Molecular and isotopic analyses of Tagish Lake alkyl dicarboxylic acids

Abstract— The Tagish Lake meteorite soluble organic suite has a general composition that differs from those of both CI and CM chondrites. These differences suggest that distinct processes may have been involved in the formation of different groups of organics in meteorites. Tagish Lake alkyl dicarboxylic acids have a varied, abundant distribution and are, with carboxylated pyridines, the only compounds to have an occurrence comparable to that of the Murchison meteorite. This study has undertaken their molecular and isotopic characterization, with the aim to understand their origin and to gain insights into the evolutionary history of the meteorite parent body. Tagish Lake alkyl dicarboxylic acids are present as a homologous series of saturated and unsaturated species with three‐ through ten‐carbon atom chain length. Linear saturated acids are predominant and show decreasing amounts with increasing chain length. A total of 44 of these compounds were detected with the most abundant, succinic acid, present at ?40 nmol/g meteorite. Overall the molecular distribution of Tagish Lake dicarboxylic acids shows a remarkable compound‐to‐compound correspondence with those observed in the Murchison and Murray meteorites. In both Tagish Lake and Murchison, the imides of the more abundant dicarboxylic acids were also observed. The hydrogen and carbon isotopic compositions of individual Tagish Lake dicarboxylic acids were determined and compared to those of the corresponding acids in the Murchison meteorite. All δD and δ¹³C values for Tagish Lake acids are positive and show a substantial isotopic enrichment. δD values vary from, approximately, +1120%_o for succinic acid to +1530%_o for methyl glutaric acid. δ¹³C values ranged from +12.6%_o for methyl glutaric acid to +22.9%_o for glutaric acid, with adipic acid having a significantly lower value (+5.5%_o). Murchison dicarboxylic acid showed similar isotopic values: their δ5¹³C values were generally higher by an average 17% and δD values were lower for succinic and glutaric acids, possibly due to contamination. The molecular and isotopic data collected for these compounds restrict their possible origin to processes, either interstellar or of very cold nebular regions, that produced significant isotopic enrichments. Saturated or partially unsaturated nitriles and dinitriles appear to be good precursor candidates as their hydrolysis, upon water exposure, would produce dicarboxylic acids and other carboxylated species found in Tagish Lake. This evolutionary course could possibly include pre‐accretionary processes.     

Isotopic and chemical variation of organic nanoglobules in primitive meteorites

Organic nanoglobules are microscopic spherical carbon‐rich objects present in chondritic meteorites and other astromaterials. We performed a survey of the morphology, organic functional chemistry, and isotopic composition of 184 nanoglobules in insoluble organic matter (IOM) residues from seven primitive carbonaceous chondrites. Hollow and solid nanoglobules occur in each IOM residue, as well as globules with unusual shapes and structures. Most nanoglobules have an organic functional chemistry similar to, but slightly more carboxyl‐rich than, the surrounding IOM, while a subset of nanoglobules have a distinct, highly aromatic functionality. The range of nanoglobule N isotopic compositions was similar to that of nonglobular ¹⁵N‐rich hotspots in each IOM residue, but nanoglobules account for only about one third of the total ¹⁵N‐rich hotspots in each sample. Furthermore, many nanoglobules in each residue contained no ¹⁵N enrichment above that of bulk IOM. No morphological indicators were found to robustly distinguish the highly aromatic nanoglobules from those that have a more IOM‐like functional chemistry, or to distinguish ¹⁵N‐rich nanoglobules from those that are isotopically normal. The relative abundance of aromatic nanoglobules was lower, and nanoglobule diameters were greater, in more altered meteorites, suggesting the creation/modification of IOM‐like nanoglobules during parent‐body processing. However, ¹⁵N‐rich nanoglobules, including many with highly aromatic functional chemistry, likely reflect preaccretionary isotopic fractionation in cold molecular cloud or protostellar environments. These data indicate that no single formation mechanism can explain all of the observed characteristics of nanoglobules, and their properties are likely a result of multiple processes occurring in a variety of environments.     

