We present a study of the formation and distribution of benzene (C6H6) on Titan. Analysis of the Cassini Mass Spectrometer (INMS) measurements of benzene densities on 12 Titan passes shows that the ...benzene signal exhibits an unusual time dependence, peaking ∼20 s after closest approach, rather than at closest approach. We show that this behavior can be explained by recombination of phenyl radicals (C6H5) with H atoms on the walls of the instrument and that the measured signal is a combination of (1) C6H6 from the atmosphere and (2) C6H6 formed within the instrument. In parallel, we investigate Titan benzene chemistry with a set of photochemical models. A model for the ionosphere predicts that the globally averaged production rate of benzene by ion‐molecule reactions is ∼107 cm−2 s−1, of the same order of magnitude as the production rate by neutral reactions of ∼4 × 106 cm−2 s−1. We show that benzene is quickly photolyzed in the thermosphere, and that C6H5 radicals, the main photodissociation products, are ∼3 times as abundant as benzene. This result is consistent with the phenyl/benzene ratio required to match the INMS observations. Loss of benzene occurs primarily through reaction of phenyl with other radicals, leading to the formation of complex aromatic species. These species, along with benzene, diffuse downward, eventually condensing near the tropopause. We find a total production rate of solid aromatics of ∼10−15 g cm−2 s−1, corresponding to an accumulated surface layer of ∼3 m.
High-energy photons, electrons, and ions initiate ion–neutral chemistry in Titan's upper atmosphere by ionizing the major neutral species (nitrogen and methane). The Ion and Neutral Mass Spectrometer ...(INMS) onboard the Cassini spacecraft performed the first composition measurements of Titan's ionosphere. INMS revealed that Titan has the most compositionally complex ionosphere in the Solar System, with roughly 50 ions at or above the detection threshold. Modeling of the ionospheric composition constrains the density of minor neutral constituents, most of which cannot be measured with any other technique. The species identified with this approach include the most complex molecules identified so far on Titan. This confirms the long-thought idea that a very rich chemistry is actually taking place in this atmosphere. However, it appears that much of the interesting chemistry occurs in the upper atmosphere rather than at lower altitudes. The species observed by INMS are probably the first intermediates in the formation of even larger molecules. As a consequence, they affect the composition of the bulk atmosphere, the composition and optical properties of the aerosols and the flux of condensable material to the surface. In this paper, we discuss the production and loss reactions for the ions and how this affects the neutral densities. We compare our results to neutral densities measured in the stratosphere by other instruments, to production yields obtained in laboratory experiments simulating Titan's chemistry and to predictions of photochemical models. We suggest neutral formation mechanisms and highlight needs for new experimental and theoretical data.
Origin of oxygen species in Titan's atmosphere Hörst, S. M.; Vuitton, V.; Yelle, R. V.
Journal of Geophysical Research - Planets,
October 2008, Letnik:
113, Številka:
E10
Journal Article
Recenzirano
Odprti dostop
The detection of O+ precipitating into Titan's atmosphere by the Cassini Plasma Spectrometer (CAPS) represents the discovery of a previously unknown source of oxygen in Titan's atmosphere. The ...photochemical model presented here shows that those oxygen ions are incorporated into CO and CO2. We show that the observed abundances of CO, CO2 and H2O can be simultaneously reproduced using an oxygen flux consistent with the CAPS observations and an OH flux consistent with predicted production from micrometeorite ablation. It is therefore unnecessary to assume that the observed CO abundance is the remnant of a larger primordial CO abundance or to invoke outgassing of CO from Titan's interior as a source of CO.
In this paper we present an in-depth study of the distributions of various neutral species in Titan's upper atmosphere, between 950 and 1500 km for abundant species (N
2, CH
4, H
2) and between 950 ...and 1200 km for other minor species. Our analysis is based on a large sample of Cassini/INMS (Ion Neutral Mass Spectrometer) measurements in the CSN (Closed Source Neutral) mode, obtained during 15 close flybys of Titan. To untangle the overlapping cracking patterns, we adopt Singular Value Decomposition (SVD) to determine simultaneously the densities of different species. Except for N
2, CH
4, H
2 and
40Ar (as well as their isotopes), all species present density enhancements measured during the outbound legs. This can be interpreted as a result of wall effects, which could be either adsorption/desorption of these molecules or heterogeneous surface chemistry of the associated radicals on the chamber walls. In this paper, we provide both direct inbound measurements assuming ram pressure enhancement only and abundances corrected for wall adsorption/desorption based on a simple model to reproduce the observed time behavior. Among all minor species of photochemical interest, we have firm detections of C
2H
2, C
2H
4, C
2H
6, CH
3C
2H, C
4H
2, C
6H
6, CH
3CN, HC
3N, C
2N
2 and NH
3 in Titan's upper atmosphere. Upper limits are given for other minor species.
