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279 - Xanes Studies on UV-Irradiated Interstellar Ice Analogs: A Comparison to STARDUST Samples

We present C-, N-, and O-XANES (X-ray Absorption Near-Edge Spectroscopy) results of organic residues produced in the laboratory from the UV irradiation of astrophysical ice analogs containing H20, CO, CH30H, NH31 in order to mimic processes that may occur in cold icy bodies of the outer Solar System, particularly in comets, Such analyses showed that laboratory-formed organic residues mainly consist of a solid phase and an oily phase. C-XANES analysis of the solid phase suggests a rich distribution of organic functionalities, among which carbonyl groups, C=C bonds, and alcohols are present. Results from N-XANES indicate the possible presence of amide, amine, and nitrile groups, The O-XANES spectra confirmed the a-bearing groups, These results are compared with the XANES spectra obtained from STARDUST cometary samples,

Milam, Stefanie N.↗

Coordinated Analyses of Mineral-organic Matter Associations in Interplanetary Dust Particles

Little is known about the timing and processes involved in the incorporation of organic matter with inorganic materials in early Solar System bodies. Recently, X-ray absorption near-edge spectroscopy (XANES) studies showed carbon-rich rims surrounding individual mineral grains in anhydrous IDPs [1,2]. These carbonaceous rims are believed to have formed prior to parent body formation and likely served to bond mineral grains during accretion into larger aggregates. We are exploring the nature of these carbonaceous rims through coordinated analyses of their chemistry, mineralogy, spectroscopy and isotopic characteristics. Here we report our preliminary mineralogical observations.

Nakamura-Messenger, K.↗

Electron Beam Damage in Apatite: Limitations for SKα Measurements of S6+/∑S

In magmatic systems, the availabil- ity of excess oxygen that can react with multivalent elements such as Fe and S to change their charge (oxi- dation of Fe2+ to Fe3+ or reduction of S6+ to S2-) is characterized by a parameter called the oxygen fugacity (ƒO2). The ƒO2 controls the availability of these ions and consequently the minerals—and the chemistry of those minerals—that crystallize from a melt. Mineral mode and chemistry control how magmas evolve, and given that ƒO2 varies by many orders of magnitude on different planets [2], understanding the ƒO2 of a mag- ma is critical to relating observations about a magma to the body on which it forms. The mineral apatite was long thought to only incor- porate S6+ in a coupled substitution for P5+, but recently natural apatites with S2- were identified in lunar mare basalts that crystallized at low ƒO2 [3]. This suggests that apatite can be used as a monitor of ƒO2 assuming that one can 1) measure S6+/∑S (S6+ over total sulfur), and 2) determine some partitioning relationship be- tween apatite and melt for S6+ and S2-. The most common method for measuring S6+/∑S is X-ray Absorption Near-Edge Spectroscopy (XANES), but given the limited access to synchrotron facilities, it is wise to explore the potential of other methods for measuring S6+/∑S. One such possible method relies upon the shift in energy of the sulfur K-α peak on the electron microprobe. However, apatite is subject to well-documented beam damage [4, 5], so it is neces- sary to evaluate under what conditions can reliable S6+ ethod.

de Chizelle, J. Kuhn↗

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.↗

XANES Analysis of Organic Residues Produced from the UV Irradiation of Astrophysical Ice Analogs

Organic residues formed in the laboratory from the ultraviolet (UV) photo-irradiation or ion bombardment of astrophysical ice analogs have been extensively studied for the last 15 years with a broad suite of techniques, including infrared (IR) and UV spectroscopies, as well as mass spectrometry. Analyses of these materials show that they consist of complex mixtures of organic compounds stable at room temperature, mostly soluble, that have not been fully characterized. However, the hydrolysis products of these residues have been partly identified using chromatography techniques, which indicate that they contain molecular precursors of prebiotic interest such as amino acids, nitrile-bearing compounds, and amphiphilic compounds. In this study, we present the first X-ray absorption near-edge structure (XANES) spectroscopy measurements of three organic residues made from the UV irradiation of ices having different starting compositions. XANES spectra confirm the presence of different chemical functions in these residues, and indicate that they are rich in nitrogenand oxygen-bearing species. These data can be compared with XANES measurements of extraterrestrial materials. Finally, this study also shows how soft X rays can alter the chemical composition of samples.

XANES(X-RAY ABSORPTION NEAR-EDGE STRUCTURE)↗

Combined Carbon, Nitrogen, and Oxygen XANES Spectroscopy on Hydrated and Anhydrous Interplanetary Dust Particles

Interplanetary dust particles (IDPs) collected from the Earth s stratosphere generally contain percent-level concentrations of organic matter. This organic matter in IDPs is important for several reasons: 1) some IDPs contain interstellar organic matter, identified by high D/H or N-15, providing the opportunity to characterize this interstellar material, 2) comparison of the organic matter in anhydrous IDPs to that in hydrated IDPs can help establish the effects of parent body aqueous alteration, and, 3) IDPs are believed to have delivered to the surface of the early Earth pre-biotic organic matter important for the origin of life. X-Ray Absorption Near-Edge Structure (XANES) spectroscopy provides information on the functional groups present in a sample, and XANES can be performed on the nano-scale, comparable to the size of some of the sub-units of the IDPs. The energies of the XANES transitions are diagnostic of the type of bonding of the C, N, and O, allowing identification of the functional groups present in the sample. As part of our ongoing effort to characterize the organic matter in the IDPs, we have performed carbon- and oxygen- and the first nitrogen-XANES spectroscopy on two IDPs and acid-insoluble residue from the CM2 meteorite Murchison.

