Titan's Aerosols Research Articles

First Optical Constants of Laboratory-generated Organic Refractory Materials (Tholins) Produced in the NASA Ames COSmIC Facility from the Visible to the Near Infrared (0.4–1.6 μm): Application to Titan’s Aerosols

We have measured the complex refractive indices, from 0.4 to 1.6 μm, of five laboratory-generated organic refractory materials (tholins) produced at low temperature (150 K) using plasma chemistry in the stream of a supersonic expansion in NASA Ames’ COsmic SImulation Chamber (COSmIC) facility. Three samples were produced from N2:CH4 gas precursors (with different voltages inducing different degrees of ionization in the plasma), one sample was produced from N2:CH4:C2H2, and one sample was produced from Ar:CH4 in order to produce a purely carbonaceous sample. The optical constants, n and k, of the samples were determined using spectral reflectance measurements. We observe that both n and k appear to be correlated with the nitrogen content in the solid sample, with samples containing more nitrogen having higher n and k. Comparisons to previous laboratory studies and Titan aerosol optical constants derived from observations show that the COSmIC tholins with a higher nitrogen content (higher n and k) are closer analogs of Titan aerosols. We also present a new analysis of Cassini Visible Infrared Mapping Spectrometer observations of Titan’s atmosphere in the visible to near infrared using the COSmIC tholin optical constants in a radiative transfer model. The COSmIC tholin sample produced from N2:CH4 with the lowest energy level has a spectral behavior that appears well suited to reproduce the observed Titan aerosol properties. This study has therefore demonstrated that this COSmIC tholin sample has valuable and promising optical properties for the analysis of Cassini’s Titan atmospheric observations.

Interaction dust–plasma in Titan's ionosphere: Feedbacks on the gas phase composition

Titan's organic aerosols are formed and spend some time in the ionosphere, an atmospheric layer ionized by solar VUV photons and energetic particles coming from the magnetosphere of Saturn, forming a natural N2-CH4-H2 plasma. Previous works showed some chemical evolution processes: VUV photons slightly alter the aerosols nitrile bands, hydrogen atoms tend to hydrogenate their surface and carbon-containing species participate to the growth of the aerosols. This work investigates the effect of the other plasma species, neglected until now, namely the N2-H2 derived ions, radicals and electronic or vibrational excited states. Industrial plasmas often use N2-H2 discharges to form ammonia-based fertilizers, for metal nitriding, and to erode organic surfaces. Consequently, these are likely to affect Titan's organic aerosols.We therefore developed the THETIS experiment (for Tholin Evolution in Titan's Ionosphere Simulation) to study the interactions between analogues of Titan's aerosols (tholins) and the erosive N2-H2 plasma species found in Titan's ionosphere. Following a first paper on the investigation of the evolution of the solid phase by Scanning Electron Microscopy and IR transmission spectroscopy (Chatain et al., 2020a), this second paper focuses on evolution of the gas phase composition, studied by neutral and ion mass spectrometry.In the presented experiments, newly formed HCN, NH3-CN and C2N2 are extracted in quantity from the tholins as well as some other carbon-containing species and their derived ions. On the other hand, the production of ammonia strongly decreases, probably because the H, NH and N radicals are rather used for the production of HCN at the surface of tholins. Heterogeneous processes are suggested based on the experimental observations: chemical processes induced by radicals at the surface would modify and weaken the tholin structure, while ion sputtering would desorb small molecules and highly unsaturated ions. The effect of plasma erosion on aerosols in Titan's ionosphere could therefore lead to the formation of CN bonds in the aerosol structure, as well as the production of HCN or R-CN species in the gas phase.