The globally averaged distributions of N
2, CH
4 and H
2 are each modeled with the diffusion approximation. The N
2 profile suggests an average thermospheric temperature of 151 K. The CH
4 and H
2 profiles constrain their fluxes to be
2.6
×
10
9
cm
−
2
s
−
1
and
1.1
×
10
10
cm
−
2
s
−
1
, referred to Titan's surface. Both fluxes are significantly higher than the Jeans escape values. The INMS data also suggest horizontal/diurnal variations of temperature and neutral gas distribution in Titan's thermosphere. The equatorial region, the ramside, as well as the nightside hemisphere of Titan appear to be warmer and present some evidence for the depletion of light species such as CH
4. Meridional variations of some heavy species are also observed, with a trend of depletion toward the north pole. Though some of the above variations might be interpreted by either the solar-driven models or auroral-driven models, a physical scenario that reconciles all the observed horizontal/diurnal variations in a consistent way is still missing. With a careful evaluation of the effect of restricted sampling, some of the features shown in the INMS data are more likely to be observational biases.
Cassini discovered a plethora of neutral and ionized molecules in Titan's ionosphere including, surprisingly, anions and negatively charged molecules extending up to 13,800 u q−1. In this Letter, we ...forward model the Cassini electron spectrometer response function to this unexpected ionospheric component to achieve an increased mass resolving capability for negatively charged species observed at Titan altitudes of 950-1300 km. We report on detections consistently centered between 25.8 and 26.0 u q−1 and between 49.0-50.1 u q−1 which are identified as belonging to the carbon chain anions, CN−/C3N− and/or C2H−/C4H−, in agreement with chemical model predictions. At higher ionospheric altitudes, detections at 73-74 u q−1 could be attributed to the further carbon chain anions C5N−/C6H− but at lower altitudes and during further encounters extend over a higher mass/charge range. This, as well as further intermediary anions detected at >100 u, provide the first evidence for efficient anion chemistry in space involving structures other than linear chains. Furthermore, at altitudes below <1100 km, the low-mass anions (<150 u q−1) were found to deplete at a rate proportional to the growth of the larger molecules, a correlation that indicates the anions are tightly coupled to the growth process. This study adds Titan to an increasing list of astrophysical environments where chain anions have been observed and shows that anion chemistry plays a role in the formation of complex organics within a planetary atmosphere as well as in the interstellar medium.
Photochemical models of Titan's atmosphere predict that three-body association reactions are the main production route for several major hydrocarbons. The kinetic rate constants of these reactions ...strongly depend on density and are therefore only important in Titan's lower atmosphere. However, radiative association reactions do not depend on pressure. The possible existence of large rates at low density suggests that association reactions could significantly affect the chemistry of Titan's upper atmosphere and better constraints for them are required. The kinetic parameters of these reactions are extremely difficult to constrain by experimental measurements as the low pressure of Titan's upper atmosphere cannot be reproduced in the laboratory. However, in the recent years, theoretical calculations of kinetics parameters have become more and more reliable. We therefore calculated several radical-radical and radical-molecule association reaction rates using transition state theory. The calculations indicate that association reactions are fast even at low pressure for adducts having as few as four C atoms. These drastic changes have however only moderate consequences for Titan's composition. Locally, mole fractions can vary by as much as one order of magnitude but the column-integrated production and condensation rates of hydrocarbons change only by a factor of a few. We discuss the impact of these results for the organic chemistry. It would be very interesting to check the impact of these new rate constants on other environments, such as giant and extrasolar planets as well as the interstellar medium.
The discovery of large (>100 u) molecules in Titan's upper atmosphere has heightened astrobiological interest in this unique satellite. In particular, complex organic aerosols produced in atmospheres ...containing C, N, O, and H, like that of Titan, could be a source of prebiotic molecules. In this work, aerosols produced in a Titan atmosphere simulation experiment with enhanced CO (N(2)/CH(4)/CO gas mixtures of 96.2%/2.0%/1.8% and 93.2%/5.0%/1.8%) were found to contain 18 molecules with molecular formulae that correspond to biological amino acids and nucleotide bases. Very high-resolution mass spectrometry of isotopically labeled samples confirmed that C(4)H(5)N(3)O, C(4)H(4)N(2)O(2), C(5)H(6)N(2)O(2), C(5)H(5)N(5), and C(6)H(9)N(3)O(2) are produced by chemistry in the simulation chamber. Gas chromatography-mass spectrometry (GC-MS) analyses of the non-isotopic samples confirmed the presence of cytosine (C(4)H(5)N(3)O), uracil (C(5)H(4)N(2)O(2)), thymine (C(5)H(6)N(2)O(2)), guanine (C(5)H(5)N(5)O), glycine (C(2)H(5)NO(2)), and alanine (C(3)H(7)NO(2)). Adenine (C(5)H(5)N(5)) was detected by GC-MS in isotopically labeled samples. The remaining prebiotic molecules were detected in unlabeled samples only and may have been affected by contamination in the chamber. These results demonstrate that prebiotic molecules can be formed by the high-energy chemistry similar to that which occurs in planetary upper atmospheres and therefore identifies a new source of prebiotic material, potentially increasing the range of planets where life could begin.