Carbon isotopic composition of acetic acid generated by hydrous pyrolysis of macromolecular organic matter from the Murchison meteorite

Abstract— Low molecular weight monocarboxylic acids, including acetic acid, are some of the most abundant organic compounds in carbonaceous chondrites. So far, the ¹³C‐ and D‐enriched signature of water‐extractable carboxylic acids has implied an interstellar contribution to their origin. However, it also has been proposed that monocarboxylic acids could be formed by aqueous reaction on the meteorite parent body. In this study, we conducted hydrous pyrolysis of macromolecular organic matter purified from the Murchison meteorite (CM2) to examine the generation of monocarboxylic acids with their stable carbon isotope measurement. During hydrous pyrolysis of macromolecular organic matter at 270–330 °C, monocarboxylic acids with carbon numbers ranging from 2 (C₂) to 5 (C₅) were detected, acetic acid (CH₃COOH; C₂) being the most abundant. The concentration of the generated acetic acid increased with increasing reaction temperature; up to 0.48 mmol acetic acid/g macromolecular organic matter at 330 °C. This result indicates that the Murchison macromolecule has a potential to generate at least ?0.4 mg acetic acid/g meteorite, which is about four times higher than the amount of water‐extractable acetic acid reported from Murchison. The carbon isotopic composition of acetic acid generated by hydrous pyrolysis of macromolecular organic matter is ?‐27‰ (versus PDB), which is much more depleted in ¹³C than the water‐extractable acetic acid reported from Murchison. Intramolecular carbon isotope distribution shows that methyl (CH₃‐)‐C is more enriched in ¹³C relative to carboxyl (‐COOH)‐C, indicating a kinetic process for this formation. Although the experimental condition of this study (i.e., 270–330 °C for 72 h) may not simulate a reaction condition on parent bodies of carbonaceous chondrite, it may be possible to generate monocarboxylic acids at lower temperatures for a longer period of time.     

Structure,composition, and location of organic matter in the enstatite chondrite Sahara 97096 (EH3)

Abstract– The insoluble organic matter (IOM) of an unequilibrated enstatite chondrite Sahara (SAH) 97096 has been investigated using a battery of analytical techniques. As the enstatite chondrites are thought to have formed in a reduced environment at higher temperatures than carbonaceous chondrites, they constitute an interesting comparative material to test the heterogeneities of the IOM in the solar system and to constrain the processes that could affect IOM during solar system evolution. The SAH 97096 IOM is found in situ: as submicrometer grains in the network of fine‐grained matrix occurring mostly around chondrules and as inclusions in metallic nodules, where the carbonaceous matter appears to be more graphitized. IOM in these two settings has very similar δ¹⁵N and δ¹³C; this supports the idea that graphitized inclusions in metal could be formed by metal catalytic graphitization of matrix IOM. A detailed comparison between the IOM extracted from a fresh part and a terrestrially weathered part of SAH 97096 shows the similarity between both IOM samples in spite of the high degree of mineral alteration in the latter. The isolated IOM exhibits a heterogeneous polyaromatic macromolecular structure, sometimes highly graphitized, without any detectable free radicals and deuterium‐heterogeneity and having mean H‐ and N‐isotopic compositions in the range of values observed for carbonaceous chondrites. It contains some submicrometer‐sized areas highly enriched in ¹⁵N (δ¹⁵N up to 1600‰). These observations reinforce the idea that the IOM found in carbonaceous chondrites is a common component widespread in the solar system. Most of the features of SAH 97096 IOM could be explained by the thermal modification of this main component.     

A XANES and Raman investigation of sulfur speciation and structural order in Murchison and Allende meteorites

