Carbonaceous matter in Stardust samples returned from comet 81P/Wild 2 is observed to contain a wide variety of organic functional chemistry. However, some of this chemical variety may be due to contamination or alteration during particle capture in aerogel. We investigated six carbonaceous Stardust samples that had been previously analyzed and six new samples from Stardust Track 80 using correlated transmission electron microscopy (TEM), X-ray absorption near-edge structure spectroscopy (XANES), and secondary ion mass spectroscopy (SIMS). TEM revealed that samples from Track 35 containing abundant aliphatic XANES signatures were predominantly composed of cometary organic matter infilling densified silica aerogel. Aliphatic organic matter from Track 16 was also observed to be soluble in the epoxy embedding medium. The nitrogen-rich samples in this study (from Track 22 and Track 80) both contained metal oxide nanoparticles, and are likely contaminants. Only two types of cometary organic matter appear to be relatively unaltered during particle capture. These are (1) polyaromatic carbonyl-containing organic matter, similar to that observed in insoluble organic matter (IOM) from primitive meteorites, interplanetary dust particles (IDPs), and in other carbonaceous Stardust samples, and (2) highly aromatic refractory organic matter, which primarily constitutes nanoglobule-like features. Anomalous isotopic compositions in some of these samples also confirm their cometary heritage. There also appears to be a significant labile aliphatic component of Wild 2 organic matter, but this material could not be clearly distinguished from carbonaceous contaminants known to be present in the Stardust aerogel collector.

Multidimensional solid-state NMR spectroscopy is used to refine the identification and abundance determination of functional groups in insoluble organic matter (IOM) isolated from a carbonaceous chondrite (Murchison, CM2). It is shown that IOM is composed primarily of highly substituted single ring aromatics, substituted furan/pyran moieties, highly branched oxygenated aliphatics, and carbonyl groups. A pathway for producing an IOM-like molecular structure through formaldehyde polymerization is proposed and tested experimentally. Solid-state C-13 NMR analysis of aqueously altered formaldehyde polymer reveals considerable similarity with chondritic IOM. Carbon X-ray absorption near edge structure spectroscopy of formaldehyde polymer reveals the presence of similar functional groups across certain Comet 81P/Wild 2 organic solids, interplanetary dust particles, and primitive IOM. Variation in functional group concentration amongst these extraterrestrial materials is understood to be a result of various degrees of processing in the parent bodies, in space, during atmospheric entry, etc. These results support the hypothesis that chondritic IOM and cometary refractory organic solids are related chemically and likely were derived from formaldehyde polymer. The fine-scale morphology of formaldehyde polymer produced in the experiment reveals abundant nanospherules that are similar in size and shape to organic nanoglobules that are ubiquitous in primitive chondrites.

Although focused ion beam (FIB) microscopy has been used successfully for milling patterns and creating ultra-thin electron and soft X-ray transparent sections of polymers and other soft materials, little has been documented regarding FIB-induced damage of these materials beyond qualitative evaluations of microstructure. In this study, we sought to identify steps in the FIB preparation process that can cause changes in chemical composition and bonding in soft materials. The impact of various parameters in the FIB-scanning electron microscope (SEM) sample preparation process, such as final milling voltage, temperature, ion beam overlap and mechanical stability of soft samples, was evaluated using two test-case materials systems: polyacrylamide, a low melting-point polymer, and Wyodak lignite coal, a refractory organic material. We evaluated changes in carbon bonding in the samples using X-ray absorption near-edge structure spectroscopy (XANES) at the carbon K edge and compared these samples with thin sections that had been prepared mechanically using ultramicrotomy. Minor chemical changes were induced in the coal samples during FIB-SEM preparation, and little effect was observed by changing ion-beam parameters. However, polyacrylamide was particularly sensitive to irradiation by the electron beam, which drastically altered the chemistry of the sample, with the primary damage occurring as an increase in the amount of aromatic carbon bonding (C=C). Changes in temperature, final milling voltage and beam overlap led to small improvements in the quality of the specimens. We outline a series of best practices for preparing electron and soft X-ray transparent samples, with respect to preserving chemical structure and mechanical stability of soft materials using the FIB.

