the spectra using an Io internal glitch present in all spectra and performing 1st derivative. - Least-square linear combination fitting of XANES or extended XANES spectra using a database of standards using 1, 2 or 3 components maximum. It also provides the 5 top combinations and provide the user for the possibility of saving the 2nd, 3rd, 4th and 5th best combinations in addition to the best one. The processed spectra (pre-edge background substracted, post-edge normalized), the fits and residuals are automatically saved. A table of the component, with fit% and SSN is provided and saved automatically as well.

Fakra, Sirine↗

Evaluating Handheld X-Ray Fluorescence (XRF) Technology in Planetary Exploration: Demonstrating Instrument Stability and Understanding Analytical Constraints and Limits for Basaltic Rocks

While large-footprint X-ray fluorescence (XRF) instruments are reliable providers of elemental information about geologic samples, handheld XRF instruments are currently being developed that enable the collection of geochemical data in the field in short time periods (approx.60 seconds) [1]. These detectors are lightweight (1.3kg) and can provide elemental abundances of major rock forming elements heavier than Na. While handheld XRF detectors were originally developed for use in mining, we are working with commercially available instruments as prototypes to explore how portable XRF technology may enable planetary field science [2,3,4]. If an astronaut or robotic explorer visited another planetary surface, the ability to obtain and evaluate geochemical data in real-time would be invaluable, especially in the high-grading of samples to determine which should be returned to Earth. We present our results on the evaluation of handheld XRF technology as a geochemical tool in the context of planetary exploration.

Young, K. E.↗

Identification of New Lithic Clasts in Lunar Breccia 14305 by Micro-CT and Micro-XRF Analysis

From 1969 to 1972, Apollo astronauts collected 382 kg of rocks, soils, and core samples from six locations on the surface of the Moon. The samples were initially characterized, largely by binocular examination, in a custom-built facility at Johnson Space Center (JSC), and the samples have been curated at JSC ever since. Despite over 40 years of study, demand for samples remains high (~500 subsamples per year are allocated to scientists around the world), particularly for plutonic (e.g., anorthosites, norites, etc.) and evolved (e.g., granites, KREEP basalts) lithologies. The reason for the prolonged interest is that as new scientists and new techniques examine the samples, our understanding of how the Moon, Earth, and other inner Solar System bodies formed and evolved continues to grow. Scientists continually clamor for new samples to test their emerging hypotheses. Although all of the large Apollo samples that are igneous rocks have been classified, many Apollo samples are complex polymict breccias that have previously yielded large (cm-sized) igneous clasts. In this work we present the initial efforts to use the non-destructive techniques of micro-computed tomography (micro-CT) and micro x-ray fluorescence (micro-XRF) to identify large lithic clasts in Apollo 14 polymict breccia sample 14305. The sample in this study is 14305,483, a 150 g slab of regolith breccia 14305 measuring 10x6x2 cm (Figure 1a). The sample was scanned at the University of Texas High-Resolution X-ray CT Facility on an Xradia MicroXCT scanner. Two adjacent overlapping volumes were acquired at 49.2 micrometer resolution and stitched together, resulting in 1766 slices. Each volume was acquired at 100 kV accelerating voltage and 98 mA beam current with a 1 mm CaF2 filter, with 2161 views gathered over 360deg at 3 seconds acquisition time per view. Micro-XRF analyses were done at Washington University in St. Louis, Missouri on an EDAX Orbis PC micro-XRF instrument. Multiple scans were made at 40 kV accelerating voltage, 800 mA beam current, 30 μm beam diameter, and a beam spacing of 30-120 micrometer. The micro-CT scan of 14305,483 (Figure 2) was able to identify several large lithic clasts (approx. 1 cm) within the interior of the slab. These clasts will be exposed by band-sawing or chipping of the slab, and their composition more fully characterized by subsequent micro-XRF analysis. In addition to lithic clasts, the micro-CT scans identified numerous mineral clasts, including many FeNi metal grains, as well as the prominent fractures within the slab. The micro-XRF analyses (Figure 1b,c) of the slab surfaces revealed the bulk chemical compositions (qualitative) of the different clast types observed. In particular, by looking at the ratios of major elements (e.g. Ca:Mg:Fe), differences among the many observed clast types are readily observed. Moreover, several clasts not apparent to the naked eye were revealed in the K:Al:Si ratio map. The scans are also able to identify small grains of Zr- and P-rich minerals (not shown), which could in turn yield important age dates for the samples.

