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At least 19 records

Electron Probe MicroAnalysis (EPMA) Standards. Issues Related to Measurement and Accuracy Evaluation in EPMA

Electron-probe microanalysis standards and issues related to measurement and accuracy of microanalysis will be discussed. Critical evaluation of standards based on homogeneity and comparison with wet-chemical analysis will be made. Measurement problems such as spectrometer dead-time will be discussed. Analytical accuracy issues will be evaluated for systems by alpha-factor analysis and comparison with experimental k-ratio databases.

Carpenter, Paul↗

A Comparison of Experimental EPMA Data and Monte Carlo Simulations

Monte Carlo (MC) modeling shows excellent prospects for simulating electron scattering and x-ray emission from complex geometries, and can be compared to experimental measurements using electron-probe microanalysis (EPMA) and phi(rho z) correction algorithms. Experimental EPMA measurements made on NIST SRM 481 (AgAu) and 482 (CuAu) alloys, at a range of accelerating potential and instrument take-off angles, represent a formal microanalysis data set that has been used to develop phi(rho z) correction algorithms. The accuracy of MC calculations obtained using the NIST, WinCasino, WinXray, and Penelope MC packages will be evaluated relative to these experimental data. There is additional information contained in the extended abstract.

Carpenter, P. K.↗

Calculated X-ray Intensities Using Monte Carlo Algorithms: A Comparison to Experimental EPMA Data

Monte Carlo (MC) modeling has been used extensively to simulate electron scattering and x-ray emission from complex geometries. Here are presented comparisons between MC results and experimental electron-probe microanalysis (EPMA) measurements as well as phi(rhoz) correction algorithms. Experimental EPMA measurements made on NIST SRM 481 (AgAu) and 482 (CuAu) alloys, at a range of accelerating potential and instrument take-off angles, represent a formal microanalysis data set that has been widely used to develop phi(rhoz) correction algorithms. X-ray intensity data produced by MC simulations represents an independent test of both experimental and phi(rhoz) correction algorithms. The alpha-factor method has previously been used to evaluate systematic errors in the analysis of semiconductor and silicate minerals, and is used here to compare the accuracy of experimental and MC-calculated x-ray data. X-ray intensities calculated by MC are used to generate a-factors using the certificated compositions in the CuAu binary relative to pure Cu and Au standards. MC simulations are obtained using the NIST, WinCasino, and WinXray algorithms; derived x-ray intensities have a built-in atomic number correction, and are further corrected for absorption and characteristic fluorescence using the PAP phi(rhoz) correction algorithm. The Penelope code additionally simulates both characteristic and continuum x-ray fluorescence and thus requires no further correction for use in calculating alpha-factors.

Carpenter, P. K.↗

Quantitative EPMA Compositional Mapping of NWA 2995: Characterization, and Petrologic Interpretation of Mafic Clasts

We present the first fully quantitative compositional maps of lunar meteorite NWA 2995 using electron microprobe stage mapping, and compare selected clast mineralogy and chemistry. NWA 2995 is a feldspathic fragmental breccia containing numerous highland fine grained lithologies, including anorthosite, norite, olivine basalt, subophitic basalt, gabbro, KREEP-like basalt, granulitic and glassy impact melts, coarse-grained mineral fragments, Fe-Ni metal, and glassy matrix [1]. Chips of NWA 2995, representing these diverse materials, were analyzed by INAA and fused-bead electron-probe microanalysis (EPMA); comparison of analytical data suggests grouping of lunar meteorites NWA 2995, 2996, 3190, 4503, 5151, and 5152. The mean composition of NWA 2995 corresponds to a 2:1 mixture of feldspathic and mare material, with approximately 5% KREEP component [2]. Clast mineral chemistry and petrologic interpretation of paired stone NWA 2996 has been reported by Mercer et al. [3], and Gross et al. [4]. This study combines advances in quantitative EPMA compositional mapping and data analysis, as applied to selected mafic clasts in a polished section of NWA 2995, to investigate the origin of mafic lithic components and to demonstrate a procedural framework for petrologic analysis.

Carpenter, P. K.↗

Characterization of Corning EPMA Standard Glasses 95IRV, 95IRW, and 95IRX

The preparation, synthesis, and characterization of Corning trace-element glasses 95IRV, 95IRW, and 95IRX by bulk chemical and electron microprobe techniques is discussed. Working values for the doped elements in the 95-series glasses are established. Blank values have been determined by both bulk chemical and electron microprobe analysis, and important x-ray interferences are highlighted. Chemical homogeneity both within a rod cross-section, and along cane length has been documented. These glasses are standard reference materials intended for use as both primary and secondary electron microprobe standards.

Carpenter, Paul K.↗

In Situ Mg/Ca Measurements on Foraminifera: Comparison Between Laser Ablation Inductively Coupled Plasma Mass Spectrometry and Wavelength-Dispersive X-Ray Spectroscopy by Electron Probe Microanalyzer

We present a comparison of two different techniques: Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) and wavelength-dispersive X-Ray Spectroscopy by electron probe microanalyzer (EPMA) for obtaining Mg/Ca ratios in individual foraminifera shells. The goal is to assess the use of EPMA as an alternative technique for Mg/Ca analyses of single foraminiferal calcite shells. Foraminifera obtained from sediments (benthic, Uvigerina spp.) and from plankton tows (planktonic, Orbulina universa) were analyzed. All specimens were prepared in epoxy mounts and exposed in cross-section such that multiple high-resolution analyses could be completed on the shells using both techniques. We examined our data using statistical methods designed for the assessment and comparison of measurement techniques. In the case of Uvigerina, the mean difference for ratios obtained using EPMA and LA-ICP-MS is very small (−0.046 mmol mol−1) and scale independent. The Limits of Agreement (LoA, the standard deviation of the bias plus the mean bias) is [−0.315, 0.223] mmol mol−1. For samples with ratios lower than 13 mmol mol−1, we found a mean EPMA–LA-ICP-MS bias of −2.44 mmol mol−1 and a corresponding LoA of [−3.85, −1.04] mmol mol−1. For ratios higher than 13 mmol mol−1, there appears to be a scale dependent bias, meaning that the EPMA measured ratios become progressively larger than those of LA-ICP-MS as the Mg/Ca ratio increases, so the mean bias and LoA metrics are not meaningful. Results indicate that it is possible to use EPMA to collect Mg/Ca data, if the ratios are lower than ∼13 mmol mol−1.