Insoluble organic matter (IOM) and hydrothermally treated IOM extracted from two carbonaceous chondrites, Murchison and Allende, was studied using sulfur K‐edge XANES (X‐ray absorption near edge structure) and μ‐Raman spectroscopy, with the aim to understand their IOM's sulfur speciation and structural order, and how aqueous alteration or thermal metamorphism may have transformed these materials. We found that the sulfur‐functional group chemistry of both the Murchison IOM and hydrothermally treated IOM samples have a large chemical variability ranging from oxidation states of S^?2 to S⁺⁶, and exhibit a transformation in their oxidation state after the hydrothermal treatment (HT) to produce thiophenes and thiol compounds. Sulfoxide and sulfite peaks are also present in Murchison. Sulfates considered intrinsic to Murchison are most likely preaccretionary in nature, and not a result of reactions with water at high temperatures on the asteroid parent body. We argue that the reduced sulfides may have formed in the CM parent body, while the thiophenes and thiol compounds are a result of the HT. Micro‐Raman spectra show the presence of aliphatic and aromatic moieties in Murchison's material as observed previously, which exhibits no change after HT. Because the Murchison IOM was modified, as seen by XANES analysis, absence of a change observed using micro‐Raman indicated that although the alkyl carbons of IOM were cleaved, the aromatic network was not largely modified after HT. By contrast, Allende IOM contains primarily disulfide and elemental sulfur, no organic sulfur, and shows no transformation after HT. This nontransformation of Allende IOM after HT would indicate that parent body alteration of sulfide to sulfate is not feasible up to temperatures of 300°C. The reduced sulfur products indicate extreme secondary chemical processing from the precursor compounds in its parent body at temperatures as high as 624°C, as estimated from μ‐Raman D band parameters. The Raman parameters in Allende IOM that was interpreted in terms of amorphous carbon with regions of large clusters of benzene rings, was transformed after the HT to those with fewer benzene rings.     

Carbonaceous materials in the acid residue from the Orgueil carbonaceous chondrite meteorite

Abstract— Insoluble organic matter (IOM) dominates the HF/HCl residue of the Orgueil (CI) carbonaceous chondrite meteorite. The IOM is composed primarily of two C‐rich particle types. The first has a fluffy texture similar to crumpled tissue paper, and the second type occurs as solid or hollow nanospheres. High‐resolution transmission electron microscope (HRTEM) images of the fluffy material show it is poorly ordered, with small, irregularly shaped regions having fringes with 0.34–0.38 nm spacings and locally 0.21 nm cross‐fringes. Nanodiamonds occur in the fluffy material. The rounded C‐rich particles are common in the residue and their HRTEM images show neither fringes nor nanodiamonds. Both types of carbonaceous materials have a high aromatic component, as revealed by electron energy‐loss spectroscopy (EELS), with up to 10 at% substitution by S, N, and O. The average compositions of the fluffy material and nanospheres are C₁₀₀S_1.9N_3.7O_4.9 and C₁₀₀S_2.4N_5.0O_3.9, respectively. The structural and chemical heterogeneity of the carbonaceous materials may represent material from multiple sources.     

Elemental and isotope behavior of macromolecular organic matter from CM chondrites during hydrous pyrolysis

Abstract— A new insight into carbon and hydrogen isotope variations of insoluble organic matter (IOM) is provided from seven CM chondrites, including Murchison and six Antarctic meteorites (Y‐791198, Y‐793321, A‐881280, A‐881334, A‐881458 and B‐7904) as well as Murchison IOM residues after hydrous pyrolysis at 270–330 °C for 72 h. Isotopic compositions of bulk carbon (δ¹³C_bulk) and hydrogen (δD) of the seven IOMs vary widely, ranging from ?15.1 to ?7.6%₀ and +133 to +986%₀, respectively. Intramolecular carboxyl carbon (δ13C_COOH) is more enriched in ¹³C by 7.5. 11%₀ than bulk carbon. After hydrous pyrolysis of Murchison IOM at 330 °C, H/C ratio, δ13C_bulk, δ13C_COOH, and δD values decrease by up to 0.31, 3.5%₀, 5.5%₀, and 961%₀, respectively. The O/C ratio increases from 0.22 to 0.46 at 270 °C and to 0.25 at 300 °C, and decreases to 0.10 at 330 °C. δ13C_bulk‐δD cross plot of Murchison IOM and its pyrolysis residues shows an isotopic sequence. Of the six Antarctic IOMs, A‐881280, A‐881458, Y‐791198 and B‐7904 lie on or near the isotopic sequence depending on the degree of hydrous and/or thermal alteration, while A‐881334 and Y‐793321 consist of another distinct isotope group. A δ13C_bulk‐δ13C_COOH cross‐plot of IOMs, including Murchison pyrolysis residues, has a positive correlation between them, implying that the oxidation process to produce carboxyls is similar among all IOMs. These isotope distributions reflect various degree of alteration on the meteorite parent bodies and/or difference in original isotopic compositions before the parent body processes.     