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 facility to produce four laboratory analogs of Titan’s aerosols, or tholins. These tholin samples were produced from four gas mixtures of initial compositions N 2 :CH 4 (90:10 and 95:5) and N 2 :CH 4 :C 2 H 2 (89.5:10:0.5 and 94.5:5:0.5) at 150 K, using a plasma discharge in the stream of a jet-cooled gas expansion. Here we present an ex situ X-ray absorption near-edge structure (XANES) spectroscopy analysis of these four tholin samples. The C- and N-XANES spectra show the presence of various functional groups (aromatic carbon, imines, nitriles, etc.) whose abundances are correlated with (i) the relative proportions between N 2 and CH 4 , and (ii) the presence or absence of C 2 H 2 in the initial mixtures. In particular, mixtures containing C 2 H 2 result in the formation of tholins consisting of more aromatic structures and displaying larger relative amounts of imines and nitriles, but lower overall nitrogen content. XANES spectroscopy also allowed for the determination of the elemental C/N ratios for the four tholins, which were all found to be low (< 2.5) and consistent with those measured for tholins produced in other, independent experimental set-ups. The C/N ratios of tholins produced from gas mixtures that contained C 2 H 2 (2.2–2.4) were found to be about twice as large as those of tholins produced from gas mixtures that did not contain C 2 H 2 (0.9–1.3). These new results from the COSmIC/THS experimental set-up demonstrate the impact initial precursors have on the nitrogen chemistry during the formation of tholins, which may help in the interpretation of observations and the development of models of Titan’s atmosphere. • Titan aerosol analogs were produced with COSmIC/THS from four gas mixtures. • XANES spectroscopy provided chemical and elemental composition of Titan tholins. • Tholins formed from N 2 :CH 4 and N 2 :CH 4 :C 2 H 2 contain aromatics, imines, and nitriles. • C 2 H 2 resulted in more aromatics, imines, and nitriles, but lower nitrogen content. • Results show effect of initial precursors on nitrogen chemistry in tholin formation.

Distribution and intensity of water ice signature in South Xanadu and Tui Regio

Titan's surface was revealed by Cassini's instruments, showing the presence of liquid hydrocarbons in lakes, and features like dry riverbed. In order to study the sediment transport in Titan's channels and to map distribution of the water-ice signature in these terrains, we use a radiative transfer model to retrieve the surface albedo, after we estimated VIMS error with an original method. We also establish a criteria related to the intensity of the water ice signature. The tuning of the radiative transfer model shows that the fractal dimension of Titan's aerosols is higher than previously thought, around 2.3–2.4. We find spots of high signal of water ice downstream, at the margins of Tui Regio, that could correspond to alluvial fans, deltas or crater rims. We also observe a very low water ice signal on Tui Regio, with a positive gradient between the central region and the boundary of the area, possibly due to the thickness variation of an evaporitic layer. The riverbeds show within the error bars a decreasing grain size from the top to the bottom of the channels. This reinforces the hypothesis of sediment transport via these river channels.

Optical constants of Pluto aerosol analogues from UV to near-IR

Photochemical aerosols were detected as high as 350 km of altitude in Pluto's atmosphere during the New Horizons fly-by. These aerosols are thought to affect Pluto's climate, by acting as cooling agents, and the colours of Pluto's surface, in particular in the dark regions named Cthulhu and Krun and at the North Pole. Pluto atmospheric and surface models have so far used the optical constants of Titan aerosol analogues (tholins), whereas their chemical composition is known to differ from that of Pluto aerosol analogues.In order to provide a new set of optical constants for Pluto tholins, we synthesized analogues of Pluto's aerosols and determined with spectroscopic ellipsometry their optical constants from 270 to 2100 nm. Three types of samples were produced from N2:CH4:CO gas mixtures differing in their CH4:N2 mixing ratio, representative of different altitudes in Pluto's current atmosphere or different seasons or epochs of Pluto.Our analysis shows a strong absorption by Pluto tholins in the UV and visible spectral ranges, with k index of a few 10−1 at 270 nm, in agreement with N- and O-bearing organic molecules. Pluto tholins are less absorbent in the near-IR than in the UV–Vis wavelength range, with k of a few 10−3 between 600 and 2100 nm. Our comparative study highlights the dependency of n and k indices to the CH4:N2 mixing ratio. Aerosols formed at different altitudes in Pluto's atmosphere or during different seasons or epochs of Pluto will therefore affect the budget of Pluto radiative transfer differently.The optical constants presented in this study were tested with a Pluto surface model and with a model of light scattering. The surface modelling results highlight the suitability of these optical constants to reproduce Pluto compositional observations in the visible spectral range by MVIC and LEISA. The atmospheric modelling results conclude that Pluto tholins absorb 5 to 10 times less than Titan tholins at 500 nm, and this lower absorption is consistent with Alice observations of Pluto's haze.