Zeigler, Ryan A.↗

In-Situ XRF Measurements in Lunar Surface Exploration Using Apollo Samples as a Standard

Samples collected during the Apollo lunar surface missions were sampled and returned to Earth by astronauts with varying degrees of geological experience. The technology used in these EVAs, or extravehicular activities, included nothing more advanced than traditional terrestrial field instruments: rock hammer, scoop, claw tool, and sample bags. 40 years after Apollo, technology is being developed that will allow for a high-resolution geochemical map to be created in the field real-time. Handheld x-ray fluorescence (XRF) technology is one such technology. We use handheld XRF to enable a broad in-situ characterization of a geologic site of interest based on fairly rapid techniques that can be implemented by either an astronaut or a robotic explorer. The handheld XRF instrument we used for this study was the Innov-X Systems Delta XRF spectrometer.

Young, Kelsey E.↗

Vacuum Attachment for XRF Scanner

Vacuum apparatuses have been developed for increasing the range of elements that can be identified by use of x-ray fluorescent (XRF) scanners of the type mentioned in the two immediately preceding articles. As a consequence of the underlying physical principles, in the presence of air, such an XRF scanner is limited to analysis of chlorine and elements of greater atomic number. When the XRF scanner is operated in a vacuum, it extends the range of analysis to lower atomic numbers - even as far as aluminum and sodium. Hence, more elements will be available for use in XRF labeling of objects as discussed in the two preceding articles. The added benefits of the extended capabilities also have other uses for NASA. Detection of elements of low atomic number is of high interest to the aerospace community. High-strength aluminum alloys will be easily analyzed for composition. Silicon, a major contaminant in certain processes, will be detectable before the process is begun, possibly eliminating weld or adhesion problems. Exotic alloys will be evaluated for composition prior to being placed in service where lives depend on them. And in the less glamorous applications, such as bolts and fasteners, substandard products and counterfeit items will be evaluated at the receiving function and never allowed to enter the operation

Schramm, Harry F.↗

XRF Characterization of MMOD Impact Damage

Introduction The Hypervelocity Impact Technology (HVIT) Group at the NASA Johnson Space Center (JSC) has performed over 150 post flight MMOD inspections on returned space-ex-posed hardware and collected over 1,600 samples. Determination of the impactor source typically requires an analysis of the projectile residue in the damage feature. At this time, about 20% of the samples have been processed. Types of Samples Samples in the HVIT group collection can be classified into two types. Indirect (non-destructive) samples are produced when a pliable material (e.g., adhesive tape or dental mold) is inserted into an impact feature. With this type of sampling technique, crater material and (hopefully) projectile residue material is embedded in the sample media and can detected using further chemical characterizing techniques. Direct (destructive) sampling involves the in-tact extraction of material from the spacecraft and is done in a manner that the entire impact feature can be excised intact. This technique provides the greatest chance of successfully determining impactor source due to the entirety of the projectile remnants being present within the collected sample. Updated Projectile Residue Detection Techniques Previous assessments of projectile provenance have involved the use of samples that are first mounted in epoxy, sectioned to expose the crater interior, imaged with a scanning electron microscope (SEM), then any observed impactor residue was then analyzed using an energy dispersive spectrometer (EDS). This technique, while proven, may be supplemented with other types of elemental analysis techniques that can observe major element chemistry, in order to improve throughput of sample analysis. The Astromaterials Research and Exploration Science (ARES) Division at JSC, for example, operates a Bruker M4 Tornado micro-X-Ray fluorescence (XRF) spectrometer, capable of creating elemental maps of areas around these small impact features in a couple of hours, with a spot size <20 μm. The potential advantage with this technique lies in sample preparation, as no polishing or conductive coatings are needed. Early trials attempted to deter-mine impactor composition by collecting spectra from intact samples by aiming the X-Rays directly into the impact feature, but the signal:noise ratio was too low for confident material identification. Sample preparation for XRF then relies on sectioning the samples parallel to the impactor trajectory in order to expose the largest area of subsurface damage possible, thus maximizing the signal from any small impactor remnants. Complementary to the use of XRF for sample analysis, ARES also houses a Nikon XTH 320 micro-X-Ray computed tomography (XCT). This instrument can be used to create 3D visualizations of impact damage for the determination of crater volumes and dimensions, as well as for the determination of the best place to section each sample for the subsequent XRF analysis.