A molecular and isotopic study of the macromolecular organic matter of the ungrouped C2 WIS 91600 and its relationship to Tagish Lake and PCA 91008

Abstract– Insight into the chemical history of an ungrouped type 2 carbonaceous chondrite meteorite, Wisconsin Range (WIS) 91600, is gained through molecular analyses of insoluble organic matter (IOM) using solid‐state ¹³C nuclear magnetic resonance (NMR) spectroscopy, X‐ray absorption near edge structure spectroscopy (XANES), and pyrolysis‐gas chromatography coupled with mass spectrometry (pyr‐GC/MS), and our previous bulk elemental and isotopic data. The IOM from WIS 91600 exhibits similarities in its abundance and bulk δ¹⁵N value with IOM from another ungrouped carbonaceous chondrite Tagish Lake, while it exhibits H/C, δ¹³C, and δD values that are more similar to IOM from the heated CM, Pecora Escarpment (PCA) 91008. The ¹³C NMR spectra of IOM of WIS 91600 and Tagish Lake are similar, except for a greater abundance of CH_xO species in the latter and sharper carbonyl absorption in the former. Unusual cross‐polarization (CP) dynamics is observed for WIS 91600 that indicate the presence of two physically distinct organic domains, in which the degrees of aromatic condensation are distinctly different. The presence of two different organic domains in WIS 91600 is consistent with its brecciated nature. The formation of more condensed aromatics is the likely result of short duration thermal excursions during impacts. The fact that both WIS 91600 and PCA 91008 were subjected to short duration heating that is distinct from the thermal history of type 3 chondrites is confirmed by Carbon‐XANES. Finally, after being briefly heated (400 °C for 10 s), the pyrolysis behavior of Tagish Lake IOM is similar to that of WIS 91600 and PCA 91008. We conclude that WIS 91600 experienced very moderate, short duration heating at low temperatures (<500 °C) after an episode of aqueous alteration under conditions that were similar to those experienced by Tagish Lake.     

Molecular distribution, 13C‐isotope,and enantiomeric compositions of carbonaceous chondrite monocarboxylic acids

The water‐soluble organic compounds in carbonaceous chondrite meteorites constitute a record of the synthetic reactions occurring at the birth of the solar system and those taking place during parent body alteration and may have been important for the later origins and development of life on Earth. In this present work, we have developed a novel methodology for the simultaneous analysis of the molecular distribution, compound‐specific δ¹³C, and enantiomeric compositions of aliphatic monocarboxylic acids (MCA) extracted from the hot‐water extracts of 16 carbonaceous chondrites from CM, CR, CO, CV, and CK groups. We observed high concentrations of meteoritic MCAs, with total carbon weight percentages which in some cases approached those of carbonates and insoluble organic matter. Moreover, we found that the concentration of MCAs in CR chondrites is higher than in the other meteorite groups, with acetic acid exhibiting the highest concentration in all samples. The abundance of MCAs decreased with increasing molecular weight and with increasing aqueous and/or thermal alteration experienced by the meteorite sample. The δ¹³C isotopic values of MCAs ranged from ?52 to +27‰, and aside from an inverse relationship between δ¹³C value and carbon straight‐chain length for C₃–C₆ MCAs in Murchison, the ¹³C‐isotopic values did not correlate with the number of carbon atoms per molecule. We also observed racemic compositions of 2‐methylbutanoic acid in CM and CR chondrites. We used this novel analytical protocol and collective data to shed new light on the prebiotic origins of chondritic MCAs.     