On an EUV Atmospheric Simulation Chamber to Study the Photochemical Processes of Titan\u2019s Atmosphere

The in situ exploration of Titan’s atmosphere requires the development of laboratory experiments to understand the molecular growth pathways initiated by photochemistry in the upper layers of the atmosphere. Key species and dominant reaction pathways are used to feed chemical network models that reproduce the chemical and physical processes of this complex environment. Energetic UV photons initiate highly efficient chemistry by forming reactive species in the ionospheres of the satellite. We present here a laboratory experiment based on a new closed and removable photoreactor coupled here to an Extreme Ultraviolet (EUV) irradiation beam produced by the high-order harmonic generation of a femtosecond laser. This type of EUV stable source allow long-term irradiation experiments in which a plethora of individual reactions can take place. In order to demonstrate the validity of our approach, we irradiated for 7 hours at 89.2 nm, a gas mixture based on N2/CH4 (5%). Using only one wavelength, products of the reaction reveal an efficient photochemistry with the formation of large hydrocarbons but especially organic compounds rich in nitrogen similar to Titan. Among these nitrogen compounds, new species had never before been identified in the mass spectra obtained in situ in Titan’s atmosphere. Their production in this experiment, on the opposite, corroborates previous experimental measurements in the literature on the chemical composition of aerosol analogues produced in the laboratory. Diazo-compounds such as dimethyldiazene (C2H6N2), have been observed and are consistent with the large nitrogen incorporation observed by the aerosols collector pyrolysis instrument of the Huygens probe. This work represents an important step forward in the use of a closed cell chamber irradiated by the innovative EUV source for the generation of photochemical analogues of Titan aerosols. This approach allows to better constrain and understand the growth pathways of nitrogen incorporation into organic aerosols in Titan’s atmosphere.

Chemical composition of Pluto aerosol analogues

Photochemical aerosols were observed in Pluto atmosphere during the New Horizons flyby on July 14th, 2015, as several thin haze layers extending at >350 km of altitude. This flyby has raised numerous questions on the aerosols formation processes and their impact on Pluto radiative transfer and climate. In order to gain a better understanding, we synthesized Pluto aerosol analogues in a room-temperature dusty plasma experiment and inferred their chemical composition from infrared spectroscopy, elemental composition analysis and very high-resolution mass spectrometry (ESI+/Orbitrap device). Three types of samples were synthesized at 0.9 ± 0.1 mbar, called P400, P600 and PCO-free. The samples P400 and P600 were produced from gas mixtures mimicking Pluto atmosphere at around 400 and 600 km of altitude, respectively, in order to determine if CH4 mixing ratio has an influence on the chemical composition of the aerosols. The sample PCO-free was produced from a gas mixture similar to the one forming the sample P400, but without carbon monoxide, in order to identify the impact of CO.Our study shows that the molecules constituting samples P400 and P600 are very rich in nitrogen atoms (up to 45% in mass of N elements) and, compared to the molecules constituting the PCO-free sample, a significant incorporation of oxygen atoms was detected. Moreover, our results on the variation of CH4 mixing ratio demonstrate that different ratios lead to different reactivity between N2, CH4 and CO. In particular, more nitrogen and oxygen atoms are detected in the bulk composition of the analogues P400. Due to the presence of nitrogenated and oxygenated molecules in the analogues of Pluto aerosols, we suggest that these aerosols will have an impact on Pluto radiative transfer, and thus on climate, that will differ from predictions based on the optical constants of Titan aerosol analogues.

