Kinetics of organic matter degradation in the Murchison meteorite for the evaluation of parent‐body temperature history

Abstract– To evaluate kinetic parameters for thermal degradation of organic matter, in situ heating experiments of insoluble organic matter (IOM) and bulk of Murchison (CM2) meteorite were conducted under Fourier transform infrared micro‐spectroscopy combined with a heating stage. Decreases of aliphatic C–H band area under Ar flow were well fitted with Ginstling‐Brounshtein three‐dimensional diffusion model, and the rate constants for decreases of aliphatic C–H were determined. Activation energies E_a and frequency factors A obtained from these rate constants at different temperatures using the Arrhenius equation were E_a = 109 ± 3 kJ mol^?1 and A = 8.7 × 10⁴ s^?1 for IOM, and E_a = 61 ± 6 kJ mol^?1 and A = 3.8 s^?1 for bulk, respectively. Activation energy values of aliphatic C–H decrease are larger for IOM than bulk. Hence, the mineral assemblage of the Murchison meteorite might have catalytic effects for the organic matter degradation. Using obtained kinetic expressions, the time scale for metamorphism can be estimated for a given temperature with aliphatic C–H band area, or the temperature of metamorphism can be estimated for a given time scale. For example, using the obtained kinetic parameters of IOM, aliphatic C–H is lost approximately within 200 years at 100 °C and 100 Myr at 0 °C. Assuming alteration period of 7.5 Myr, alteration temperatures could be calculated to be <15 ± 12 °C. Aliphatic C–H decrease profiles in a parent body can be estimated using time–temperature history model. The kinetic expression obtained by the infrared spectral band of aliphatic C–H could be used as an alternative method to evaluate thermal processes of organic matter in carbonaceous chondrites.     

The Temperature-Dependent Spectrum of Methane Ice I between 0.7 and 5 μm and Opportunities for Near-Infrared Remote Thermometry

New infrared absorption coefficient spectra of pure methane ice I were measured at temperatures between 30 and 90 K, over wavelengths from 0.7 to 5 μm, along with spectra of methane ice II at 20 K and liquid methane at 93 K. The spectra were derived from transmission measurements through monocrystalline samples grown in a series of closed cells having interior dimensions ranging from 100 μm to 1 cm. The thicker samples permitted measurement of extremely weak absorption bands, with absorption coefficients as small as 0.003 cm⁻¹. We report 14 new absorption bands, which we tentatively assign to specific vibrational transitions. Two of the new bands are attributed to CH₃D. Measurements of the weaker CH₄ bands are particularly needed for interpreting spectral observations of Pluto and Triton, where a number of weak CH₄-ice absorption bands have been observed. The data presented in this paper complement studies of spectral transmission by thin films of methane ice, which are most suitable for measuring the stronger absorption bands. Temperature-dependent spectral features revealed by the new data offer the opportunity to determine CH₄-ice temperatures remotely, via near-infrared reflectance spectroscopy. This approach could prove particularly valuable for future spacecraft exploration of Pluto.     

Cassini CIRS update on stratospheric ices at Titan's winter pole

A strong, broad spectral emission feature at 85° N latitude centered at 221 cm⁻¹ remains unidentified after candidate ices of H₂O and pure crystalline CH₃CH₂CN are unambiguously ruled out. A much shallower weak emission feature starts at 160 cm⁻¹ and blends into the strong feature at ∼190 cm⁻¹. This feature is consistent with one formed by an HCN ice cloud composed of ?5 μm radius particles that resides in the lower stratosphere somewhere below an altitude of 160 km. Titan's stratospheric aerosol appears to have a spectral emission feature at about 148 cm⁻¹. The aerosol abundance at 85° N is about a factor 2.2 greater than at 55° S.     