EPMA↗

Pink Spinel in Apollo Impact Melt Rock 68815: Implications for Mg-Suite Magmatism

Introduction: Magnesian rocks from the lunar highlands are collectively termed the Mg-suite. Characterized by high (>60) Mg# (molar 100×Mg/[Mg+Fe]) in mafic phases and calcic plagioclase, these rocks are plutonic to hypabyssal in origin, and include a range of bulk mineralogies such as troctolites, dunites, norites, gabbronorites, and spinel troctolites [1]. These Mg-suite lithologies have distinct trace element concentrations and ratios that differentiate them from other lunar rock types. These rocks are ancient, generally dated to between 4.5 and 4.1 Ga, although it is unknown if this represents the full range of Mg-suite ages [1–2]. Among the Mg-suite lithologies, the spinel troctolites are relatively rare, to date only found in polymict breccias [3]. Spinel troctolites, as their name suggests, consist of calcic plagioclase and forsteritic olivine, with minor amounts of spinel (MgAl2O4), ± pyroxene and cordierite [1,4]. This form of spinel is often called ‘pink’ spinel because of its appearance in thin section under plane polarized light (PPL; Fig. 1), due to minor amounts of Cr. Spinel troctolites are generally plutonic or hypabyssal in origin (subsequently exhumed and incorporated into polymict breccias), or formed through impact processes (e.g., crystalline impact melt) [5]. A spinel-rich lithology has also been found in the Moscoviense region of the Moon via the Moon Mineralogy Mapper (M3) and lacks other mafic phases [6]. Finally, while the Mg-suite sampled thus far consists of plutonic (or hypabyssal) rocks, the question remains if such magmas could have erupted on the surface of the Moon [7]. These magmas have much lower density than mare basalts, but little sample or remote sensing evidence has been found to support the idea that extrusive Mg-suite volcanism occurred [7]. Here, we present a coordinated microanalytical study of spinel-bearing lithic and mineral clasts found in Apollo sample 68815. These data will be used to understand their petrogenesis (magmatic or impact) and modification histories, and to shed light on the existence of volcanic Mg-suite rocks. Sample Description: Apollo sample 68815 is a polymict impact melt breccia containing a variety of lithic and mineral fragments embedded in devitrified impact melt. This sample was chipped off the top of a boulder at Station 8 during the Apollo 16 mission and had an original weight of nearly 1.8 kg. In this study, we investigated two polished thin sections of 68815: 68815,17 and 68815,148, both containing spinel. Methods: The thin sections of 68815 were studied using optical light microscopy (PPL, cross-polarized light, and reflected light) with a Keyence VHX-7100 Digital Microscope. Each section was then X-ray mapped for 13–14 elements using a Cameca SX100 electron probe microanalyzer (EPMA) located in the Kuiper Materials Imaging and Characterization Facility (KMICF) at the University of Arizona. We have obtained geochemical information about the phases (olivine, plagioclase, spinel, pyroxene) in the thin sections also using the EPMA. In addition, we have used ThermoScientific Helios NanoLab 660 Focused-Ion-Beam Scanning-Electron Microscope (FIB-SEM) and a Hitachi S-4800 SEM (both in KMICF) to obtain backscattered electron (BSE) images and energy dispersive Xray spectrometry (EDS) maps of areas of interest. Using a JEOL 7900F SEM at the Astromaterials Research & Exploration Science (ARES) at NASA Johnson Space Center (JSC), we have obtained electron backscatter diffraction (EBSD) maps of the spinel-bearing portions of the thin sections. The EBSD data were collected under beam conditions of 20 kV, and ~90 μA, with step sizes varying from 0.05 to 2 μm. Following EBSD data collection, we processed the data using AZtecCrystal and MTEX, a free MATLAB toolbox. Results: We have found clasts with subophitic textures, that consist of primarily olivine and plagioclase, with minor amounts of pink Mg-Al spinel and pyroxene (Fig. 1). These clasts are up to ~1 mm in length and contain spinels up to 50 μm across. We have additionally identified pink Mg-Al spinels within the impact melt (i.e., not contained in lithic clasts) in both thin sections. In one instance, a single spinel grain is approximately 300 μm across (Fig. 1b, 2). The spinel fragments embedded in impact melt have varying compositions, typically distinct from the compositions of spinels in the lithic clasts. Spinel-Bearing Clasts: Ten lithic clasts with similar textures and mineral compositions were identified between 68815,17 (two clasts) and ,148 (eight clasts). These clasts fall into two groups. The first has skeletal olivine with intergranular plagioclase, with minor amounts of pyroxene and spinel (Fig. 1a, 2c, 2d). The spinel in these clasts are found amid the plagioclase. The second group have an intergranular texture of olivine and plagioclase, again with minor spinel and pyroxene. The second group may contain spinels surrounded by plagioclase, and spinels enclosed in olivine. Spinels located within both clast types range from no apparent Cr zoning, to reverse zoning (Cr-enrichment inward; Fig. 2d), to normal zoning (Cr-enrichment outward). In the clasts thus far investigated with EPMA, plagioclase compositions range from An# (molar 100×Ca/[Ca+Na+K]) 92–96. Olivine Mg# ranged from 77 to 94, while pyroxene had Mg# from 54–84. Spinel in the clasts have Cr# (molar 100×Cr/[Cr+Al]) 2–4 and Mg# 88–91, which is within the range of pristine and plutonic spinel troctolites [8]. Isolated Spinels: These crystals are generally euhedral to subhedral, and can exhibit reverse Cr zoning (Cr enrichment inward) or no apparent Cr zoning. The spinels thus far investigated via EPMA have Cr# 9–14 and Mg# 65–82. The Cr# for these spinels is within the range reported by [8], but have lower Mg#. Future Work: We will continue to process the EBSD data for these lithic and mineral clasts. We will also continue to characterize these clasts using EPMA and SEM. By thoroughly characterizing the various spinels and spinel-bearing clasts, we aim to constrain the petrogenesis of these minerals and rock fragments. Acknowledgments: We thank NASA for the loan of these thin sections. We thank Ken Domanik and Jerry Chang for their support with data collection. Work was supported by a University of Arizona RII Core Facilities Pilot Program grant and start-up funds to JJB. We acknowledge support from NASA’s Planetary Science Research program for analysis performed at JSC. References: [1] Shearer C. K. et al. (2015) Am. Min. 100, 294–325. [2] Borg L. E. et al. (2020) GCA 290, 312–332. [3] Warren P. H. (1993) Am. Min. 78, 360–376. [4] Dymek R. F. et al. (1976) LPS VII, 2335–2378. [5] Treiman et al. (2019) Am. Min. 104, 370–384. [6] Pieters et al. (2011) JGR: Plan. 116:E00G08. [7] Prissel et al. (2016) Icarus 277, 319–329. [8] Prissel et al. (2016) Am. Min. 101, 1624–1635.