Feser, M.↗

Evidence for Terrestrial Organic Contamination of the Tagish Lake Meteorite

The Tagish Lake meteorite is a rare discovery in the meteorite world. Tentatively classified as an ungrouped type 2 carbonaceous chondrite, it is the first known CI2 meteorite [1, 2, 3]. Tagish Lake is the first meteorite to exhibit a reflectance spectrum showing the red color characteristic of the D- and P-type asteroids that populate the outer main-belt [2], although many interplanetary dust particles collected from the Earth s stratosphere exhibit a similar spectrum [4]. Several large pieces of the Tagish Lake meteorite were recovered on Jan. 18, 2000. We obtained two samples of the Tagish Lake meteorite, both collected on April 24, 2000, designated MG02 and MG03, from A. Hildebrand (Univ. of Calgary) and P. Brown (Univ. of Western Ontario). Smaller fragments collected in May 2000 were purchased from the The Meteorite Market (samples designated "MM"). We have reported preliminary results from infrared and X-ray Absorption Near-edge Structure (XANES) spectroscopy on the MM samples [5]. We report evidence to suggest that there was terrestrial contamination of the meteorite, even in fragments in contact with the lake ice for only a few months .

Wirick, S.↗

Comparison of the Organic Composition of Cometary Samples with Residues Formed from the UV Irradiation of Astrophysical Ice Analogs

The NASA Stardust mission successfully collected material from Comet 81P/Wild 2 [1], including authentic cometary grains [2]. X-ray absorption near-edge structure (XANES) spectroscopy analysis of these samples indicates the presence of oxygen-rich and nitrogen-rich organic materials, which contain a broad variety of functional groups (carbonyls, C=C bonds, aliphatic chains, amines, arnides, etc.) [3]. One component of these organics appears to contain very little aromatic carbon and bears some similarity to the organic residues produced by the irradiation of ices of interstellar/cometary composition, Stardust samples were also recently shown to contain glycine, the smallest biological amino acid [4]. Organic residues produced froth the UV irradiation of astrophysical ice analogs are already known to contain a large suite of organic molecules including amino acids [5-7], amphiphilic compounds (fatty acids) [8], and other complex species. This work presents a comparison between XANES spectra measured from organic residues formed in the laboratory with similar data of cometary samples collected by the Stardust mission

Milam, S. N.↗

The oxidation state of sulfur in lunar apatites in meteorites versus Apollo rocks

Sulfur can be present in apatite mineral grains as S6+ [1], S2- [2], or a mixture of the two [3, 4]. The proportion of S6+ to S2- present in the apatite is thought to be predominantly controlled by the prevailing oxygen fugacity (fO2) conditions during crystallization (along with temperature, pressure, and major element composition; [2-4]). Measurements of apatites and proximal residual glass in the lunar basalts 12039 and 10044 by X-ray absorption near-edge structure (XANES) spectroscopy show that sulfur occurs as S2- in both the mesostasis glass and apatite when measurements are performed far from cracks or pits in the thin section [2], consistent with other mineralogical indications of low fO2 (∆IW-1) during petrogenesis. However, analyses of apatite grains in both samples that were acquired near cracks or pits in the thin section sometimes revealed minor but nonnegligible spectral evidence for the presence of S6+ (e.g., S6+/ΣS > 0.03; [2]). This evidence was interpreted as either primary S2- altered to S6+ in the thin section, or S6+ of secondary origin, deposited in the fractures of the samples [2, 5]. It is unknown whether this alteration is lunar or terrestrial in origin, with implications for lunar petrogenesis if lunar [e.g., 5], or sample handling and curation if terrestrial [e.g., 6]. Note: Extended abstract on document.

M. Brounce↗

The Titan Haze Simulation (THS) Experiment on COSmIC. Part III. XANES Study of Laboratory Analogs of Titan Tholins