J L Hyde↗

Finding a needle in a haystack: quantitative HERFD-XRF imaging and HERFD-XANES characterization of trace platinum in gold solidi from the Late Roman and Byzantine Empires

High-Energy Resolution Fluorescence Detection X-Ray Fluorescence (HERFD-XRF) imaging and HERFD X-ray Absorption Near Edge Structure (XANES) spectroscopy are used to quantify and characterize trace platinum (Pt) in gold solidi from the Late Roman and Byzantine Empires. Historically, the elemental analysis of coins has been pivotal in distinguishing authentic artifacts from forgeries, elucidating minting practices, and understanding economic shifts. Notably, a new gold source with high platinum content appeared in the fourth century CE, transforming the Roman economy. Traditional methods struggled to detect platinum due to the overwhelming gold matrix. Here, this study demonstrates the effectiveness of HERFD techniques in resolving this challenge. Three gold solidi, minted between 654 and 659 CE, were analyzed alongside reference gold materials with known Pt concentrations. The HERFD-XRF imaging revealed spatial distributions of platinum, highlighting non-uniformities within the coins. Additionally, HERFD-XANES spectroscopy identified the oxidation states and chemical speciation of platinum. Results demonstrate that platinum in the solidi primarily exists as metallic Pt, with some surface oxidation. The findings align with previous measurements but reveal higher Pt concentrations and significant inhomogeneities. This research confirms the reliability of HERFD methods for quantifying trace elements and provides new insights into the raw material sources and minting techniques of ancient gold coins. The non-destructive nature of this approach allows for extensive analyses, offering valuable data for historical, economic, and archaeological studies. This innovative application of HERFD-XRF imaging and XANES in cultural heritage research underscores the potential for detailed material characterization and conservation, enhancing our understanding of ancient economies and trade patterns.

Van Loon, Lisa L.↗

Confirmation of the E(sup src)(sub Peak)-E(sub iso) (Amati) relation from the x-ray flash XRF 050416A observed by the Swift burst alert telescope

We report Swift Burst Alert Telescope (BAT) observations of the X-ray flash (XRF) XRF 050416A. The fluence ratio between the 15-25 and 25-50 keV energy bands of this event is 1.5, thus making it the softest gamma-ray burst (GRB) observed by BAT so far. The spectrum is well fitted by a Band function with E(sup obs)(sub peak) of 15.0(sup +2.3)(sub -2.7) keV. Assuming the redshift of the host galaxy (z = 0.6535), the isotropic equivalent radiated energy E(sub iso) and the peak energy at the GRB rest frame (E(sup src)(sub peak)) of XRF 050416A are not only consistent with the correlation found by Amati et al. and extended to XRFs by Sakamoto et al. but also fill in the gap of this relation around the 30-80 keV range of E(sup src)(sub peak). This result tightens the validity of the E(sup src)(sub Peak)-E(sup src)(sub peak) relation from XRFs to GRBs. We also find that the jet break time estimated using the empirical relation between E(sup src)(sub peak) and the collimation corrected energy E(sub gamma), is inconsistent with the afterglow observation by the Swift X-Ray Telescope. This could be due to the extra external shock emission overlaid around the jet break time or to the nonexistence of a jet break feature for XRFs, which might be a further challenge for GRB jet emission models and XRF/GRB unification scenarios.