Organic and inorganic correlations for Northwest Africa 852 by synchrotron‐based Fourier transform infrared microspectroscopy

Relationships between organic molecules and inorganic minerals are investigated in a single 34 μm diameter grain of the CR2 chondrite Northwest Africa 852 (NWA) 852 with submicron spatial resolution using synchrotron‐based imaging micro‐FTIR spectroscopy. Correlations based on absorption strength for the various constituents are determined using statistical correlation analysis. The silicate band is found to be correlated with the hydration band, and the latter is highly correlated with stretching modes of aliphatic hydrocarbons. Spatial distribution maps show that water+organic combination, silicate, OH, and C‐H distributions overlap, suggesting a possible catalytic role of phyllosilicates in the formation of organics. In contrast, the carbonate band is anticorrelated with water+organic combination, however uncorrelated with any other spectral feature. The average ratio of asymmetric CH₂ and CH₃ band strengths (CH₂/CH₃ = 2.53) for NWA 852 is similar to the average ratio of interplanetary dust particles (~2.40) and Wild 2 cometary dust particles (2.50), but it significantly exceeds that of interstellar medium objects (~1.00) and several aqueously altered carbonaceous chondrites (~1.40). This suggests organics of similar length/branching, and perhaps similar formation regions, for NWA 852, Wild 2 dust particles, and interplanetary dust particles. The heterogeneous spatial distribution of ratio values indicates the presence of a mixture of aliphatic organic material with different length/branching, and thus a wide range of parent body processes, which occurred before the considered grain was formed.     

Infrared imaging spectroscopy with micron resolution of Sutter's Mill meteorite grains

Synchrotron‐based Fourier transform infrared spectroscopy and Raman spectroscopy are applied with submicrometer spatial resolution to multiple grains of Sutter's Mill meteorite, a regolith breccia with CM1 and CM2 lithologies. The Raman and infrared active functional groups reveal the nature and distribution of organic and mineral components and confirm that SM12 reached higher metamorphism temperatures than SM2. The spatial distributions of carbonates and organic matter are negatively correlated. The spatial distributions of aliphatic organic matter and OH relative to the distributions of silicates in SM2 differ from those in SM12, supporting a hypothesis that the parent body of Sutter's Mill is a combination of multiple bodies with different origins. The high aliphatic CH₂/CH₃ ratios determined from band intensities for SM2 and SM12 grains are similar to those of IDPs and less altered carbonaceous chondrites, and they are significantly higher than those in other CM chondrites and diffuse ISM objects.     

Infrared micro-spectroscopy of the martian meteorite Zagami: Extraction of individual mineral phase spectra

Zagami, a well characterized SNC meteorite, represents a reference sample to verify the feasibility of the non-destructive infrared micro-spectroscopy technique to extract spectral signatures from individual mineral phases in a meteorite sample. For the first time individual infrared spectra of the major mineral phases, in the 6000-600 cm⁻¹ (1.67-16.7 μm) spectral interval, whose identification is confirmed by energy dispersive X-ray analysis and backscattered imaging, are measured. The signatures of the main mineral phases we identified in the Zagami chip are: (1) maskelynite characterized by broad and smooth SiO vibrational bands in the 1000 cm⁻¹ spectral region; (2) crystalline pyroxenes showing well defined fine structures; and (3) an oxide mineral phase with an almost featureless and flat spectrum. In the part of the spectrum centered around 2 μm, by analyzing the different positions of the Fe²⁺ bands, we were able to discern the high-Ca from the low-Ca pyroxene phases. This result demonstrates that by means of the infrared micro-spectroscopy technique it is possible to retrieve directly the composition of pyroxenes in the En-Fs-Wo system, without relying on the use of deconvolution techniques. In addition IR signatures due to water and aliphatic hydrocarbons were observed to be more abundant in the pyroxenes than in maskelynite. This could be an indication that the organic and water signatures are due to indigenous compounds in Zagami rather than laboratory contamination, however, further investigations are necessary before this conclusion can be confirmed.     