Interaction dust – plasma in Titan's ionosphere: An experimental simulation of aerosols erosion

Organic aerosols accumulated in Titan's orange haze start forming in its ionosphere. This upper part of the atmosphere is highly reactive and complex ion chemistry takes place at altitudes from 1200 to 900 km. The ionosphere is a nitrogen plasma with a few percent of methane and hydrogen. Carbon from methane enables the formation of macromolecules with long organic chains, finally leading to the organic aerosols. On the other hand, we suspect that hydrogen and the protonated ions have a different erosive effect on the aerosols.Here we experimentally studied the effect of hydrogen and protonated species on organic aerosols. Analogues of Titan's aerosols were formed in a radiofrequency capacitively coupled plasma (RF CCP) discharge in 95% N2 and 5% CH4. Thereafter, the aerosols were exposed to a DC plasma in 99% N2 and 1% H2. Samples were analysed by scanning electron microscopy and in situ infrared transmission spectroscopy. Two pellet techniques – KBr pressed pellets and thin metallic grids - were compared to confirm that modifications seen are not due to the material used to make the pellet.We observed that the spherical aerosols of ~500 nm in diameter were eroded under N2-H2 plasma exposure, with the formation of holes of ~10 nm at their surface. Aerosols were globally removed from the pellet by the plasma. IR spectra showed a faster disappearance of isonitriles and/or carbo-diimides compared to the global band of nitriles. The opposite effect was seen with β-unsaturated nitriles and/or cyanamides. Double bonds as CC and CN were more affected than amines and CH bonds. NH and CH absorption bands kept a similar ratio in intensity and their shape did not vary.Therefore, it seems that carbon and hydrogen play opposite roles in Titan's ionosphere: the carbon from methane leads to organic growth while hydrogen and protonated species erode the aerosols and react preferentially with unsaturated chemical functions.

Propane clusters in Titan’s lower atmosphere: insights from a combined theory/laboratory study

ABSTRACT In spite of the considerable advances made by Cassini–Huygens in our understanding of Titan, many questions endure. In particular, the detailed processes that lead to the formation of haze aerosols in Titan’s atmosphere, found in high concentrations at low altitudes, are not well identified. Hydrocarbons, which are abundant constituents of Titan’s cold atmosphere originating from photochemical processes, may simultaneously condense on the surface of existing aerosols, nucleate and grow to generate new aerosol seeds. The relative importance of the various processes depends on several factors, including the saturation ratio. The dynamics of hydrocarbon condensation and nucleation in Titan’s atmosphere remains poorly known. Aiming to progress on these issues, we investigate here the kinetics of propane dimer formation at low temperature through state-of-the-art laboratory experiments combined with theoretical calculations. Our results provide an estimate of the rate coefficients, which are then employed to evaluate the abundance of propane dimers in the lower atmosphere of Titan. The mixing ratios of propane dimers inferred, with a maximum abundance of 10 cm−3 near 100 km, is found to be under the detection limit of the Composite Infrared Spectrometer of the Cassini spacecraft. Based on our results, homogeneous nucleation of the most abundant species appears not to be relevant for the growth of aerosols. Future studies should focus on homogeneous nucleation of polar molecules or alternatively on heterogeneous processes, which are usually more efficient.