Quantifying hydrogen‐deuterium exchange of meteoritic dicarboxylic acids during aqueous extraction

Abstract— Hydrogen isotope ratios of organic compounds in carbonaceous chondrites provide critical information about their origins and evolutionary history. However, because many of these compounds are obtained by aqueous extraction, the degree of hydrogen‐deuterium (H/D) exchange that occurs during the process needs to be quantitatively evaluated. This study uses compound‐specific hydrogen isotopic analysis to quantify the H/D exchange during aqueous extraction. Three common meteoritic dicarboxylic acids (succinic, glutaric, and 2‐methyl glutaric acids) were refluxed under conditions simulating the extraction process. Changes in δD values of the dicarboxylic acids were measured following the reflux experiments. A pseudo‐first order rate law was used to model the H/D exchange rates which were then used to calculate the isotope exchange resulting from aqueous extraction. The degree of H/D exchange varies as a result of differences in molecular structure, the alkalinity of the extraction solution and presence/absence of meteorite powder. However, our model indicates that succinic, glutaric, and 2‐methyl glutaric acids with a δD of 1800%***_o would experience isotope changes of 38_o, 10_o, and 6_o, respectively during the extraction process. Therefore, the overall change in δD values of the dicarboxylic acids during the aqueous extraction process is negligible. We also demonstrate that H/D exchange occurs on the chiral α‐carbon in 2‐methyl glutaric acid. The results suggest that the racemic mixture of 2‐methyl glutaric acid in the Tagish Lake meteorite could result from post‐synthesis aqueous alteration. The approach employed in this study can also be used to quantify H/D exchange for other important meteoritic compounds such as amino acids.     

UV photolysis of quinoline in interstellar ice analogs

Abstract— The polycyclic aromatic nitrogen heterocycle (PANH) quinoline (C₉H₇N) was frozen at 20 K in interstellar ice analogs containing either pure water or water mixed with methanol or methane and exposed to ultraviolet (UV) radiation. Upon warming, the photolysis products were analyzed by high‐performance liquid chromatography and nanoscale liquid chromatography‐electrospray ionization mass spectrometry. A suite of hydroxyquinolines, which were formed by the addition of oxygen atoms to quinoline, was observed as the primary product in all the ices. Quinoline N oxide was not formed, but five hydroxyquinoline isomers were produced with no clear dominance of one isomer. Reduction products, formed by hydrogen atom addition, were also created. Ices created at 20 K with H₂O: quinoline ratios of 10:1 to 100:1 showed similar product distributions to those at 122 K, with no apparent temperature or concentration dependence. Increasing the UV dose led to a decrease in overall yield, indicating that quinoline and its products may be photo‐destroyed. Methylquinolines were formed upon photolysis of the methanol‐ and methane‐containing ices. In addition, possible methoxyquinolines or quinoline methylene alcohols were formed in the methanol‐containing ice, while methylhydroxyquinolines were created in the methane‐containing ice. This work indicates that oxidation of PANHs could occur in icy extraterrestrial environments and suggests that a search for such compounds in carbonaceous meteorites could illuminate the possible link between interstellar ice chemistry and meteoritic organics. Given the importance of oxidized and alkylated PANHs to biochemistry, the formation and delivery of such molecules to the early Earth may have played a role in the origin and evolution of life.     

Elemental,isotopic, and structural changes in Tagish Lake insoluble organic matter produced by parent body processes

Here, we present the results of a multitechnique study of the bulk properties of insoluble organic material (IOM) from the Tagish Lake meteorite, including four lithologies that have undergone different degrees of aqueous alteration. The IOM C contents of all four lithologies are very uniform and comprise about half the bulk C and N contents of the lithologies. However, the bulk IOM elemental and isotopic compositions vary significantly. In particular, there is a correlated decrease in bulk IOM H/C ratios and δD values with increasing degree of alteration—the IOM in the least altered lithology is intermediate between CM and CR IOM, while that in the more altered lithologies resembles the very aromatic IOM in mildly metamorphosed CV and CO chondrites, and heated CMs. Nuclear magnetic resonance (NMR) spectroscopy, C X‐ray absorption near‐edge (XANES), and Fourier transform infrared (FTIR) spectroscopy confirm and quantitate this transformation from CR‐like, relatively aliphatic IOM functional group chemistry to a highly aromatic one. The transformation is almost certainly thermally driven, and probably occurred under hydrothermal conditions. The lack of a paramagnetic shift in ¹³C NMR spectra and 1s‐σ* exciton in the C‐XANES spectra, both typically seen in metamorphosed chondrites, shows that the temperatures were lower and/or the timescales were shorter than experienced by even the least metamorphosed type 3 chondrites. Two endmember models were considered to quantitatively account for the changes in IOM functional group chemistry, but the one in which the transformations involved quantitative conversion of aliphatic material to aromatic material was the more successful. It seems likely that similar processes were involved in producing the diversity of IOM compositions and functional group chemistries among CR, CM, and CI chondrites. If correct, CRs experienced the lowest temperatures, while CM and CI chondrites experienced similar more elevated temperatures. This ordering is inconsistent with alteration temperatures based on mineralogy and O isotopes.     