Methane evolution from UV-irradiated spacecraft materials under simulated martian conditions: Implications for the Mars Science Laboratory (MSL) mission

Fifteen organic and three inorganic compounds were tested for methane (CH₄) evolution under simulated martian conditions of 6.9 mbar; UVC (200-280 nm) flux of 4 W m⁻²; 20 °C; simulated optical depth of 0.1; and a Mars gas composition of CO₂ (95.3%), N₂ (2.7%), Ar (1.7%), O₂ (0.13%), and water vapor (0.03%). All three inorganic compounds (i.e., NaCl, CaCO₃, graphite) failed to evolve methane at the minimum detection level 0.5 ppm, or above. In contrast, all organic compounds evolved methane when exposed to UV irradiation under simulated martian conditions. The polycyclic aromatic hydrocarbon, pyrene, released the most methane per unit of time at 0.175 nmol CH₄ g⁻¹ h⁻¹, and a spectral reflectance target material used for the MER rovers and Phoenix lander released the least methane at 0.00065 nmol CH₄ cm⁻² h⁻¹. Methane was also released from UV-killed bacterial endospores of Bacillus subtilis. Although all organic compounds evolved methane when irradiated with UV photons under martian conditions, the concentrations of residual organics, biogenic signature molecules, and dead microbial cells should be relatively low on the exterior surfaces of the MSL rover, and, thus, not significant sources of methane contamination. In contrast, kapton tape was found to evolve methane at the rate of 0.00165 nmol CH₄ cm⁻² h⁻¹ (16.5 nmol m⁻² h⁻¹) under the UV and martian conditions tested. Although the evolution of methane from kapton tape was found to decline over time, the large amount of kapton tape used on the MSL rover (lower bound estimated at 3 m²) is likely to create a significant source of terrestrial methane contamination during the early part of the mission.     

Titan: Far-infrared and microwave remote sensing of methane clouds and organic haze

It is shown that Titan's surface and plausible atmospheric thermal opacity sources—gaseous N₂, CH₄, and H₂, CH₄ cloud, and organic haze—are sufficient to match available Earth-based and Voyager observations of Titan's thermal emission spectrum. Dominant sources of thermal emission are the surface for wavelenghts λ ? 1 cm, atmospheric N₂ for 1 cm ? λ ? 200 μm,, condensed and gaseous CH₄ for 200 μm ? λ ? 20 μm, and molecular bands and organic haze for λ ? 20 μm. Matching computed spectra to the observed Voyager IRIS spectra at 7.3 and 52.7° emission angles yields the following abundances and locations of opacity sources: CH₄ clouds: 0.1 g cm^? at a planetocentric radius of 2610–2625 km, 0.3 g cm^?2 at 2590–2610 km, total 0.4 ± 0.1 g cm^–2 above 2590 km; organic haze: $\text{4 ± 2 × 10}{}^{\mathrm{?6}}\text{,}\text{g cm}\text{,}{}^{\mathrm{?2}}$ above 2750 km; tropospheric H₂: 0.3 ± 0.1 mol%. This is the first quantitative estimate of the column density of condensed methane (or CH₄/C₂H₆) on Titan. Maximum transparency in the middle to far IR occurs at 19 μm where the atmospheric vertical absorption optical depth is $\text{?0.6}$ A particle radius $\text{r}\text{? 2 μ}\text{m}$ in the upper portion of the CH₄ cloud is indicated by the apparent absence of scattering effects.     

Raman spectroscopic properties and Raman identification of CaS‐MgS‐MnS‐FeS‐Cr2FeS4 sulfides in meteorites and reduced sulfur‐rich systems

Raman spectra were acquired on a series of natural and synthetic sulfide minerals, commonly found in enstatite meteorites: oldhamite (CaS), niningerite or keilite ((Mg,Fe)S), alabandite (MnS), troilite (FeS), and daubreelite (Cr₂FeS₄). Natural samples come from three enstatite chondrites, three aubrites, and one anomalous ungrouped enstatite meteorite. Synthetic samples range from pure endmembers (CaS, FeS, MgS) to complex solid solutions (Fe, Mg, Ca)S. The main Raman peaks are localized at 225, 285, 360, and 470 cm^?1 for the Mg‐rich sulfides; at 185, 205, and 285 cm^?1 for the Ca‐rich sulfides; at 250, 370, and 580 cm^?1 for the Mn‐rich sulfides; at 255, 290, and 365 cm^?1 for the Cr‐rich sulfides; and at 290 and 335 cm^?1 for troilite with, occasionally, an extra peak at 240 cm^?1. A peak at 160 cm^?1 is present in all Raman spectra and cannot be used to discriminate between the different sulfide compositions. According to group theory, none of the cubic monosulfides oldhamite, niningerite, or alabandite should present first‐order Raman spectra because of their ideal rocksalt structure. The occurrence of broad Raman peaks is tentatively explained by local breaking of symmetry rules. Measurements compare well with the infrared frequencies calculated from first‐principles calculations. Raman spectra arise from activation of certain vibrational modes due to clustering in the solid solutions or to coupling with electronic transitions in semiconductor sulfides.     