Photoreactivity of condensed acetylene on Titan aerosols analogues

Volatile organic molecules formed by photochemistry in the upper atmosphere of Titan can undergo condensation as pure ices in the stratosphere and the troposphere as well as condense as ice layers onto the organic aerosols that are visible as the haze layers of Titan. As solar photons penetrate through Titan's atmosphere, shorter-wavelength photons are attenuated and longer-wavelength photons make it into the lower altitudes, where aerosols become abundant. We conducted an experimental study to evaluate the long wavelength (λ > 300 nm) photoreactivity of these ices accreted on the Titan aerosol-analogs (also known as tholins) made in the laboratory. We have focused on acetylene, the third most abundant hydrocarbon in Titan's atmosphere (after CH4 and C2H6). Further, acetylene is the most abundant unsaturated hydrocarbon in Titan's atmosphere. Our results indicate that the aerosols can act as activation centers to drive the photoreactivity of acetylene with the aerosols at the accretion interface at wavelengths where acetylene-ice alone does not show photoreactivity. We found that along with photochemistry, photodesorption plays an important role. We observed that about 15% of the initial acetylene is photodesorbed, with a photodesorption rate of (2.1 ± 0.2) × 10−6 molecules•photon−1 at 355 nm. This photodesorption is wavelength-dependent, confirming that it is mediated by the UV absorption of the aerosol analogues, similar to photochemistry. We conclude that the UV–Vis properties of aerosols would determine how they evolve further in Titan's atmosphere and on the surface through photochemical alterations involving longer-wavelength photons. Stronger extinction coefficients in the longer wavelength UV–Vis regions (> 300 nm) of the aerosol give higher efficiencies of photodesorption of accreted volatiles as well as photochemical incorporation of unsaturated condensates (such as acetylene) into the aerosols.

FUV Photoionization of Titan Atmospheric Aerosols

Abstract Thanks to the Cassini–Huygens mission, it is now established that the first aerosols in Titan’s upper atmosphere are found from an altitude of ∼1200 km. Once they are formed and through their descent toward the surface, these nanoparticles are submitted to persistent far-ultraviolet (FUV) radiation that can reach lower atmospheric layers. Such an interaction has an impact, especially on the chemistry and charge budget of the atmospheric compounds. Models are useful to understand this photoprocessing, but they lack important input data such as the photoemission threshold or the absolute photoabsorption/emission cross sections of the aerosols. In order to quantify the photoemission processes, analogs of Titan’s aerosols have been studied with the DESIRS FUV beamline at the synchrotron SOLEIL as isolated substrate-free nanoparticles. We present here the corresponding angle-resolved photoelectron spectroscopy data recorded at different FUV photon energies. The results show a very low photoionization threshold (6.0 ± 0.1 eV ∼ 207 nm) and very high absolute ionization cross sections (∼106 Mb), indicating that FUV photoemission from aerosols is an intense source of slow electrons that has to be taken into account in photochemical models of Titan’s atmosphere.

Low-temperature formation of polycyclic aromatic hydrocarbons in Titan’s atmosphere

The detection of benzene in Titan’s atmosphere led to the emergence of polycyclic aromatic hydrocarbons (PAHs) as potential nucleation agents triggering the growth of Titan’s orange-brownish haze layers. However, the fundamental mechanisms leading to the formation of PAHs in Titan’s low-temperature atmosphere have remained elusive. We provide persuasive evidence through laboratory experiments and computations that prototype PAHs like anthracene and phenanthrene (C14H10) are synthesized via barrierless reactions involving naphthyl radicals (C10H7•) with vinylacetylene (CH2=CH–C≡CH) in low-temperature environments. These elementary reactions are rapid, have no entrance barriers, and synthesize anthracene and phenanthrene via van der Waals complexes and submerged barriers. This facile route to anthracene and phenanthrene—potential building blocks to complex PAHs and aerosols in Titan—signifies a critical shift in the perception that PAHs can only be formed under high-temperature conditions, providing a detailed understanding of the chemistry of Titan’s atmosphere by untangling elementary reactions on the most fundamental level. Small polycyclic aromatic hydrocarbons (PAHs) are thought to be nucleation sites for the growth of Titan’s haze layers. Using laboratory experiments and electronic structure calculations, Zhao et al. show that small PAHs can by synthesized by rapid, barrierless reactions in Titan’s low-temperature environments.