The amino acid and hydrocarbon contents of the Paris meteorite: Insights into the most primitive CM chondrite

The Paris meteorite is one of the most primitive carbonaceous chondrites. It is reported to be the least aqueously altered CM chondrite, and to have experienced only weak thermal metamorphism. We have analyzed for the first time the amino acid and hydrocarbon contents of this pristine meteorite by gas chromatography–mass spectrometry (GC–MS). When plotting the relative amino acids abundances of several CM chondrites according to the increasing hydrothermal scale (petrologic subtypes), from the CM2.7/2.8 Paris to the CM2.0 MET 01070, Paris has the lowest relative abundance of β‐alanine/glycine (0.15), which fits with the relative abundances of β‐alanine/glycine increasing with increasing aqueous alteration for CM chondrites. These results confirm the influence of aqueous alteration on the amino acid abundances and distribution. The amino acid analysis shows that the isovaline detected in this meteorite is racemic (d /l  = 0.99 ± 0.08; l ‐enantiomer excess = 0.35 ± 0.5%; corrected d /l  = 1.03; corrected l ‐enantiomer excess = ?1.4 ± 2.6%). The identified hydrocarbons show that Paris has n‐alkanes ranging from C₁₆ to C₂₅ and 3‐ to 5‐ring nonalkylated polycyclic aromatic hydrocarbons (PAHs). The lack of alkylated PAHs in Paris seems to be also related to this low degree of aqueous alteration on its parent body. The extraterrestrial hydrocarbon content, suggested by the absence of any biomarker, may well have a presolar origin. The chemistry of the Paris meteorite may thus be closely related to the early stages of the solar nebula with a contribution from interstellar (molecular cloud) precursors.     

An abiotic origin for hydrocarbons in the Allan Hills 84001 martian meteorite through cooling of magmatic and impact‐generated gases

Abstract— Thermodynamic calculations of metastable equilibria were used to evaluate the potential for abiotic synthesis of aliphatic and polycyclic aromatic hydrocarbons (PAHs) in the martian meteorite Allan Hills (ALH) 84001. The calculations show that PAHs and normal alkanes could form metastably from CO, CO², and H² below approximately 250–300°C during rapid cooling of trapped magmatic or impact‐generated gases. Depending on temperature, bulk composition, and oxidation‐reduction conditions, PAHs and normal alkanes can form simultaneously or separately. Moreover, PAHs can form at lower H/C ratios, higher CO/CO² ratios, and higher temperatures than normal alkanes. Dry conditions with H/C ratios less than approximately 0.01–0.001 together with high CO/CO² ratios also favor the formation of unalkylated PAHs. The observed abundance of PAHs, their low alkylation, and a variable but high aromatic to aliphatic ratio in ALH 84001 all correspond to low H/C and high CO/CO² ratios in magmatic and impact gases and can be used to deduce spatial variations of these ratios. Some hydrocarbons could have been formed from trapped magmatic gases, especially if the cooling was fast enough to prevent reequilibration. We propose that subsequent impact heating(s) in ALH 84001 could have led to dissociation of ferrous carbonates to yield fine‐grain magnetite, formation of a CO‐rich local gas phase, reduction of water vapor to H², reequilibration of the trapped magmatic gases, aromatization of hydrocarbons formed previously, and overprinting of the synthesis from magmatic gases, if any. Rapid cooling and high‐temperature quenching of CO‐, H²‐rich impact gases could have led to magnetite‐catalyzed hydrocarbon synthesis     

Formation of CmSn compounds by photopolymerization of CS2 in the atmosphere of Jupiter