Raman spectroscopic investigation of two grains from comet 81P/Wild 2: Information that can be obtained beyond the presence of sp2‐bonded carbon

Abstract– Raman analyses were performed of individual micrometer‐sized fragments of material returned to Earth by the NASA Stardust mission to comet 81P/Wild 2. The studied fragments originated from grains (C2054,0,35,91,0 and C2092,6,80,51,0) of two different penetration tracks that occurred in two different silica aerogel collector cells. All fragments of both particles have Raman spectra characteristic of amorphous sp²‐bonded carbon that are in general agreement with the results published in previous Stardust particle studies. The present study, however, does not focus on the discussion of specific details of the D and G band parameters, but rather reports on additional information that can be obtained from returned Stardust samples via Raman spectroscopy. Most notably, the Raman spectra show that all analyzed fragments of the particles were contaminated with the capture medium (i.e., aerogel). The silica aerogel is laced with organic aliphatic and aromatic hydrocarbon impurities that resulted in strong bands in the ～ 2900 Δcm^?1 spectral range (C‐H stretching modes). Aerogel bands are also found in the 1000–1600 Δcm^?1 spectral range, where they overlap with the bands of the amorphous sp²‐bonded carbon. The peaks associated with the aerogel contamination differ between the two grains that originated from two different aerogel cells. In addition to the bands due to aerogel contamination and the always present sp²‐bonded carbon bands, fragments of particle C2092,6,80,51,0 also show Raman peaks for pyrrhotite and Fa₃₀Fo₇₀ olivine. Complete (up to 4000 Δcm^?1) raw and baseline‐corrected Raman spectra of the Stardust particles are shown and discussed in detail.     

Probing molecular and isotopic features of meteoritic insoluble organic matter by solid‐state nuclear magnetic resonance spectroscopy with sub‐milligram sample

We recorded one‐ and two‐dimensional solid‐state nuclear magnetic resonance spectra of meteoric insoluble organic matter with unprecedented sensitivity and resolution permitting us to reveal unambiguous spectroscopic fingerprints relevant to its molecular and isotopic features. Two‐dimensional ¹H‐¹H and ¹H‐¹³C correlation experiments have unveiled the spatial proximity between aliphatic and aromatic groups proving a highly branched character of a rigid macromolecular network composed of short aliphatic chains linking together small aromatic units. One‐dimensional ²H and two‐dimensional ¹H‐²H correlation spectroscopy delivered evidence of significant reduction in the deuterium enrichment of aromatic species relevant to interstellar processes, proto‐planetary disk chemistry, and to determining the origin of the meteoritic insoluble organic matter. The experimental approach developed in this work opens new perspectives for systematic and nondestructive analysis at the molecular level of meteoritic insoluble organic matter even with a very small amount of sample from some particularly rare chondrites.     

Comparison of FT‐IR spectra of bulk and acid insoluble organic matter in chondritic meteorites: An implication for missing carbon during demineralization

Past studies of the various separable carbonaceous fractions have been unable to account for all of C in primitive chondrites. In particular, up to 20–50% of the C is lost during acid leaching of bulk samples even after the C in carbonates and soluble organic matter is accounted for. To try to better characterize the nature of this “missing C,” we have compared the bulk infrared (IR) absorption spectra of a number of primitive chondrites with those of their previously reported insoluble organic matter (IOM). The aliphatic C–H stretching bands, in particular, allow us to compare the molecular structures of bulk C with that of IOM. The spectral differences between bulk C and IOM reflect “missing C” phases that were lost during acid leaching, although we cannot completely exclude the possibility that the OM was modified after demineralization. Comparing IR spectra of bulk meteorite powder and IOM suggests that the missing C varies in its molecular structure, and that mildly thermally metamorphosed type 3 chondrites tend to be richer in an aliphatic fraction with lower CH₂/CH₃ ratios, relative to IOM, compared to aqueously altered carbonaceous chondrites (CI/CM/CR). The missing C is most likely released from acid‐labile functional groups, such as esters, acetals, and amides, during demineralization, although it cannot be ruled out that some fraction of the missing C is in small grains that are difficult to recover from suspension, or in water‐soluble compounds trapped in phyllosilicates.     