spinel↗

Precision Oxygen Isotope Measurements of Two C-Rich Hydrated Interplanetary Dust Particles

Introduction: Chondritic-smooth IDPs (Interplanetary Dust Particles) are low porosity objects whose mineralogy is dominated by aqueous alteration products such as Mg-rich phyllosilicates (smectite and serpentine group) and Mg-Fe carbonate minerals. Their hydrated mineralogy combined with low atmospheric entry velocities have been used to infer an origin largely from asteroidal sources. Spectroscopic studies show that the types and abundance of organic matter in CS IDPs is similar to that in CP IDPs. Although CS IDPs show broad similarities to primitive carbonaceous chondrites, only a few particles have been directly linked to specific meteorite groups such as CM and CI chondrites based on the presence of diagnostic minerals. Many CS IDPs however, have carbon contents that greatly exceed that of known meteorite groups suggesting that they either may derive from comets or represent samples of more primitive parent bodies than do meteorites. It is now recognized that many large, dark primitive asteroids in the outer main belt, as well as some trans-Neptunian objects, show spectroscopic evidence for aqueous alteration products on their surfaces. Some CS IDPs exhibit large bulk D enrichments similar to those observed in the cometary CP IDPs. While hydrated minerals in comets have not been unambiguously identified to date, the presence of the smectite group mineral nontronite has been inferred from infrared spectra obtained from the ejecta from comet 9P/Tempel 1 during the Deep Impact mission. Recent observations of low temperature sulfide minerals in Stardust mission samples suggest that limited aqueous activity occurred on comet Wild-2. All of these observations, taken together, suggest that the high-carbon hydrated IDPs are abundant and important samples of primitive solar system objects not represented in meteorite collections. Oxygen isotopic compositions of chondrites reflect mixing between a 16O-rich reservoir and a 17O,18O-rich reservoir produced via mass-independent fractionation. The composition of the 16O-rich reservoir is well constrained but material representing the 17O,18O-rich end-member is rare. Self-shielding models predict that cometary water, presumed to represent this reservoir, should be enriched in 17O and 18O by greater than 200 per mille. The high-carbon hydrated IDPs may be among the best materials available to search for preserved "cometary" H2O signatures. In order to better understand the origin and evolution of these particles, we have obtained 10 hydrated interplanetary dust particles for coordinated mineralogical, isotopic and organic analyses. We have previously reported the results of mineralogical and O isotopic measurements of two hydrated IDPs; here we present results of O isotopic measurements of three additional IDPs. Samples and Methods: Three interplanetary dust particles (L2079C35, L2083D46 and L2083E46) were embedded in S and partially ultramicrotomed into approximately 70 nanometer sections for analysis via transmission electron microscopy (TEM). The remainders of the unsliced particles were removed from S and pressed into high purity Au foil that was cleaned with HF acid and annealed at 800 degrees Centigrade. The pressed IDPs were analyzed via electron microprobe analysis (EPMA) for quantitative bulk chemical analysis. After EPMA analysis, the IDPs were subjected to precision O isotope analysis with the UCLA Cameca IMS-1270 ion probe. A 20 kiloelectronvolt, 0.5 nanoangstrom Cs+ primary beam of approximately 15 micrometers diameter was used for each measurement. Small particles of San Carlos olivine and Burma spinel were pressed into the Au foil for use as standards to correct for instrumental mass fractionation. The detection system was configured for multicollection, with 16O measured on a Faraday cup, and 17O and 18O measured on electron multipliers (EMs). Individual analyses consisted of 15 cycles of 10 seconds per cycle. Additionally, two microtome thin sections were measured for H isotopic compositions with the JSC NanoSIMS 50L ion probe. An 8 picoangstrom, 16 kiloelectronvolt Cs plus primary beam was used. Measurements consisted of H, C, 12C, 16O, and 18O collected with EMs in multicollection. Terrestrial biotite and kerogen were used for isotopic standards. A significant challenge in O isotope measurement of hydrated minerals is the interference from 16OH at mass 17O. We ensured that the 17O and 16OH peaks were fully resolved by using a mass resolution of greater than 7000 and by careful analyses of San Carlos olivine, Burma spinel and chlorite hydrated mineral standards. The hydride was further suppressed with a cold finger attached to an LN2 dewar to trap volatiles in the sample chamber. All sputtered ions were counted (i.e. presputtering was not used); after applying background, yield and deadtime corrections, we performed a change-point analysis on our data via R in order to determine when the sample reached sputtering equilibrium; data points collected prior to the change point were excluded. Change-point analysis was also used to determine whether the IDP had completely sputtered. Results: Mineralogy. IDPs C35 and E46 exhibited hydrated mineralogies, Fe-Ni sulfide grains, nanoglobules and occasional enstatite grains distributed throughout a fine-grained Mg-Fe saponite matrix. C35 also contained breunnerite (Mg,Fe)CO3; solar flare tracks were observed in enstatite, indicating minimal atmospheric entry heating. The mineralogy of D46 is dominated by a large FeS grain with a minor component of adhering silicate material. D46 was strongly heated during atmorpheric entry as evidenced by a well-developed magnetite rim. EPMA analyses show that both C35 and E46 have high carbon contents of 20 weight percentage (approximately 6X CI). D46 contains approximately 6 wt.weight percentage C. A significant amount of the carbon is present as carbon nanoglobules. Results: Hydrogen isotopes: Although the bulk delta D values of both sections of L2079C35 were within error of SMOW (minus 33 plus or minus 19 per mille, 1 plus or minus 14 per mille 1 sigma), several delta D-rich hotspots were also identified, reaching 2000 per mille. As shown in Fig. 1, these hotspots are clearly associated with discrete carbonaceous inclusions that are akin to nanoglobules found in many meteorites and other IDPs. Oxygen Isotopes. Results of the oxygen isotope measurements are shown in Figure 1. The oxygen isotope composition for L2079C35 was delta 18O equals plus11.6 plus or minus 1.9per mille, delta 17O equals plus 7.9 plus or minus 1.9per mille (2 standard errors). The oxygen isotope composition for L2083D46 was delta 18O equals minus 8.1 plus or minus 1.9 per mille, delta 17O equals minus 6.4 plus or minus 3.1 per mille (2 standard errors). The oxygen isotope composition for L2083E46 was delta 18O equals plus 12.0 plus or minus 1.9 per mille, delta 17O equals plus 9.2 plus or minus 2.0 per mille (2 standard errors). Discussion: Despite mineralogical similarities to highly aqueously altered carbonaceous chondrites, the hydrated IDPs we analyzed have oxygen isotopic compositions that are distinct from matrix materials in the CI, CM, and CR chondrites. The IDPs plot along the Young-Russell line, with delta 17O values for C35 and E46 suggestive of interaction with a 16O-poor reservoir. However, we have thus far not observed evidence of extreme 16O-poor reservoirs expected from self-shielding models and observed in Acfer 094 simplectite. The high carbon contents of the IDPs also set them apart from known meteoritic samples. The lack of atmospheric entry heating effects are consistent with low encounter velocities and suggest either an asteroidal source, or a low inclination, low eccentricity cometary origin. Conclusions: The unusual oxygen isotopic compositions, high carbon contents, and the abundance of Drich nanoglobules, together, suggest that the high-carbon, hydrated IDPs are derived from a primitive source that is not yet represented in meteorite collections.

Snead, C. J.↗

Mineralogical Analysis of Calcium-Aluminum-Rich Inclusions Provides Insight Into Post-Formation Processes