Abstract— Toluene extracts from two (CS_n)_x photopolymers were examined with high‐performance liquid chromatography (HPLC), matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF) mass spectrometry, particle‐induced x‐ray emission (PIXE), and ¹²C(d,p)¹³C nuclear microprobing. the extracts contained elemental s and at least from 17 to 20 distinct c_ms_n compounds with m/z less than ～500 amu. Whereas H₂S is the dominant S‐bearing compound of the normal jovian atmosphere, elemental S, CS, and CS₂ were observed at Shoemaker‐Levy 9 cometary impact sites and at altitudes of the transiently disturbed jovian atmosphere where photodissociation and photopolymerization occur. It is uncertain whether the CS₂ molecular densities were sufficiently large for both to occur, but photopolymerization could have occurred during larger impacts of Jupiter's history. Because the known stable C_mS_n compounds are yellow, orange and deep red, they could contribute significantly to the colors of the jovian clouds.     

Molecular study of insoluble organic matter in Kainsaz CO3 carbonaceous chondrite: Comparison with CI and CM IOM

Abstract— Kainsaz CO3 insoluble organic matter (IOM) was studied using Curie point pyrolysis, electronic paramagnetic resonance (EPR), and high‐resolution transmission electron microscopy (HRTEM) to determine the effect of thermal metamorphism on molecular chondritic fingerprints. Pyrolysis released a very low amount of products that consist of one‐ and two‐ring aromatic units with methyl, dimethyl, and ethyl substituents. Moreover, Kainsaz IOM contains two orders of magnitude fewer radicals than Orgueil, Murchison, and Tagish Lake IOM. In addition, no diradicaloids were found in Kainsaz, although they are thought to constitute a specific signature for weakly organized extraterrestrial organic compounds in contrast to terrestrial ones. HRTEM reveals a very heterogeneous structure, with microporous disordered carbon, mesoporous graphitic carbons and graphite. Graphitization likely occurs and explains the differences between Kainsaz and CI or CM IOM. Heating stress experienced by Kainsaz IOM, on the parent body and/or prior its accretion, is likely responsible for the differences in molecular and structural organizations compared with those of CI and CM IOM.     

Model of molecular structure of the insoluble organic matter isolated from Murchison meteorite

Abstract– The molecular structure of the insoluble organic matter (IOM) from Murchison meteorite has been investigated by our group for several years using a large set of analytical methods including various spectroscopies (Fourier transform infrared spectroscopy, nuclear magnetic resonance, electron paramagnetic resonance, X‐ray absorption near‐edge spectroscopy), high resolution electron microscopy, and thermal (pyrolyses in the presence or not of tetramethylammonium hydroxide) and chemical (RuO₄ oxidation) degradations. Taken together, these techniques provided a wealth of qualitative and quantitative information, from which we derived 11 elemental and molecular parameters on the same IOM residue. In addition to the basic elemental composition, these parameters describe the distribution of the different types of carbon, nitrogen, and sulfur atoms as well as the size of the polyaromatic units. For this molecular structure, we therefore propose a model which fits with these 11 molecular quantitative parameters. Several cosmochemical implications are derived from this structure. Based on the fact that aromatic moieties are highly substituted and aliphatic chains highly branched, it can be anticipated that the synthesis of this IOM occurred through successive additions of single carbon units in the gas‐phase ending by a spontaneous cyclization for chain length ≥7 C. As a whole, these observations favor an organosynthesis in the solar T‐Tauri disk.     

The ORGANICS experiment on BIOPAN V: UV and space exposure of aromatic compounds

We studied the stability of aromatic compounds in low Earth orbit environment and describe the scientific results and successful flight of the ORGANICS experiment on-board the BIOPAN V space exposure facility. This experiment investigated the photo stability of large organic molecules in low Earth orbit. Thin films of selected organic molecules, such as polycyclic aromatic hydrocarbons (PAHs) and the fullerene C₆₀ were subjected to the low Earth orbit environment and the samples were monitored before and after flight. PAHs and fullerenes have been proposed as carriers for a number of astronomical absorption and emission features and are also identified in meteorites. Our experiment on BIOPAN V was exposed to a total fluence of 602.45 kJ m⁻² for photons in the range 170–280 nm. The experiment was also intended as a hardware test-flight for a long-term exposure experiment (Survival of organics in space) on the EXPOSE facility on the International Space Station (ISS). For the small fluence that was collected during the BIOPAN V experiment we found little evidence of photo-destruction. The results confirm that PAH molecules are very stable compounds in space. The small differences in destruction rates that are expected to arise among the PAH samples as a function of molecular size and structure will only show after the longer irradiation fluences that are expected in the exposure experiment on the ISS.     