Near-infrared spectra of laboratory H2O-CH4 ice mixtures

We present 1.25-19 μm infrared spectra of pure solid CH₄ and H₂O/CH₄=87, 20, and 3 solid mixtures at temperatures from 15 to 150 K. We compare and contrast the absorptions of CH₄ in solid H₂O with those of pure CH₄. Changes in selected peak positions, profiles, and relative strength with temperature are presented, and absolute strengths for absorptions of CH₄ in solid H₂O are estimated. Using the two largest (ν₃+ν₄) and (ν₁+ν₄) near-IR absorptions of CH₄ at 2.324 and 2.377 μm (4303 and 4207 cm⁻¹), respectively, as examples, we show that peaks of CH₄ in solid H₂O are at slightly shorter wavelength (higher frequency) and broader than those of pure solid CH₄. With increasing temperature, these peaks shift to higher frequency and become increasingly broad, but this trend is reversible on re-cooling, even though the phase transitions of H₂O are irreversible. It is to be hoped that these observations of changes in the positions, profiles, and relative intensities of CH₄ absorptions with concentration and temperature will be of use in understanding spectra of icy outer Solar System bodies.     

A study of the 3ν3CH4 region in a high-resolution spectrum of Jupiter recorded by Fourier transform spectroscopy

A spectrum of Jupiter between 6000 and 12 000 cm^? at high resolution (0.05 cm^?) was recorded with a Michelson interferometer at Palomar Mountain in October 1974. An analysis of the R branch of the 3ν₃CH₄ band with the reflecting-layer model, taking into account the H₂ absorption which occurs in the same spectral range, leads to a Lorentzian half-width of 0.09 ± 0.02 cm^?1, a rotational temperature of 175 ± 10° K, and a CH₄ abundance of order 52m atm. Five lines of the ¹³CH₄3ν₃ band have been identified; a comparison with new laboratory spectra indicates that the ¹³CH₄/¹²CH₄ ratio in the Jupiter atmosphere is close to the terrestrial ratio.     

Collision-induced absorption in the far infrared spectrum of Titan

The effects of collision-induced absorption on the far infrared spectrum of Titan have been investigated. After a review of the procedure for the theoretical calculation of the N₂ translation-rotational spectrum, new results for the temperature range of 70 to 120°K are reported. These are used as input data for a simple atmospheric model in order to compute the far infrared radiance, brightness temperature, and spectral limb function. This source of opacity alone is not capable of explaining the Voyager results. When the collision-induced methane is included, the results are in closer agreement in the range between 200 and 300 cm^?1, suggesting that a more complete treatment of collision-induced absorption including particularly CH₄N₂, N₂H₂, and H₂H₂ results, may provide sufficient opacity to reduce or obviate the need for opacities due to clouds or aerosols in order to explain the observed spectra.     

Ground-Based Observations of the Martian Atmosphere in Support of Space Missions

Although Mars is a favored target for planetary exploration, there is still a need for complementary ground-based observing programs of the Martian atmosphere, and this need will remain in the future. Indeed, as the atmosphere is very tenuous (less than 0.01 bar at the surface), the lines are very narrow and a high spectral resolving power (above 10⁴) is required over large spectral intervals. In addition, ground-based observations of Mars allow the instantaneous mapping of the whole planet, and thus the study of diurnal effects, which cannot be achieved from an orbiter. Recent ground-based achievements about the Martian atmospheric science include the first detection of H₂O₂ in the submillimeter range, the measurement of winds from CO millimetric transitions, the first detection of CH₄ and the O₃, H₂O₂, H₂O, and CH₄ mapping in the infrared. With an ELT, it will be possible to study at high spatial resolution transient atmospheric phenomena and to search for traces of minor constituents with unprecedented sensitivity. With ALMA, it will be also possible to search for minor species and to map the mesospheric winds for better constraining the climate models.     