Comparison of soluble and insoluble organic matter in analogues of Titan's aerosols

Titan, the biggest moon of Saturn, has a thick atmosphere which presents similarities with the one thought to be on Earth at its beginning. The study of Titan's photochemical haze is thus a precious tool in gaining knowledge of the primitive atmosphere of Earth. The chemistry occurring in Titan's atmosphere and the exact processes at act in the formation of the hazes remain largely unknown. The production of analogs samples on Earth has proved to be a useful tool to improve our knowledge of the aerosols formation on Titan. Such solid organic analogs samples, named tholins, were produced with the PAMPRE experiment (French acronym for Aerosols Microgravity Production by Reactive Plasma). PAMPRE tholins were found to be mostly insoluble, with only one-third of the bulk sample that can be dissolved in methanol. This partial solubility limited the previous studies in mass spectrometry, which were done only on the soluble fraction. The goal of the present study is to compare the two fractions of PAMPRE's tholins (insoluble and soluble) using a ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometer (FTICR) equipped with a laser desorption/ionization source. Using modified Van Krevelen diagrams, we compare the global distribution of the molecules within the samples according to their Hydrogen/Carbon ratio and Nitrogen/Carbon ratio. Major differences are observed in the molecular composition of the soluble and the insoluble fraction. The soluble fraction of tholins was previously identified as a set of polymers of average formula (C2H3N)n. In this work we observe that the insoluble fraction of tholins is comprised of a significantly different set of polymers with an average composition of (C4H3N2)n.

Direct Measurement of Interparticle Forces of Titan Aerosol Analogs (“Tholin”) Using Atomic Force Microscopy

AbstractTo understand the origin of the dunes on Titan, it is important to investigate the material properties of Titan's organic sand particles on Titan. The organic sand may behave distinctively compared to the quartz/basaltic sand on terrestrial planets (Earth, Venus, and Mars) due to differences in interparticle forces. We measured the surface energy (through contact angle measurements) and elastic modulus (through Atomic Force Microscopy) of the Titan aerosol analog (tholin). We find that the surface energy of a tholin thin film is about 70.9 mN/m, and its elastic modulus is about 3.0 GPa (similar to hard polymers like PMMA and polystyrene). For two 20 μm diameter particles, the theoretical cohesion force is therefore 3.3 μN. We directly measured interparticle forces for relevant materials: tholin particles are 0.8 ± 0.6 μN, while the interparticle cohesion between walnut shell particles (a typical model materials for the Titan Wind Tunnel, TWT) is only 0.4 ± 0.1 μN. The interparticle cohesion forces are much larger for tholins and presumably Titan sand particles than materials used in the TWT. This suggests that we should increase the interparticle force in both analog experiments (TWT) and threshold models to correctly translate the results to real Titan conditions. The strong cohesion of tholins may also inform us how the small aerosol particles (∼1 μm) in Titan's atmosphere are transformed into large sand particles (∼200 μm). It may also support the cohesive sand formation mechanism suggested by Rubin and Hesp (2009), where only unidirectional wind is needed to form linear dunes on Titan.

Photochemistry on Pluto - I. Hydrocarbons and aerosols.

In light of the recent New Horizons flyby measurements, we present a coupled ion-neutral-photochemistry model developed for simulating the atmosphere of Pluto. Our model results closely match the observed density profiles of CH4, N2 and the C2 hydrocarbons in the altitude range where available New Horizons measurements are most accurate (above ~ 100-200 km). We found a high eddy coefficient of 106 cm2 s-1 from the surface to an altitude of 150 km, and 3 × 106 cm2 s-1 above 150 km for Pluto's atmosphere. Our results demonstrate that C2 hydrocarbons must stick to and be removed by aerosol particles in order to reproduce the C2 profiles observed by New Horizons. Incorporation into aerosols in Pluto's atmosphere is a significantly more effective process than condensation, and we found that condensation alone cannot account for the observed shape of the vertical profiles. We empirically determined the sticking efficiency of C2 hydrocarbons to aerosol particles as a function of altitude, and found that the sticking efficiency of C2 hydrocarbons is inversely related to the aerosol surface area. Aerosols must harden and become less sticky as they age in Pluto's atmosphere. Such hardening with ageing is both necessary and sufficient to explain the vertical profiles of C2 hydrocarbons in Pluto's atmosphere. This result is in agreement with the fundamental idea of aerosols hardening as they age, as proposed for Titan's aerosols.