Introduction: Calcium-aluminum inclusions (CAIs) are cm- to mm-sized intergrowths of refractory phases found in chondritic meteorites [1]. Their mineral compositions closely match the compositions of the solids thought to condense from an extremely hot (>1500K) gas with a bulk solar composition [2-4], suggesting that CAIs were the earliest solids within the Solar System [2-4]. These inclusions provide invaluable insights into the conditions and dynamics of the early Solar System. CAIs must be transported from their formation region near the protosun to the chondrite parent-body accretion region. The nature of their journey could affect how, when, and where the secondary processes recorded in these CAIs occurred [4]. Did these secondary processes occur in the solar nebula or during accretion with the parent body, or both? How were the CAIs affected by varying thermochemical processes? To better answer these questions, we have undertaken an in-depth, textural study of the secondary alteration of select CAI samples. Methods: We chose three CAIs that experienced a range of post-formation processing to gain better understanding of secondary alteration based on previous preliminary examination [5]. Representative CAIs were chosen from NWA 5508 (CV3), NWA 12772 (CV3), and Coolidge (CL4) carbonaceous chondrites. We used scanning electron microscopy (SEM) and electron backscatter diffraction (EBSD) techniques for detailed chemical, mineralogical, and textural analysis of the CAIs. Backscattered electron (BSE) images and X-ray elemental maps were taken of Coolidge and NWA 5508 using the Lunar and Planetary Institute (LPI) Phenom SEM. The JEOL 7900F SEM at NASA Johnson Space Center (JSC) was used to obtain energy dispersive spectroscopy (EDS) chemical maps of all samples. High resolution EBSD analysis identified the mineral phases and textures, providing key information on their nature. Based on the SEM and EBSD data, minerals of interest were selected for quantitative chemical electron probe micro-analysis (EPMA) using the JEOL JXA-8530F at NASA JSC. Results and Discussion: The EDS maps show that the NWA 5508 and NWA 12772 CAIs designated “Saguaro” and “Hoopoe” respectively [5] are enriched in calcium while the Coolidge CAI designated “Cottonwood” is aluminum and magnesium rich. Saguaro. A ~1.5cm diameter igneous Type B CAI with a rounded shape. The dominant phases are melilite, spinel, and Al-Ti pyroxene with minor anorthite. Spinel is subhedral and occurs in clusters. Some of these clusters have a circular geometry which encloses other minerals, known as a palisade structure [6] (Fig. 1). Some palisades form near perfect circles while others are more irregular in shape. Melilite in Saguaro ranges in size from coarse (>250m) to fine-grained (5-7m) and forms intergrown laths. A third of the melilite grains exhibit simple twinning about their <001> axis. The spinel palisades and twinned melilite in Saguaro suggest an igneous history, and the lack of secondary minerals suggests minimal aqueous alteration. At some point in time after the initial condensation of the minerals and formation of the inclusion, the sample was remelted and quickly solidified. The formation of the palisades is still heavily debated. One hypothesis is that the palisades are the rims of smaller CAIs that accreted early on, essentially acting as xenoliths within the larger CAIs [7]. Another hypothesis suggests an igneous origin for palisade structures [6-8] wherein the melt traps gas bubbles, and the spinel nucleates on the surface of this bubble. Based on the WDS spot analyses of 41 melilite grains using EPMA, the data suggest that the composition inside and outside the palisades is nearly identical. This finding indicates that these palisades are likely not exogenous but rather formed from melt-vapor reactions. Our results are consistent with studies by Simon and Grossman,1997 [6] and Zhang et al. (2019) [8]. Hoopoe. A ~0.5cm compact Type A CAI with an irregular shape. The dominant mineral phases are melilite, spinel, and hibonite with minor amounts of anorthite, augite, and perovskite. The melilite ranges in size from ~500 to 50µm. The larger melilite grains have simple twinning along the <001> axis like melilite in Saguaro. Melilite in Hoopoe exhibits crystal-plastic strain with misorientation dominantly about the <010> and <110> axes. Spinel shows subhedral to euhedral morphology and appears in clusters. Hibonite grains are similar to spinel in habit and size but show more plastic strain. The two minerals are often found together with one appearing to replace the other. Perovskite appears in fine grained recrystallized regions alongside fine augite and spinel. The abundant strain and deformation features in the melilite and hibonite suggest that Hoopoe experienced shock. This shock could have occurred in the nebula [9] or from an impact of another body on the parent body asteroid. The appearance of fine-grained (<10m) areas of augite, perovskite, and spinel in the dominantly coarse-grained inclusion suggest recrystallization, possibly due to the sudden increase in pressure and temperature. Cottonwood. This ~0.5cm CAI exhibits distinct mineralogy and textures suggesting a high degree of alteration. It is irregular in shape. The dominant mineral phases are spinel and anorthite with minor amounts of augite and rutile. The two main texture types can be seen in Fig. 2. The first type consists of coarse euhedral to subhedral spinel and anorthite. The second includes fine grained spinel, anorthite, rutile, and iron sulfides. Within these fine-grained regions, the anorthite grains are clustered into domains exhibiting the same crystallographic orientation. Rutile exclusively occurs with fine anorthite indicating a potential relationship between the two. Cottonwood has a clear and unbroken Wark-Lovering [10] rim (Fig. 2) on one side that consists of a sequence of spinel followed by anorthite and an outer layer of augite. The abundance of the fine-grained regions containing iron oxides and iron sulfides, secondary phases such as rutile, and oriented anorthite grains is evidence for recrystallization associated with a high degree of thermal metamorphism. The EPMA analyses on both coarse- and fine-grained spinel show that the fine spinel grains are more enriched in Cr (1-2 wt. %) than their coarse counterparts (0.1-0.5 wt. %). The data suggest thermal metamorphism drove chemical exchange of the previously refractory inclusion, introducing chromium and iron as well as sulfur, which is moderately volatile. Conclusions: The three CAIs analyzed record distinct secondary nebular and parent body processes. Saguaro melted in the nebula as seen by the twinned melilite and spinel palisades. Hoopoe experienced intense shock which deformed its melilite and recrystallized perovskite, augite, and spinel in fine-grained regions. Cottonwood shows evidence of recrystallization and chemical changes consistent with thermal metamorphism occurring after accretion into the parent-body.

V E Burnette↗

Aubrite basalt vitrophyres: High sulfur silicate melts and a snapshot of aubrite formation

Two aubrite basalt vitrophyre clasts have been found within AMNH thin sections from the Parsa EH3 chondrite and the Khor Temiki aubrite. Polished sections of the Parsa Aubrite Inclusion (PAI) and the Khor Temiki Inclusion (KTI) were studied by optical, electron probe microanalysis (EPMA), and scanning electron microscopy (SEM) techniques with broad-beam and low absorbed EPMA currents used to minimize glass volatile loss. Some data have previously been reported for PAI and KTI may possibly correlate to a previously reported inclusion in Khor Tiimiki. In polished sections, PAI and KTI are approximately equal 4 mm in diameter and contain a large volume of glass. The clasts have similar textural characteristics and are akin to lunar vitrophyre textures. The glasses have high alkali rhyodacitic compositions Al-though PAI is peraluminous, KTI is significantly peralkaline. Additionally, the glasses have elevated sulfur concentrations that are extremely high by geochemical standards. SEM examination for beam overlap of microscopic CaS, FeS, and (Mg, Mn, Fe) S inclusions showed no such contamination. Furthermore, homogeneity of glass S content and low FeO contents help rule out contamination. Materials research data show that under reducing conditions alumino-silicate melts can dissolve up to several weight percent sulfur in the absence of Fe. The high S and alkali contents, the lack of associated high shock features, and the rationalized phase equilibria suggest that PAI and KTI are igneous melting products of an E-chondrite-like source material. Although large-scale impact melting cannot totally be ruled out, the above observations eliminate the possibility of in-situ shock melting.