We have used the Titan Haze Simulation (THS) experimental set-up at NASA Ames’ COSmIC 19 facility to produce four laboratory analogs of Titan’s aerosols, or tholins. These tholin samples 20 were produced from four gas mixtures, representative of Titan’s atmosphere, of initial 21 compositions N2:CH4 (90:10 and 95:5) and N2:CH4:C2H2 (89.5:10:0.5 and 94.5:5:0.5) at 150 K, 22 using a plasma discharge in the stream of a jet-cooled gas expansion. Here we present an ex-situ 23 X-ray absorption near-edge structure (XANES) spectroscopy analysis of these four tholin 24 samples. The C- and N-XANES spectra show the presence of various functional groups 25 (aromatic carbon, imines, nitriles, etc.) whose abundances are correlated with (i) the relative 26 proportions between N2 and CH4, and (ii) the presence or absence of C2H2 in the initial mixtures. 27 In particular, mixtures containing C2H2 result in the formation of tholins consisting of more 28 aromatic structures and displaying larger relative amounts of imines and nitriles, but lower 29 overall nitrogen content. XANES spectroscopy also allowed for the determination of the 30 elemental C/N ratios for the four tholins, which were all found to be low (< 2.5) and consistent 31 with those measured for tholins produced in other, independent experimental set-ups. The C/N 32 ratios of tholins produced from gas mixtures that contained C2H2 (2.2–2.4) were found to be 33 about twice as large as those of tholins produced from gas mixtures that did not contain C2H234 (0.9–1.3). These new experimental results from the COSmIC/THS experiment demonstrate the 35 impact initial precursors have on the nitrogen chemistry during the formation of tholins, which 36 may help in the interpretation of observations and the development of models of Titan’s 37 atmosphere.

Titan↗

Coordinated Microanalyses of Seven Particles of Probable Interstellar Origin from the Stardust Mission

Stardust, a NASA Discovery-class mission, was the first sample-return mission to return solid samples from beyond the Moon. Stardust was effectively two missions in one spacecraft: it returned the first materials from a known primitive solar system body, the Jupiter-family comet Wild 2; Stardust also returned a collector that was exposed to the contemporary interstellar dust stream for 200 days during the interplanetary cruise. Both collections present severe technical challenges in sample preparation and in analysis. By far the largest collection is the cometary one: approximately 300 micro g of material was returned from Wild 2, mostly consisting of approx. 1 ng particles embedded in aerogel or captured as residues in craters on aluminum foils. Because of their relatively large size, identification of the impacts of cometary particles in the collection media is straightforward. Reliable techniques have been developed for the extraction of these particles from aerogel. Coordinated analyses are also relatively straightforward, often beginning with synchrotron-based x-ray fluorescence (S-XRF), X-ray Absorption Near-Edge Spectoscopy (XANES) and x-ray diffraction (S-XRD) analyses of particles while still embedded in small extracted wedges of aerogel called ``keystones'', followed by ultramicrotomy and TEM, Scanning Transmission X-ray Microscopy (STXM) and ion microprobe analyses (e.g., Ogliore et al., 2010). Impacts in foils can be readily analyzed by SEM-EDX, and TEM analysis after FIB liftout sample preparation. In contrast, the interstellar dust collection is vastly more challenging. The sample size is approximately six orders of magnitude smaller in total mass. The largest particles are only a few pg in mass, of which there may be only approx.10 in the entire collection. The technical challenges, however, are matched by the scientific importance of the collection. We formed a consortium carry out the Stardust Interstellar Preliminary Examination (ISPE) to carry out an assessment of this collection, partly in order to characterize the collection in sufficient detail so that future investigators could make well-informed sample requests. The ISPE is the sixth PE on extraterrestrial collections carried out with NASA support. Some of the basic questions that we asked were: how many impacts are there in the collector, and what fraction of them have characteristics consistent with extraterrestrial materials? What is the elemental composition of the rock-forming elements? Is there crystalline material? Are there organics? Here we present coordinated microanalyses of particles captured in aerogel, using S-FTIR, S-XRF, STXM, S-XRD; and coordinated microanalyses of residues in aluminum foil, using SEMEDX, Auger spectroscopy, STEM, and ion microprobe. We discuss a novel approach that we employed for identification of tracks in aerogel, and new sample preparation techniques developed during the ISPE. We have identified seven particles - three in aerogel and four in foils - that are most consistent with an interstellar origin. The seven particles exhibit a large diversity in elemental composition. Dynamical evidence, supported supported by laboratory simulations of interstellar dust impacts in aerogel and foils, and numerical modeling of interstellar dust propagation in the heliosphere, suggests that at least some of the particles have high optical cross-section, perhaps due to an aggregate structure. However, the observations are most consistent with a variety of morphologies

Westphal, Andrew J.↗

Interstellar X-Ray Absorption Spectroscopy of the Crab Pulsar with the LETGS

We study the interstellar X-ray absorption along the line of sight to the Crab Pulsar. The Crab was observed with the Low Energy Transmission Grating Spectrometer on the Chandra X-ray Observatory, and the pulsar, a point source, produces a full resolution spectrum. The continuum spectrum appears smooth, and we compare its parameters with other measurements of the pulsar spectrum. The spectrum clearly shows absorption edges due to interstellar Ne, Fe, and O. The O edge shows spectral structure that is probably due to O bound in molecules or dust. We search for near-edge structure (EXAFS) in the O absorption spectrum. The Fe L absorption spectrum is largely due to a set of unresolved discrete n=2-3 transitions in neutral or near-neutral Fe, and we analyze it using a new set of dedicated atomic structure calculations, which provide absolute cross sections. In addition to being interesting in its own right, the ISM absorption needs to be understood in quantitative detail in order to derive spectroscopic constraints on possible soft thermal radiation from the pulsar.

Paerels, Frits↗