Insoluble organic matter (IOM) isolated from 22 carbonaceous and ordinary chondrites spanning a wide range of groups and petrologic types were analyzed using Fourier transform infrared spectroscopy (FTIR). Based on common IR spectral features, it is observed that IOM falls into 4 molecularly distinct groups (designated here as A through D). Spectral group A includes type 1 and 2 chondrites and exhibits intense aliphatic C-H and carboxyl vibrational peaks. Spectral group B includes the least metamorphosed type 3 chondrites and Tagish Lake, and exhibits weaker aliphatic and carboxyl vibrational intensity. Spectral groups C and D include metamorphosed type >= 3.1 chondrites and a heated CM chondrite. The carbonyl stretching features in spectral groups C and D differ from that in spectral groups A and B and from each other. In spectral group C, the carbonyl stretching is assigned to cyclic unsaturated lactones; in spectral group D carbonyl exists predominantly in the form of unsaturated ketone moieties. Both spectral groups C and D have a relatively narrow band structure around 1210 cm(-1) (assigned to aromatic skeletal modes) as compared with spectral groups A and B, which is consistent with the formation of more condensed aromatics by extensive thermal metamorphism. The differences in carbonyl structures in spectral groups C and D are not the result of different effective metamorphic temperatures, rather these differences likely result from variation in the activity of water and oxygen at different stages of parent body metamorphism. Such environmental variations must be local phenomena in the parent bodies as there is no correlation between spectral grouping and chondrite class or group. (C) 2011 Elsevier Ltd. All rights reserved.

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 nitrogen- and 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. (C) 2011 COSPAR. Published by Elsevier Ltd. All rights reserved.

The adsorption configuration of organic molecules on mineral surfaces is of great interest because it can provide fundamental information for both engineered and natural systems. Here we have conducted surface-enhanced Raman spectroscopy (SERS) measurements to probe the attachment configurations of DOPA on nanorutile particles under different pH and surface coverage conditions. The Raman signal enhancement arises when a charge transfer (CT) complex forms between the nanopartides and adsorbed DOPA This Raman signal is exdusively from the surface-bound complexes with great sensitivity to the binding and orientation of the DOPA attached to the TiO2 surface. Our SERS spectra show peaks that progressively change with pH and surface coverage, indicating changing surface speciation. At low pH and surface coverage, DOPA adsorbs on the surface lying down, with probably three points of attachment, whereas at higher pH and surface coverage DOPA stands up on the surface as a species involving two attachment points via the two phenolic oxygens. Our results demonstrate experimentally the varying proportions of the two surface species as a function of environmental conditions consistent with published surface complexation modeling. This observation opens up the possibility to manipulate organic molecule attachment in engineered systems such as biodetection devices. Furthermore, it provides a perspective on the possible role of mineral surfaces in the chemical evolution of biomolecules on the early Earth. Adsorbed biomolecules on mineral surface in certain configurations may have had an advantage for subsequent condensation reactions, facilitating the formation of peptides.

Recent studies reveal substantial variability in biosynthetic H-2/H-1 fractionation between lipids and water, which highlights the effect of central metabolic pathways on the H isotopic composition of the end products. Using multi-nuclear (H-1, H-2 and C-13) solid state nuclear magnetic resonance (NMR) spectroscopy and gas chromatography-mass spectrometry (GC-MS), we were able to track the incorporation of H-1 and H-2 metabolic fluxes into different cellular components of Escherichia coli during growth on two sets of media: (i) 10% deuterated water and non-deuterated glucose, and (ii) non-deuterated water and 10% deuterated glucose. In the 10% H-2 water experiment, the H-2 abundance of the bulk cell was 4.5%; the H-2 uptake by membrane lipids, aliphatic H in proteins, and all the non-aliphatic H positions (including nucleic acids and sugars) was 6.2%, 2.3% and 6.2%, respectively. In the 10% H-2 glucose experiment, the corresponding H-2 uptake was 2.0%, 1.4% and 2.5%, respectively, and 1.9% for the bulk cell. The net fractionation of fatty acids (FAs) relative to water and glucose was consistent with that in studies employing natural H-2 abundance, suggesting the 10% deuterated environment does not alter isotope fractionation during FA biosynthesis. Aliphatic H in proteins was significantly depleted in H-2 relative to FAs by 290-640 parts per thousand. This depletion is likely related to the dynamic regulation of central metabolic pathways that gradually builds up H-2 in tricarboxylic acid (TCA) cycle intermediates though continuous interaction with water, leading to the rapid synthesis of isotopically light amino acids early in the cell cycle and the production of isotopically enriched FAs late in the cell cycle. Besides, enzyme malfunctioning caused by H-2 substitution is likely to promote proteolysis, which could also contribute to the H-2 depletion in proteins. Non-aliphatic H positions as a whole exhibited similar net fractionation factors to the lipids. The study provides an overview of H isotope distribution in the major molecular constituents of intact bacterial cells, offering insight into the mechanisms underlying the metabolic control on the H isotopic composition of biomarker precursors. (c) 2013 Elsevier Ltd. All rights reserved.