Fogel, R. A.↗

Improvements in Electron-Probe Microanalysis: Applications to Terrestrial, Extraterrestrial, and Space-Grown Materials

Improvement in the accuracy of electron-probe microanalysis (EPMA) has been accomplished by critical assessment of standards, correction algorithms, and mass absorption coefficient data sets. Experimental measurement of relative x-ray intensities at multiple accelerating potential highlights errors in the absorption coefficient. The factor method has been applied to the evaluation of systematic errors in the analysis of semiconductor and silicate minds. Accurate EPMA of Martian soil stimulant is necessary in studies that build on Martian rover data in anticipation of missions to Mars.

Carpenter, Paul↗

Quantitative Electron Probe Microanalysis: State of the Art

Quantitative electron-probe microanalysis (EPMA) has improved due to better instrument design and X-ray correction methods. Design improvement of the electron column and X-ray spectrometer has resulted in measurement precision that exceeds analytical accuracy. Wavelength-dispersive spectrometer (WDS) have layered-dispersive diffraction crystals with improved light-element sensitivity. Newer energy-dispersive spectrometers (EDS) have Si-drift detector elements, thin window designs, and digital processing electronics with X-ray throughput approaching that of WDS Systems. Using these systems, digital X-ray mapping coupled with spectrum imaging is a powerful compositional mapping tool. Improvements in analytical accuracy are due to better X-ray correction algorithms, mass absorption coefficient data sets,and analysis method for complex geometries. ZAF algorithms have ban superceded by Phi(pz) algorithms that better model the depth distribution of primary X-ray production. Complex thin film and particle geometries are treated using Phi(pz) algorithms, end results agree well with Monte Carlo simulations. For geological materials, X-ray absorption dominates the corretions end depends on the accuracy of mass absorption coefficient (MAC) data sets. However, few MACs have been experimentally measured, and the use of fitted coefficients continues due to general success of the analytical technique. A polynomial formulation of the Bence-Albec alpha-factor technique, calibrated using Phi(pz) algorithms, is used to critically evaluate accuracy issues and can be also be used for high 2% relative and is limited by measurement precision for ideal cases, but for many elements the analytical accuracy is unproven. The EPMA technique has improved to the point where it is frequently used instead of the petrogaphic microscope for reconnaissance work. Examples of stagnant research areas are: WDS detector design characterization of calibration standards, and the need for more complete treatment of the continuum X-ray fluorescence correction.

Carpernter, P. K.↗

Analysis of Iron Meteorites Using Computed Tomography and Electron-probe Microanalysis

Computed tomography (CT) imaging and electron-probe microanalysis (EPMA) have been used to study samples of the Mundrabilla and Colomera iron meteorites in order to perform structural, textural, and mineralogical analysis. Both gamma-ray (Co-60 source, essentially monochromatic 1.25MeV avg.) and x-ray (420 KeV, continuous) sources have been used, with effective resolution of approximately 1 mm and 0.25 mm, respectively. The gamma-ray source provides approx. 15 cm penetration through steel and is used for larger samples, whereas the x-ray source provides superior resolution at reduced penetration but exhibits beam hardening artifacts. Here we present a combined approach where CT and EPMA imaging and microanalysis aid in the identification of structural and compositional features in iron meteorites.

Carpenter, P. K.↗

X-ray Mapping of Terrestrial and Extraterrestrial Materials Using the Electron Microprobe