Influence of trace aromatics on the chemical growth mechanisms of Titan aerosol analogues

The chemical structure and formation pathways of Titan aerosols remain largely unknown. In this work, we studied the effect of trace aromatics on the chemical composition and formation pathways of laboratory analogues of Titan's organic aerosols. The aerosol analogues were produced using four different trace aromatic molecules, comprised of one or two aromatic rings, each with or without a nitrogen heteroatom. Samples were then analyzed by laser desorption/ionization Mass Spectrometry (LDMS), revealing a high variability in the sample composition depending on the trace aromatic used. Our work reveals that the final chemical structure of the aerosols depends strongly on the number of aromatic rings in the trace molecule, leading either to a polymeric or to a random co-polymeric growth of the sample. These different chemical structures can affect the physical properties of the aerosol. Future analysis of Titan's aerosols using better resolution could potentially determine whether either of the growth hypotheses are preferred.

The Titan Haze Simulation (THS) experiment on COSmIC. Part II. Ex-situ analysis of aerosols produced at low temperature

This paper presents the first results of the solid phase analysis of the Titan tholins generated in the Titan Haze Simulation (THS) experiments. This study complements the gas phase analysis study that was presented in a previous publication introducing the THS capabilities. In the THS experiment, the chemistry is simulated by plasma in the stream of a supersonic jet expansion. With this unique design, the gas is jet-cooled to Titan-like temperature (∼150K) before inducing the chemistry by plasma, and remains at low temperature in the plasma discharge (∼200K).Here, we present and discuss the results of scanning electron microscopy and infrared spectroscopy studies of THS solid aerosols produced in the four gas mixtures already studied by mass spectrometry in the gas phase: N2CH4, N2CH4C2H2, N2CH4C6H6 and N2CH4C2H2C6H6. Differences in the morphology of the grains and aggregates produced in the volume of the gas phase in the plasma cavity, depending on the initial precursors, have been observed by scanning electron microscopy, that appear to be linked to differences in the growth processes and might have an impact on microphysical models. The mid-infrared spectroscopic analysis highlights changes in the nitrogen chemistry, and the abundance of aromatic compounds, depending on the initial gas mixture. A preliminary study of the aging and degradation of the THS samples with time and exposure to air and light has shown the importance, for future studies of laboratory-generated planetary aerosol analogs, of collecting, storing and characterizing samples under controlled environment. A comparison to VIMS data shows that the THS tholins produced in simpler mixtures, i.e., with a higher level of nitrogen incorporation, are more representative of Titan's aerosols.

Low-Temperature Alkaline pH Hydrolysis of Oxygen-Free Titan Tholins: Carbonates' Impact.

Titan, the largest moon of Saturn, is one of the key planetary objects in the field of exobiology. Its dense, nitrogen-rich atmosphere is the site of important organic chemistry. This paper focuses on the organic aerosols produced in Titan's atmosphere that play an important role in atmospheric and surface processes and in organic chemistry as it applies to exobiological interests. To produce reliable laboratory analogues of these aerosols, we developed, tested, and optimized a device for the synthesis of clean tholins. The potential chemical evolution of Titan aerosols at Titan's surface has been studied, in particular, the possible interaction between aerosols and putative ammonia-water cryomagma. Modeling of the formation of Saturn's atmosphere has permitted the characterization of a composition of salts in the subsurface ocean and cryolava. From this new and original chemical composition, a laboratory study of several hydrolyses of tholins was carried out. The results obtained show the formation of many organic compounds, among them, species identified only in the presence of salts. In addition, a list of potential precursors of these compounds was established, which could provide a database for research of the chemical composition of tholins and/or aerosols of Titan. Key Words: Titan tholins-Titan aerosols-Hydrolysis-Carbonates-Titan's surface. Astrobiology 17, 8-26.