High‐mass resolution molecular imaging of organic compounds on the surface of Murchison meteorite

High‐resolution mass spectrometry (HRMS) imaging by desorption electrospray ionization (DESI) coupled with Orbitrap MS using methanol (MeOH) spray was performed on a fragment of the Murchison (CM2) meteorite in this study. Homologues of C_nH_2n–1N₂⁺ (n = 7–9) and C_nH_2nNO⁺ (n = 9–14) were detected on the sample surface by the imaging. A high‐performance liquid chromatography (HPLC)/HRMS analysis of MeOH extracts from the sample surface after DESI/HRMS imaging indicated that the C_nH_2n–1N₂⁺ homologues corresponds to alkylimidazole, and that a few isomers of the C_nH_2nNO⁺ homologues present in the sample. The alkylimidazoles and C_nH_2nNO⁺ homologues displayed different spatial distributions on the surface of the Murchison fragment, indicating chromatographic separation effects during aqueous alteration. Moreover, the distribution pattern of compounds is also different among homologues. This is probably also resulting from the separation of isomers by similar chromatographic effects, or different synthetic pathways. Alkylimidazoles and the C_nH_2nNO⁺ homologues are mainly distributed in the matrix region of the Murchison by mineralogical observations, which is consistent with previous reports. Altered minerals (e.g., Fe‐oxide, Fe‐sulfide, and carbonates) occurred in this region. However, no clear relationship was found between these minerals and the organic compounds detected by DESI/HRMS imaging. Although this result might be due to scale differences between the spatial resolution of DESI/HRMS imaging and the grain size in the matrix of the Murchison, our results would indicate that alkylimidazoles and the C_nH_2nNO⁺ homologues in the Murchison fragment were mainly synthesized by different processes from hydrothermal alteration on the parent body.     

Indigenous aliphatic amines in the aqueously altered Orgueil meteorite

The CI1 Orgueil meteorite is a highly aqueously altered carbonaceous chondrite. It has been extensively studied, and despite its extensive degree of aqueous alteration and some documented instances of contamination, several indigenous organic compounds including amino acids, carboxylic acids, and nucleobases have been detected in its carbon‐rich matrix. We recently developed a novel gas chromatographic method for the enantiomeric and compound‐specific isotopic analyses of meteoritic aliphatic monoamines in extracts and have now applied this method to investigate the monoamine content in Orgueil. We detected 12 amines in Orgueil, with concentrations ranging from 1.1 to 332 nmol g^?1 of meteorite and compared this amine content in Orgueil with that of the CM2 Murchison meteorite, which experienced less parent‐body aqueous alteration. Methylamine is four times more abundant in Orgueil than in Murchison. As with other species, the amine content in Orgueil extracts shows less structural diversity than that in Murchison extracts. We measured the compound‐specific stable carbon isotopic ratios (δ¹³C) for 5 of the 12 monoamines detected in Orgueil and found a range of δ¹³C values from –20 to +59‰. These δ¹³C values fall into the range of other meteoritic organic compounds, although they are ¹³C‐depleted relative to their counterparts extracted from the Murchison meteorite. In addition, we measured the enantiomeric composition for the chiral monoamines (R)‐ and (S)‐sec‐butylamine in Orgueil, and found it was racemic within experimental error, in contrast with the l ‐enantiomeric excess found for its amino acid structural analog isovaline. The racemic nature of sec‐butylamine in Orgueil was comparable to that previously observed in Murchison, and to other CM2 and CR2 carbonaceous chondrites measured in this work (ALH 83100 [CM1/2], LON 94101 [CM2], LEW 90500 [CM2], LAP 02342 [CR2], and GRA 95229 [CR2]). These results allow us to place some constraints on the effects of aqueous alteration observed over the monoamine concentrations in Orgueil and Murchison, and to evaluate the primordial synthetic relationships between meteoritic monoamines and amino acids.