Lunar samples returned from the Apollo program motivated development of the Bence-Albee algorithm for the rapid and accurate analysis of lunar materials, and established interlaboratory comparability through its common use. In the analysis of mineral and rock fragments it became necessary to combine micro- and macroscopic analysis by coupling electron-probe microanalysis (EPMA) with automated stage point counting. A coarse grid that included several thousand points was used, and initially wavelength-dispersive (WDS) and later energydispersive (EDS) data were acquired at discrete stage points using approx. 5 sec count times. A approx 50 micrometer beam diameter was used for WDS and up to 500 micrometer beam diameter for EDS analysis. Average analyses of discretely sampled phases were coupled with the point count data to calculate the bulk composition using matrix algebra. Use of a defocused beam resulted in a contribution from multiple phases to each analytical point, and the analytical data were deconvolved relative to end-member phase chemistry on the fly. Impressive agreement was obtained between WDS and EDS measurements as well as comparison with bulk chemistry obtained by other methods. In the 30 years since these methods were developed, significant improvements in EPMA automation and computer processing have taken place. Digital beam control allows routine collection of x-ray maps by EDS, and stage mapping for WDS is conducted continuously at slew speed and incrementally by sampling at discrete points. Digital pulse processing in EDS systems has significantly increased the throughput for EDS mapping, and the ongoing development of Si-drift detector systems promises mapping capabilities rivaling WDS systems. Spectrum imaging allows a data cube of EDS spectra to be acquired and sophisticated processing of the original data is possible using matrix algebra techniques. The study of lunar and meteoritic materials includes the need to conveniently: (1) Characterize the sample at microscopic and macroscopic scales with relatively high sensitivity, (2) Determine the modal abundance of minerals, and (3) Identify and relocate discrete features of interest in terms of size and chemistry. The coupled substitution of cations in minerals can result in significant variation in mineral chemistry, but at similar average Z, leading to poor backscattered-electron (BSE) contrast discrimination of mineralogy. It is necessary to discriminate phase chemistry at both the trace element level and the major element level. To date, the WDS of microprobe systems is preferred for mapping due to high throughput and the ability to obtain the necessary intensity to discriminate phases at both trace and major element concentrations. It is desirable to produce fully quantitative compositional maps of geological materials, which requires the acquisition of k-ratio maps that are background and dead-time corrected, and which have been corrected by phi(delta z> or an equivalent algorithm at each pixel. To date, turnkey systems do not allow the acquisition of k-ratio maps and the rigorous correction in this manner. X-ray maps of a chondrule from the Ourique meteorite, and a comb-layered xenolith from the San Francisco volcanic field, have been analyzed and processed to extract phase information. The Ourique meteorite presents a challenge due to relatively low BSE contrast, and has been studied using spectrum imaging. X-ray maps for Si, Mg, and FeK(alpha) were used to produce RGB images. The xenolith sample contains sector-zoned augite, olivine, plagioclase, and basaltic glass. X-ray maps were processed using Lispix and ImageJ software to produce mineral phase maps. The x-ray maps for Mg, Ca, and Ti were used with traceback to generate binary images that were converted to RGB images. These approaches are successful in discriminating phases, but it is desirable to achieve the methods that were used on lunar samples 30 years ago on current microprobe systems. Curnt research includes x-ray mapping analysis of the Dalgety Downs chondrite by micro x-ray fluorescence and spectrum imaging, in collaboration with Kenny Witherspoon of IXRF Systems and Dale Newbury of NIST.

Carpenter, P.↗

Calibration Issues and Operating System Requirements for Electron-Probe Microanalysis