Near-infrared laboratory spectra of solid H2O/CO2 and CH3OH/CO2 ice mixtures

We present near-IR spectra of solid CO₂ in H₂O and CH₃OH, and find they are significantly different from that of pure solid CO₂. Peaks not present in either pure H₂O or pure CO₂ spectra become evident when the two are mixed. First, the putative theoretically forbidden CO₂ (2ν₃) overtone near 2.134 μm (4685 cm⁻¹), that is absent from our spectrum of pure solid CO₂, is prominent in the spectra of H₂O/CO₂=5 and 25 mixtures. Second, a 2.74-μm (3650 cm⁻¹) dangling OH feature of H₂O (and a potentially related peak at 1.89 μm) appear in the spectra of CO₂-H₂O ice mixtures, but are probably not diagnostic of the presence of CO₂. Other CO₂ peaks display shifts in position and increased width because of intermolecular interactions with H₂O. Warming causes some peak positions and profiles in the spectrum of a H₂O/CO₂=5 mixture to take on the appearance of pure CO₂. Absolute strengths for absorptions of CO₂ in solid H₂O are estimated. Similar results are observed for CO₂ in solid CH₃OH. Since the CO₂ (2ν₃) overtone near 2.134 μm (4685 cm⁻¹) is not present in pure CO₂ but prominent in mixtures, it may be a good observational (spectral) indicator of whether solid CO₂ is a pure material or intimately mixed with other molecules. These observations may be applicable to Mars polar caps as well as outer Solar System bodies.     

Airborne interferometric measurement of the infrared spectrum of Jupiter from 6 to 14 μm

A new spectrum of Jupiter from 700 to 1600 cm^?1 was obtained with an interferometric experiment using the 91.5 cm telescope of the NASA Airborne Infrared Observatory. The spectral resolution is 10 cm^?1 and the signal-to-noise ratio is 30 at 900 cm^?1. NH₃ absorption lines are observed between 820 and 1020 cm^?1. The 1306 cm^?1ν₄CH₄ band strongly appears in emission at a temperature of at least 145° K. The Jovian brightness temperature between 1400 and 1600 cm^?1, according to our measurement, is lower than 170° K.     

Infrared spectroscopy of Wild 2 particle hypervelocity tracks in Stardust aerogel: Evidence for the presence of volatile organics in cometary dust

Abstract— Infrared spectroscopy maps of some tracks made by cometary dust from 81P/Wild 2 impacting Stardust aerogel reveal an interesting distribution of organic material. Out of six examined tracks, three show presence of volatile organic components possibly injected into the aerogel during particle impacts. When particle tracks contained volatile organic material, they were found to be ‐CH₂‐rich, while the aerogel is dominated by the ‐CH₃‐rich contaminant. It is clear that the population of cometary particles impacting the Stardust aerogel collectors also includes grains that contained little or none of this organic component. This observation is consistent with the highly heterogeneous nature of collected grains, as seen by a multitude of other analytical techniques.     

Comparative Raman microscopy of a Martian meteorite and Antarctic lithic analogues

The Raman microspectra of the Nakhla SNC meteorite, which probably originates from Mars, are reported here for the first time. The specimen is shown to be heterogeneous, even at a sampling level of 2 μm, but several important mineralogical features have been identified, including clinopyroxene, olivine and plagioclase. In some sampling regions, α-quartz particles are evident and in one sample region the ν(CO²⁻₃) mode of calcite at 1086 cm⁻¹ is found. There is no evidence for organic chemical content detectable in this meteorite specimen, based on an absence of ν(CH) and δ(CH₂) modes near 3000 and 1400 cm⁻¹, respectively. Comparative Raman spectroscopic analyses were made on epilithic examples of Xanthoria elegans from Crater Cirque, northern Victoria Land, Antarctica, and cryptoendoliths from East Beacon, McMurdo Dry Valleys, as positive controls for microbial organics in cold, arid habitats analogous to former Martian conditions. Finally, an assessment is made of the potential role of Raman spectroscopy for extra-terrestrial characterisation of geological specimens.