Environmental temperature effect on the far-infrared absorption features of aromatic-based Titan's aerosol analogs

Benzene detection has been reported in Titan's atmosphere both in the stratosphere at ppb levels by remote sensing (Coustenis et al., 2007; Vinatier et al., 2007) and in the thermosphere at ppm levels by the Cassini's Ion and Neutral Mass Spectrometer (Waite et al., 2007). This detection supports the idea that aromatic and heteroaromatic reaction pathways may play an important role in Titan's atmospheric chemistry, especially in the formation of aerosols. Indeed, aromatic molecules are easily dissociated by ultraviolet radiation and can therefore contribute significantly to aerosol formation. It has been shown recently that aerosol analogs produced from a gas mixture containing a low concentration of aromatic and/or heteroaromatic molecules (benzene, naphthalene, pyridine, quinoline and isoquinoline) have spectral signatures below 500cm−1, a first step towards reproducing the aerosol spectral features observed by Cassini's Composite InfraRed Spectrometer (CIRS) in the far infrared (Anderson and Samuelson 2011, and references therein). In this work we investigate the influence of environmental temperature on the absorption spectra of such aerosol samples, simulating the temperature range to which aerosols, once formed, are exposed during their transport through Titan's stratosphere. Our results show that environmental temperature does not have any major effect on the spectral shape of these aerosol analogs in the far-infrared, which is consistent with the CIRS observations.

Titan's organic aerosols: Molecular composition and structure of laboratory analogues inferred from pyrolysis gas chromatography mass spectrometry analysis

Analogues of Titan's aerosols are of primary interest in the understanding of Titan's atmospheric chemistry and climate, and in the development of in situ instrumentation for future space missions. Numerous studies have been carried out to characterize laboratory analogues of Titan aerosols (tholins), but their molecular composition and structure are still poorly known. If pyrolysis gas chromatography mass spectrometry (pyr-GCMS) has been used for years to give clues about their chemical composition, highly disparate results were obtained with this technique. They can be attributed to the variety of analytical conditions used for pyr-GCMS analyses, and/or to differences in the nature of the analogues analyzed, that were produced with different laboratory set-ups under various operating conditions.In order to have a better description of Titan's tholin's molecular composition by pyr-GCMS, we carried out a systematic study with two major objectives: (i) exploring the pyr-GCMS analytical parameters to find the optimal ones for the detection of a wide range of chemical products allowing a characterization of the tholins composition as comprehensive as possible, and (ii) highlighting the role of the CH4 ratio in the gaseous reactive medium on the tholin's molecular structure. We used a radio-frequency plasma discharge to synthetize tholins with different concentrations of CH4 diluted in N2. The samples were pyrolyzed at temperatures covering the 200–700°C range. The extracted gases were then analyzed by GCMS for their molecular identification.The optimal pyrolysis temperature for characterizing the molecular composition of our tholins by GCMS analysis is found to be 600°C. This temperature choice results from the best compromise between the number of compounds released, the quality of the signal and the appearance of pyrolysis artifacts. About a hundred molecules are identified as pyrolysates. A common major chromatographic pattern appears clearly for all the samples even if the number of released compounds can significantly differ. The hydrocarbon chain content increases in tholins when the CH4 ratio increases. A semi-quantitative study of the nitriles (most abundant chemical family in our chromatograms) released during the pyrolysis shows the existence of a correlation between the amount of a nitrile released and its molecular mass, similarly to the previous quantification of nitriles in the plasma gas-phase. Moreover, numerous nitriles are present both in tholins and in the gas phase, confirming their suspected role in the gas phase as precursors of the solid organic particles.