Instrument purchase requirements and dialogue with manufacturers have established hardware parameters for alignment, stability, and reproducibility, which have helped improve the precision and accuracy of electron microprobe analysis (EPMA). The development of correction algorithms and the accurate solution to quantitative analysis problems requires the minimization of systematic errors and relies on internally consistent data sets. Improved hardware and computer systems have resulted in better automation of vacuum systems, stage and wavelength-dispersive spectrometer (WDS) mechanisms, and x-ray detector systems which have improved instrument stability and precision. Improved software now allows extended automated runs involving diverse setups and better integrates digital imaging and quantitative analysis. However, instrumental performance is not regularly maintained, as WDS are aligned and calibrated during installation but few laboratories appear to check and maintain this calibration. In particular, detector deadtime (DT) data is typically assumed rather than measured, due primarily to the difficulty and inconvenience of the measurement process. This is a source of fundamental systematic error in many microprobe laboratories and is unknown to the analyst, as the magnitude of DT correction is not listed in output by microprobe operating systems. The analyst must remain vigilant to deviations in instrumental alignment and calibration, and microprobe system software must conveniently verify the necessary parameters. Microanalysis of mission critical materials requires an ongoing demonstration of instrumental calibration. Possible approaches to improvements in instrument calibration, quality control, and accuracy will be discussed. Development of a set of core requirements based on discussions with users, researchers, and manufacturers can yield documents that improve and unify the methods by which instruments can be calibrated. These results can be used to continue improvements of EPMA.

Carpenter, P.↗

Connecting Lunar Meteorites to Source Terrains on the Moon

The number of named stones found on Earth that have proven to be meteorites from the Moon is approx. 180 so far. Since the Moon has been mapped globally in composition and mineralogy from orbit, it has become possible to speculate broadly on the region of origin on the basis of distinctive compositional characteristics of some of the lunar meteorites. In particular, Lunar Prospector in 1998 [1,2] mapped Fe and Th at 0.5 degree/pixel and major elements at 5 degree/pixel using gamma ray spectroscopy. Also, various multispectral datasets have been used to derive FeO and TiO2 concentrations at 100 m/pixel spatial resolution or better using UV-VIS spectral features [e.g., 3]. Using these data, several lunar meteorite bulk compositions can be related to regions of the Moon that share their distinctive compositional characteristics. We then use EPMA to characterize the petrographic characteristics, including lithic clast components of the meteorites, which typically are breccias. In this way, we can extend knowledge of the Moon's crust to regions beyond the Apollo and Luna sample-return sites, including sites on the lunar farside. Feldspathic Regolith Breccias. One of the most distinctive general characteristics of many lunar meteorites is that they have highly feldspathic compositions (Al2O3 approx. 28% wt.%, FeO <5 wt.%, Th <1 ppm). These compositions are significant because they are similar to a vast region of the Moon's farside highlands, the Feldspathic Highlands Terrane, which are characterized by low Fe and Th in remotely sensed data [4]. The meteorites provide a perspective on the lithologic makeup of this part of the Moon, specifically, how anorthositic is the surface and what, if any, are the mafic lithic components? These meteorites are mostly regolith breccias dominated by anorthositic lithic clasts and feldspathic glasses, but they do also contain a variety of more mafic clasts. On the basis of textures, we infer these clasts to have formed by large impacts that excavated and mixed rocks from depth within the lunar crust and possibly the upper mantle. One of the key questions is whether the mafic materials are ferroan or magnesian, which remote sensing does not clearly distinguish, and if mafic, whether they might contain mantlederived components such as olivine (dunite). Many but not all have mainly ferroan mafic components, consistent with a ferroan crustal source that is complementary to the ferroan anorthositic suite and that represents primary magma-ocean-derived feldspathic crust. Meteorites such as ALH 81005 [5] and Shişr 161 [6], however, contain coarse-grained magnesian mafic clasts (Fig. 1a) derived from deeply seated and melted material associated with impact basins. Comparison to LP gamma-ray data [2] supports an origin for magnesian feldspathic meteorites such as these (e.g., Shişr 161) as shown in Fig. 1b. Sayh al Uhaymir (SaU) 169. Another distinctive but much less common composition is represented by relatively mafic impact-melt breccia that is rich in incompatible elements known as KREEP. These meteorites can be related to the western nearside Procellarum KREEP Terrane, especially through a combination of Fe and Th contents. Among the most enriched is SaU 169, which has been related to high- Th impact-melt breccia found at the Apollo 12 site [7]. Through detailed EPMA and ion microprobe analysis we have shown that these two rock types are related in age and origin.