Sakamoti, T.↗

Nondestructive Analysis of Astromaterials by Micro-CT and Micro-XRF Analysis for PET Examination

An integral part of any sample return mission is the initial description and classification of returned samples by the preliminary examination team (PET). The goal of the PET is to characterize and classify returned samples and make this information available to the larger research community who then conduct more in-depth studies on the samples. The PET tries to minimize the impact their work has on the sample suite, which has in the past limited the PET work to largely visual, nonquantitative measurements (e.g., optical microscopy). More modern techniques can also be utilized by a PET to nondestructively characterize astromaterials in much more rigorous way. Here we discuss our recent investigations into the applications of micro-CT and micro-XRF analyses with Apollo samples and ANSMET meteorites and assess the usefulness of these techniques in future PET. Results: The application of micro computerized tomography (micro-CT) to astromaterials is not a new concept. The technique involves scanning samples with high-energy x-rays and constructing 3-dimensional images of the density of materials within the sample. The technique can routinely measure large samples (up to approx. 2700 cu cm) with a small individual voxel size (approx. 30 cu m), and has the sensitivity to distinguish the major rock forming minerals and identify clast populations within brecciated samples. We have recently run a test sample of a terrestrial breccia with a carbonate matrix and multiple igneous clast lithologies. The test results are promising and we will soon analyze a approx. 600 g piece of Apollo sample 14321 to map out the clast population within the sample. Benchtop micro x-ray fluorescence (micro-XRF) instruments can rapidly scan large areas (approx. 100 sq cm) with a small pixel size (approx. 25 microns) and measure the (semi) quantitative composition of largely unprepared surfaces for all elements between Be and U, often with sensitivity on the order of a approx. 100 ppm. Our recent testing of meteorite and Apollo samples on micro-XRF instruments has shown that they can easily detect small zircons and phosphates (approx. 10 m), distinguish different clast lithologies within breccias, and identify different lithologies within small rock fragments (2-4 mm soil Apollo soil fragments).

Zeigler, R. A.↗

In situ XRF and gamma ray spectrometer for Mars sample return mission

A combined in situ X-ray fluorescence (XRF) and passive gamma ray spectrometer instrument is proposed for the chemical elemental analysis of various Martian surfaces and samples. The combined instrument can be carried on board a rover. The passive gamma ray or the neutron excited gamma ray system would be used to determine the elemental composition of the Martian surface while the rover is in motion. The XRF system would be used to perform analysis either on the Martian surface or on collected samples when the rover is stationary. The latter function is important both in cataloging the collected samples and in the selection of samples to be returned to earth. For both systems, data accumulation time would be on the order of 30 minutes. No sample preparation would be necessary.

Lo, I. Yin↗

Temporal Profiles and Spectral Lags of XRF 060218

The spectral and temporal properties of the nonthermal emission of the nearby XRF 060218 in the 0.3-150 keV band are studied. We show that both the spectral energy distribution and the light-curve properties suggest the same origin of the nonthermal emission detected by Swift BAT and XRT. This event has the longest pulse duration and spectral lag observed to date among the known GRBs. The pulse structure and its energy dependence are analogous to typical GRBs,. By extrapolating the observed spectral lag to the Compton Gamma Ray Observatory (CGRO) BATSE bands we find that the hypothesis that this event complies with the same luminosity-lag relation with bright GRBs cannot be ruled out at 2 sigma significance level. These intriguing facts, along with its compliance with the Amati relation, indicate that XRF 060218 shares the similar radiation physics as typical GRBs.