Titan's atmosphere is unique because dissociation of N sub(2) and CH sub(4), the primary atmospheric constituents, provides the H, C, and N atoms necessary for the synthesis of complex organic ...molecules. The first steps in the synthesis of organic molecules occur in the upper atmosphere where energetic photons and electrons dissociate N sub(2) and CH sub(4). We determine the abundance of a suite of nitrogen-bearing molecules in Titan's upper atmosphere through analysis of measurements of the ionospheric composition made by the Ion Neutral Mass Spectrometer (INMS) on the Cassini spacecraft. We show that the density of ions in Titan's upper atmosphere depends closely on the composition of the neutral atmosphere and that, for many species, measurement of associated ions coupled with simple chemical models provides the most sensitive determination of their abundance. With this technique we determine the densities of C sub(2)H sub(4), C sub(4)H sub(2), HCN, HC sub(3)N, CH sub(3)CN, NH sub(3), C sub(2)H sub(3)CN, C sub(2)H sub(5)CN, and CH sub(2)NH. The latter four species have not previously been detected in the gas phase on Titan, and none of these species have been accurately measured in the upper atmosphere. The presence of these species implies that nitrogen chemistry on Titan is more extensive than previously realized.
Studying the chemical composition of organic matter in astrophysical environments is an important means to improve our understanding of its origin and evolution. This organic matter evolves from ...molecular clouds to protoplanetary disks, and as a final destination, takes part in the formation of many objects of our solar system, such as primitive chondritic material, planetesimals and finally planets. In this contribution, we perform experimental simulations based on the VUV irradiation and warming-up of primitive interstellar ice analogs (CH3OH:NH3:H2O), and characterize, for the first time, the resulting refractory residue, using very high resolution mass spectrometry (VHRMS) with an LTQ-orbitrap-XL instrument. An electrospray source allows ionizing all the molecules having proton donor or acceptor chemical functions, while limiting as much as possible their damages. Thus, this method provides the analysis of the whole ionizable molecules making up the residue. The analysis of the spectra shows that these residues contain a large number of molecules formed of CHNO elements, including macromolecular entities beyond 4000Da. The average elemental composition of the residue is of H/C=1.5, N/C=0.4, O/C=0.4. These first results are tentatively compared to VHRMS analyses of the soluble organic matter (SOM) present in the Murchison’s meteorite, a primitive chondrite of the CM class. The molecular richness observed can be considered as the “first step” of the complex abiotic organic matter in extraterrestrial media. This initial matter, that may be rather universal, could then evolve toward more processed materials in parent bodies, such as comets and asteroids, materials that are then observed and subsequently analyzed in meteorites found on Earth. In addition to providing some insight on the mixture complexity, VHRMS allows for the search of specific molecules. For instance, hexamethylenetetramine (HMT) and some of its derivatives are identified in these residues. With the possibility to characterize the whole residue as well as some specific molecules, we consider that VHRMS is a powerful analytical tool for the understanding of the chemical evolution of organic matter in astrophysical environments.
We use laboratory experiments to derive information on the chemistry occurring during the evolution of astrophysical ices from dense molecular clouds to interplanetary objects. Through a new strategy ...that consists of coupling very high resolution mass spectrometry and infrared spectroscopy (FT-IR), we investigate the molecular content of the organic residues synthesized from different initial ice compositions. We also obtain information on the evolution of the soluble part of the residues after their over-irradiation. The results give insight into the role of water ice as a trapping and diluting agent during the chemical evolution. They also give information about the importance of the amount of ammonia in such ices, particularly regarding its competition with the carbon chemistry. All of these results allow us to build a first mapping of the evolution of soluble organic matter based on its chemical and physical history. Furthermore, our results suggest that interstellar ices should lead to organic materials enriched in heteroatoms that present similarities with cometary materials but strongly differ from meteoritic organic material, especially in their C/N ratios.
PDF