Jolliff, B. L.↗

Discreditation of Bobdownsite and the Establishment of Criteria for the Identification of Minerals with Essential Monofluorophosphate (PO3F2-)

Bobdownsite, IMA number 2008-037, was approved as a new mineral by the Commission on New Minerals, Nomenclature and Classification (CNMNC) as the fluorine endmember of the mineral whitlockite. The type locality of bobdownsite is in Big Fish River, Yukon Canada, and bobdownsite was reported to be the first naturally occurring mineral with essential monofluorophosphate (PO3F2-). The type specimen of bobdownsite has been reinvestigated by electron probe microanalysis (EPMA), and our data indicate that fluorine abundances are below detection in the mineral. In addition, we conducted detailed analysis of bobdownsite from the type locality by gas chromatography isotope ratio mass spectrometry, Raman spectroscopy, EPMA, and NMR spectroscopy. These data were compared with previously published data on synthetic monofluorophosphate salts. Collectively, these data indicate that bobdownsite is indistinguishable from whitlockite with a composition along the whitlockite-merrillite solid solution. Bobdownsite is therefore discredited as a valid mineral species. An additional mineral, krásnoite, has been purported to have monofluorophosphate components in its structure, but reexamination of those data indicate that F- in krásnoite forms bonds with Al, similar to OH- bonded to Al in perhamite. Consequently, krásnoite also lacks monofluorophosphate groups, and there are currently no valid mineral species with monofluorophosphate in their structure. We recommend that any future reports of new minerals that contain essential monofluorophosphate anions be vetted by abundance measurements of fluorine, vibrational spectroscopy (both Raman and FTIR), and where paramagnetic components are permissibly low, NMR spectroscopy. Furthermore, we emphasize the importance of using synthetic compounds containing monofluorophosphate anions as a point of comparison in the identification of minerals with essential monofluorophosphate. Structural data that yield satisfactory P-F bond lengths determined by X-ray crystallography, coupled with direct chemical analyses of fluorine in a material do not constitute sufficient evidence alone to identify a new mineral with essential monofluorophosphate anions.

McCubbin, Francis M.↗

Water-Rock Interactions in Outer Solar System Bodies: Evidence from the Coordinated Analysis of Interplanetary Dust

NASA has an ongoing program of collecting interplanetary dust particles (IDPs) in the stratosphere using high altitude research aircraft. The collected IDPs are derived from asteroids and comets and here we report studies of a subset of hydrated IDPs rich in carbonaceous matter that are proposed to have a cometary origin. Our studies are aimed at understanding the evolution of oxygen reservoirs in the Solar System and their interaction with cometary minerals and organic matter. The small size (<20 μm) and fragility of these IDPs present a number of analytical challenges. We have pioneered techniques for performing chemical, mineralogical, isotopic, and spectroscopic measurements on the same sample in a carefully coordinated sequence. Coordinated analyses of nanogram-size samples is made possible by several delicate sample preparation techniques. To avoid organic contamination, we embed IDPs in elemental sulfur and use ultramicrotomy to partly section the particles (the first few micrometers). Multiple thin sections (50-70 nm thick) are placed on different substrates depending on the analysis technique. We use a JEOL 2500SE scanning, transmission electron microscope (STEM) to determine the mineralogy, microstructure, and elemental compositions of constituent minerals in the thin sections through a combination of high resolution imaging, electron diffraction, quantitative energy-dispersive x-ray mapping, and electron energy-loss spectroscopy. Following the STEM analyses, we use a NanoSIMS 50L for high spatial resolution isotopic measurements of H, C, N, and O to search for presolar grains and to understand the origin of the indigenous organic matter. The isotopic analyses are performed on the same sections analyzed in the STEM in order to correlate isotopic properties with the elemental and mineralogical data. We reserve other thin sections for non-destructive analyses utilizing synchrotron-based techniques including Fourier-transform infrared (FTIR) micro-spectroscopy and X-ray absorption near-edge structure (XANES) analyses, especially for functional group analysis of organic matter in the particles. The remainder of the IDP is extracted from the sulfur bead that was used for microtomy and is pressed into Au foil for quantitative analysis (including light elements) using a JEOL 8530F field emission electron probe microanalyzer (EPMA). After the EPMA measurements, high precision oxygen isotopic analyses are obtained using Cameca IMS1270/1290 instruments at UCLA. The hydrated IDPs in this study are dominated by saponitic clays, with minor magnetite, carbonate and abundant organic matter. The remarkable oxygen isotopic compositions, high carbon contents, and the abundance of isotopically anomalous organic matter, together suggest that the high carbon, hydrated IDPs are derived from primitive sources not yet represented in meteorite collections such as outer main belt P- and D-type asteroids or comets.

Keller, Lindsay P.↗