Liang, En-Wei↗

A Spectacular Radio Flare from XRF 050416a at 40 Days and Implications for the Nature of X-Ray Flashes

We present detailed optical, near-infrared, and radio observations of the X-ray flash 050416a obtained with Palomar and Siding Springs Observatories as well as HST and the VLA, placing this event among the best-studied X-ray flashes to date. In addition, we present an optical spectrum from Keck LRIS from which we measure the redshift of the burst, Z=0.6528. At this redshift the isotropic-equivalent prompt energy release was about 10(exp 51) erg, and using a standard afterglow synchrotron model we find that the blastwave kinetic energy is a factor of 10 larger, E-K,iso approximately equals 10 (exp 52) erg. The lack of an observed jet break to t - 20 days indicates that the opening angle is larger than 7 deg and the total beaming-corrected relativistic energy is larger than 10 exp (50) erg. We further show that the burst produced a strong radio flare at t is similar to 40 days accompanied by an observed flattening in the X-ray band which we attribute to an abrupt circumburst density jump or an episode of energy injection (either from a refreshed shock or off-axis ejecta). Late-time observations with HST show evidence for an associated supernova with peak optical luminosity roughly comparable to that of SN 1998bw. Next, we show that the host galaxy of XRF 050416a is actively forming stars at a rate of at least 2 M-solar per year with a luminosity of L-B is similar to 0.5L* and metallicity of Z is similar to 0.2-0.8 Z-solar. Finally, we discuss the nature of XRF 050416a in the context of short-hard gamma-ray bursts and under the framework of off-axis and dirty fireball models for X-ray flashes.

Soderberg, A. M.↗

The Fast Evolution of SN 2010bh Associated with XRF 100316D

The first observational evidence of a connection between supernovae (SNe) and gamma-ray bursts (GRBs) was found about a decade ago. Since then, only half a dozen spectroscopically confirmed associations have been discovered and XRF 1003160 associated with the type-Ic SN 20lObh is among the latest. Aims. We constrain the progenitor radius, the host-galaxy extinction, and the physical parameters of the explosion of XRF l00316D/SN 20lObh at z 0.059. We study the SN brightness and colours in the context of GRB-SNe. Methods. We began observations with the Gamma-Ray burst Optical and Near-infrared Detector (GROND) 12 hours after the GRB trigger and continued until 80 days after the burst. GROND provided excellent photometric data in six filter bands covering a wavelength range from approximately 350 to 1800 nm, significantly expanding the pre-existing data set for this event. Combining GROND and Swift data, the early broad-band spectral energy distribution (SED) is modelled with a blackbody and afterglow component attenuated by dust and gas absorption. The temperature and radius evolution of the thermal component are analysed and combined with earlier measurements available from the literature. Templates of SN 1998bw are fitted to the SN itself to directly compare the lightcurve properties. Finally, a two-component parametrized model is fitted to the quasi-bolometric light curve. which delivers physical parameters of the explosion. Results. The best-fit models to the broad-band SEDs imply moderate reddening along the line of sight through the host galaxy (A(sub v.host = 1.2 +/- 0.1 mag). Furthermore, the parameters of the blackbody component reveal a cooling envelope at an apparent initial radius of 7 x 10(exp 11) cm, which is compatible with a dense wind surrounding a Wolf-Rayet star. A multicolor comparison shows that SN 2010bh is 60 - 70% as bright as SN 1998bw. Reaching maximum brightness at 8 - 9 days after the burst in the blue bands, SN 20lObh proves to be the most rapidly evolving GRB-SNe to date. Modelling of the quasi-bolometric light curve yields M(sub Ni) = 0.21 +/- 0.03 solar M and M(sub ej) = 2.6 +/- 0.2 solar M, typical of values within the GRB-SN population. The kinetic energy is E(sub k) = (2.4 +/- 0.7) x 10(exp 52) erg, which is making this SN the second most energetic GRB-SN after SN 1998bw. Conclusions. This supernova has one of the earliest peaks ever recorded and thereafter fades more rapidly than other GRB-SNe, hypernovae, or typical type-Ic SNe. This could be explained by a thin envelope expanding at very high velocities, which is therefore unable to retain the gamma-rays that would prolong the duration of the SN event.

Olivares E., F.↗